Preparation of polydiorganosiloxanes

Abstract

A process for endcapping a dimethylsilanol-terminated polydiorganosiloxane with one or more di-, tri-, and / or tetraalkoxysilanes in the presence of an endcapping catalyst starting material consisting of one or more linear, branched, or cyclic molecules containing at least one amidine group, guanidine group, or derivative of said amidine and / or guanidine group, or mixtures thereof. The resulting endcapping polymeric material can be utilized as a polymer, for example, in a polydiorganosiloxane elastomer composition.

Description

Technical Field

[0001] The present invention relates to a method for preparing an alkoxy-terminated polydiorganosiloxane by end-capping a silanol-terminated polydiorganosiloxane. The present invention also relates to the use of an alkoxy-terminated polydiorganosiloxane as one of the essential components of a condensation-curable polydiorganosiloxane elastomer composition that is storage-stable in the absence of moisture and crosslinked by atmospheric moisture at ambient temperature.

[0002] Several routes for preparing polydiorganosiloxane polymers having alkoxy end groups are known in the art. It is known in the art that an alkoxy-terminated polydiorganosiloxane polymer can be prepared by reacting a di-, tri-, or tetraalkoxysilane (polyalkoxysilane) with a silanol-terminated polydiorganosiloxane polymer in the presence of a catalyst.

[0003] As one might expect, this reaction is not easy. In fact, silanol groups do not readily react with alkoxysilane groups at ambient temperature in the absence of a catalyst. A wide variety of compounds have been proposed as suitable catalysts for this purpose. Some, such as sulfuric acid, hydrochloric acid, Lewis acids, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide, are generally chemically harsh and have been found to cause bond cleavage and random rearrangement when involved in the condensation of silanol and alkoxysilane. Other compounds proposed as suitable catalysts, including amines, inorganic oxides, potassium acetate, titanium / amine combinations, carboxylic acid / amine combinations, alkoxyaluminum chelates, N,N'-disubstituted hydroxylamines, carbamates, metal hydroxides such as lithium hydroxide, and oxime-containing organic compounds, are undesirable for various reasons. For example, amine catalyst systems are slow, especially considering the reactivity levels of many of the alkoxysilanes involved in the process. Furthermore, amine and carboxylic acid catalysts are corrosive and require special handling and removal processes once the reaction has proceeded to the desired completed state. Lithium hydroxide, being an inorganic solid, requires a polar solvent such as methanol to be introduced into the reaction as a solution. However, the presence of methanol continuously regenerates catalysts, such as lithium methoxide, resulting in a rapid decrease in viscosity of the resulting polymer reaction product due to its interaction with the regenerated lithium catalyst. Furthermore, many of these catalysts emit unpleasant odors that are dangerous to the eyes and skin, and their removal is often difficult, requiring cumbersome and costly extra steps.

[0004] Organotitanium catalysts such as titanium tetraisopropionate have already been studied for the preparation of alkoxy-terminated polydiorganosiloxane polymers. However, they form complexes with silanol-terminated polydiorganosiloxane starting materials, significantly thickening the polymer matrix. While this titanium-silicon complex formation is reversible, it requires high-shear mixing to decompose the thick phase, which is undesirable for industry due to the additional cost and time involved.

[0005] Furthermore, failure to remove the catalyst can be detrimental to the storage stability of polymer reaction products or polymer-containing compositions due to gelation (sometimes called pre-cure reversion) resulting from crosslinking, polymer growth, or polymer chain severance, for example. Moreover, failure to remove a portion of the amine catalyst can cause discoloration during storage of the compound or the sealants, adhesives, caulking compositions, etc., subsequently prepared, and / or their respective elastomer products after curing.

[0006] Therefore, there is still a need for a process to produce viscosity-stable alkoxy-terminated polydiorganosiloxane polymers by rapidly occluding silanol-terminated polydiorganosiloxanes using a catalyst that is not plagued by the problems of prior art catalysts.

[0007] A process for preparing alkoxy-terminated polydiorganosiloxanes from silanol-terminated polydiorganosiloxane starting materials, (i) The silanol-terminated polydiorganosiloxane starting material is used to obtain one or more polyalkoxysilane starting materials having the following structures [ka] (In the formula, b is 0, 1, or 2, R 2 R is an alkyl group which may be linear or branched and have 1 to 15 carbon atoms. 1 is any suitable group, namely, R 2 (This may include monovalent hydrocarbon groups such as cycloalkyl groups; alkenyl groups, aryl groups; aralkyl groups, aminoalkyl groups, (meth)acrylate groups, glycidyl ether groups, and groups obtained by replacing all or part of the hydrogen atoms in the aforementioned organic groups with halogens.) The present invention provides a process comprising reacting in the presence of one or more linear, branched, or cyclic end-bound catalyst starting materials comprising at least one amidine group, guanidine group, or derivatives thereof, or mixtures thereof, in an amount of 0.0005 to 0.75% by weight of the starting material composition at the completion of the reaction.

[0008] Furthermore, (i) a silanol-terminated polydiorganosiloxane starting material is used as one or more polyalkoxysilane starting materials having the following structures [ka] (In the formula, b is 0, 1, or 2, R 2 R is an alkyl group which may be linear or branched and have 1 to 15 carbon atoms. 1 is any suitable group, namely, R 2 (This may include monovalent hydrocarbon groups such as cycloalkyl groups; alkenyl groups, aryl groups; aralkyl groups, aminoalkyl groups, (meth)acrylate groups, glycidyl ether groups, and groups obtained by replacing all or part of the hydrogen atoms in the aforementioned organic groups with halogens.) Provided herein are alkoxy-end-bound polydiorganosiloxanes that can be obtained by reacting in the presence of a terminal-bound catalyst starting material comprising one or more linear, branched, or cyclic molecules containing at least one amidine group, guanidine group, or derivatives thereof, in an amount of 0.0005 to 0.75% by weight of the starting material composition.

[0009] The following processes are also provided herein for preparing alkoxy-terminated polydiorganosiloxanes from the above-mentioned silanol-terminated polydiorganosiloxanes by mixing the following components together, and then for preparing polydiorganosiloxane elastomer compositions: (a) The alkoxy-terminated polydiorganosiloxane polymer obtained by the process described herein, (b) Fillers, (d) Condensation curing catalyst, and optionally (e) Adhesion promoters and / or (c) Crosslinking agent.

[0010] Furthermore, the use of alkoxy-end sealed polydiorganosiloxane polymers prepared by the processes described herein as polymers in the preparation of organopolysiloxane elastomer compositions is also provided.

[0011] Silanol-terminated polydiorganosiloxane starting materials have at least two silanol groups per molecule and may have the following formula: [ka] (In the formula, each R is an alkyl group, an alkenyl group, or an aryl group, and Z is a divalent organic group.) d is 0 or 1, q is 0 or 1, d+q=1, n is 0, 1, or 2, y is 0, 1, or 2, and z is an integer such that the polydiorganosiloxane polymer starting material has a viscosity of 30-100,000 MPa·s at 25°C, or 1,000-90,000 mPa·s at 25°C, by using either a Brookfield® rotational viscometer with spindle LV-4 (designed for viscosities in the range of 1,000-2,000,000 mPa·s) or a Brookfield® rotational viscometer with spindle LV-1 (designed for viscosities in the range of 15-20,000 mPa·s) for viscosities less than 1,000 mPa·s, and adjusting the rate (shear rate) according to the polymer viscosity.

[0012] Typically, in the above, d is 0, q is 1, and n is 1 or 2. In such cases, the silanol-terminated polydiorganosiloxane starting material has the following structure: [ka] If R, y, and z are as described above, the mean value of y is approximately 2, i.e., the silanol-terminated polymer is substantially (i.e., (>)90% superlinear or >97% linear).

[0013] Each R is individually selected from alkyl groups, or alkyl groups having 1 to 10 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or methyl or ethyl groups, alkenyl groups, or alkenyl groups having 2 to 10 carbon atoms, or 2 to 6 carbon atoms, such as vinyl, allyl, and hexenyl groups, aromatic groups, or aromatic groups having 6 to 20 carbon atoms, substituted aliphatic organic groups such as 3,3,3-trifluoropropyl groups, aminoalkyl groups, polyaminoalkyl groups, and / or epoxyalkyl groups.

[0014] Each Z is independently selected from alkylene groups having 1 to 10 carbon atoms. In one alternative example, each Z is independently selected from alkylene groups having 2 to 6 carbon atoms, and in a further alternative example, each Z is independently selected from alkylene groups having 2 to 4 carbon atoms. Each alkylene group can be individually selected from, for example, ethylene, propylene, butylene, pentylene, and / or hexylene groups. However, as previously shown, in this example, d is usually 0 (zero).

[0015] Silanol-terminated polydiorganosiloxane starting materials are measured using either a Brookfield® rotational viscometer with spindle LV-4 (designed for viscosities in the range of 1,000 to 2,000,000 mPa.s) or a Brookfield® rotational viscometer with spindle LV-1 (designed for viscosities in the range of 15 to 20,000 mPa.s) for viscosities less than 1,000 mPa.s, adjusting the rate (shear rate) according to the polymer viscosity to achieve viscosities of 1,000 to 100,000 MPa·s at 25°C, or 5,000 to 90,000 mPa.s at 25°C, where z is an integer that allows such viscosities, or z is an integer between 200 and 5000.

[0016] The silanol-terminated polydiorganosiloxane polymer starting material may be a single siloxane represented by formula (1), or a mixture of polydiorganosiloxane polymers represented by the above formula. Therefore, the term "siloxane polymer mixture" with respect to silanol-terminated polydiorganosiloxane starting materials means that it includes any individual polydiorganosiloxane polymer starting material or a mixture of polydiorganosiloxane polymer starting materials.

[0017] The degree of polymerization (DP) (i.e., essentially z in the above formula) is usually defined as the number of monomer units in a silicone macromolecule, polymer, or oligomer molecule. Synthetic polymers essentially consist of a mixture of macromolecular species with different degrees of polymerization, and therefore with different molecular weights. Different types of average polymer molecular weights exist, and they can be measured by different experiments. The two most important are the number average molecular weight (Mn) and the weight average molecular weight (Mw). The Mn and Mw of silicone polymers can be measured by gel permeation chromatography (GPC) with an accuracy of about 10-15%. This technique is standard and yields Mw, Mn, and the polydispersity index (PI). Degree of polymerization (DP) = Mn / Mu, where Mn is the number average molecular weight from the GPC measurement and Mu is the molecular weight of the monomer unit. PI = Mw / Mn. DP is related to the viscosity of the polymer by Mw, and the higher the DP, the higher the viscosity.

[0018] In the first step of the process, the silanol-terminated polydiorganosiloxane starting material described above is reacted with one or more polyalkoxysilane starting materials having the following structures: [ka] (where b is 0, 1, or 2, or 0 or 1, and R 2 is an alkyl group having 1 to 15 carbons, or 1 to 10 carbons, or 1 to 6 carbons, which may be linear or branched, for example, methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, and hexyl, or methyl or ethyl, or R 2 may be a methyl group. R 1 is any suitable group, that is, it may be substituted or unsubstituted, and may be substituted by a halogen such as fluorine and chlorine. Examples of monovalent hydrocarbon groups such as R 2 include trifluoropropyl and / or perfluoropropyl; cycloalkyl groups (e.g., cyclopentyl group and cyclohexyl group); alkenyl groups (e.g., vinyl group and allyl group); aryl groups (e.g., phenyl group and tolyl group); aralkyl groups (e.g., 2-phenyl ethyl group), and groups obtained by replacing all or part of the hydrogen in the aforementioned organic groups with halogen. In one embodiment, R 1 may be a vinyl, methyl, or ethyl group, or a vinyl or methyl group, or a methyl group. When b is 0 or 1, this means that the polyalkoxysilane has 4 or 3 alkoxy groups. Typically, the silanol-terminated polydiorganosiloxane starting material has one terminal silanol bond (-Si-OH) per terminal silicon. In such a case, by the end-capping reaction, end groups containing 3 Si-alkoxy bonds or 2 Si-alkoxy bonds (-Si-OH) are replaced, for example, alkyl or vinyl groups are generated.

[0019] Typically, the amount of polyalkoxysilane starting material present in the starting material for the end-blocking reaction is determined such that at least equimolar amounts of polyalkoxysilane are present relative to the amount of -OH groups on the polymer. Therefore, the higher the viscosity / chain length of the polymer used as the starting material, the fewer -OH groups are typically present in the polymer, and consequently, less polyalkoxysilane is required. Conversely, the lower the viscosity / chain length of the polymer used as the starting material, the more -OH groups are typically present in the polymer, and consequently, more polyalkoxysilane is required. However, in some cases, it is preferable to include a significantly molar excess of polyalkoxysilane, and when the final product of the alkoxy end-blocking polydiorganosiloxane polymer reaction is used as an ingredient in an organopolysiloxane elastomer composition for use, for example, as a silicone sealant composition, the remaining unreacted polyalkoxysilane present at the end of the end-blocking reaction, i.e., in the final product of the alkoxy end-blocking polydiorganosiloxane polymer reaction, is utilized as a crosslinking agent. Therefore, in one embodiment of this specification, preferably, there is a molar excess of polyalkoxysilane with respect to the -OH groups on the end-bound polymer. Thus, the final product of the alkoxy-end-bound polydiorganosiloxane polymer reaction may be an alkoxy-end-bound polydiorganosiloxane polymer, or an alkoxy-end-bound polydiorganosiloxane polymer mixed with / containing unreacted polyalkoxysilane.

[0020] The end-sealed catalyst starting materials used in accordance with the disclosure herein are selected from one or more linear, branched, or cyclic molecules comprising one or more groups selected from an amidine group, a guanidine group, a derivative of said amidine group and / or a guanidine group, or a mixture thereof.

[0021] One or more linear, branched, or cyclic molecules containing one or more groups selected from an amidine group, a guanidine group, a derivative of said amidine group and / or a guanidine group, or a mixture thereof may include linear, branched, or cyclic silicon-containing molecules or linear, branched, or cyclic organic molecules containing one or more of the following groups (1) to (4). [ka] [ka] [ka] [ka] In the formula, each R 4 , R 5 , R 6 , R 7 , and R 8 They may be the same or different, and may be selected from hydrogen, alkyl groups, cycloalkyl groups, phenyl groups, and aralkyl groups, or R 4 and R 5 , or R 6 and R 5 , or R 7 and R 5 , or R 8 and R 4 The ring structure may optionally be formed by creating a ring structure, for example, a heterogeneously substituted alkylene group, using oxygen or nitrogen atoms for the heterogeneous substitution.

[0022] In one embodiment, formulas (1) to (4) may be part of a silane structure in which nitrogen is bonded to a silicon atom via an alkylene group, for example, [ka] (In the formula, Z is as described above, and each R 10A may be the same or different and may be a hydroxyl group and / or a hydrolyzable group (such as those described later in this specification in relation to crosslinking agent (c)), an alkyl group; a cycloalkyl group; an alkenyl group, an aryl group, or an aralkyl group; A is one of the above (1) to (4).

[0023] In further alternative examples, any one of the above structures (1) to (4) may be linked to a polymer group selected from the group consisting of alkyd resins, oil-modified alkyd resins, saturated or unsaturated polyesters, natural oils, epoxides, polyamides, polycarbonates, polyethylene, polypropylene, polybutylene, polystyrene, ethylene-propylene copolymers, (meth)acrylates, (meth)acrylamides, and their salts, phenolic resins, polyoxymethylene homopolymers and copolymers, polyurethanes, polysulfones, polysulfide rubbers, nitrocellulose, vinyl butyrate, vinyl polymers, ethylcellulose, acetic acid and / or cellulose butyrate, rayon, shellac, waxes, ethylene copolymers, organic rubbers, polysiloxanes, polyethersiloxanes, silicone resins, polyethers, polyether esters, and / or polyether carbonates. When structures (1) to (4) are linked to siloxane radicals, they can be bonded to polysiloxane groups having an average molecular weight in the range of 206 to 50,000 g / mol, particularly 280 to 25,000 g / mol, and especially preferably 354 to 15,000 g / mol. End-sealed catalysts having such polysiloxane groups are typically liquid at room temperature, have a low vapor pressure, are particularly easily compatible in silicone polymer-based curable compositions, and consequently tend to separate or migrate very little.

[0024] For example, end-bound catalyst starting materials have a structure [ka] It may be 1,1,3,3-tetramethylguanidine (TMG) having the following structure, or it may be a silane with the following structure: [ka] (In the formula, R 2 , R 1 , and b are as described above, a is 1, R 3 teeth, [ka] (In the formula, R 5 and R 4 As defined above, Z 1 (where a is an alkylene or oxyalkylene group having 2 to 6 carbon atoms, and a is 1). Specific examples include 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine and 2-[3-(methyldimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine.

[0025] Alternatively, the end-bound catalyst starting material may be, for example, triazabicyclodecene (1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) as shown below, [ka] Alternatively, cyclic guanidines such as 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene (mTBD), as shown below, may be used. [ka]

[0026] Alternatively, the end-bound catalyst starting material may be, for example, 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), as shown below. [ka] Alternatively, cyclic amidines such as 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU), as shown below, may be used. [ka]

[0027] If the reactants can be continuously mixed (e.g., using a magnetic stirrer or overhead mechanical stirrer), the end-sealing catalyst may be added directly as a solid. Furthermore, the end-sealing catalyst may be introduced into the reaction environment in the form of a fine powder. When the reactants are mixed and allowed to stand, the end-sealing catalyst is delivered as a solution to ensure uniform dispersion. When delivered as a solution, the solvent may, for illustrative purposes, be a compatible silicone or organic solvent such as trimethyl-terminated polydimethylsiloxane or toluene. However, to minimize VOC issues, it has been found that the preferred liquid for delivering the end-sealing catalyst is, in practice, one of the polyalkoxysilanes used to end-seal silanol-terminated polydiorganosiloxane starting materials, e.g., vinyltrimethoxysilane and / or methyltrimethoxysilane.

[0028] The primary advantage described herein is that the process minimizes crosslinking or polymer growth, allowing for polymer encapsulation while maintaining polymer viscosity stability. Stability refers to a period of 3–7 days during which the polymer does not undergo significant changes due to crosslinking, gelation, or cleavage (i.e., more than 10% of the alkoxy-end-sealed polydiorganosiloxane polymer). This can be determined by periodically testing the sample with quantitative NMR (to determine the degree of polymerization) or by viscosity measurement. The NMR used was proton NMR measured using a 400 MHz instrument with a deuterated solvent (e.g., CDCl3δ7.26) as an internal standard. 29Si NMR was measured using an 80 MHz instrument with a solution of 0.02 M chromium(III) acetylacetonate (Cr(acac)3) in a deuterated solvent (e.g., deuterated chloroform (CDCl3)). Viscosity was measured using a TA Instruments ARES Rheometer with a cone and plate configuration having a 0.051 mm gap. Viscosity was measured 1–10 s on a logarithmic scale with 10 points / decade. -1 This was reported as the average viscosity.

[0029] Typically, the end-sealing process described above is carried out in the absence of other components; however, if necessary, additional components that do not interfere with the end-sealing process described herein, such as plasticizers / bulkers and / or pigments, may be present in the composition prior to the process, if desired. However, these are generally added during the preparation of subsequent compositions utilizing the end-sealed polymer provided by the process described herein, as described later herein.

[0030] Furthermore, if desired, a chain extender may be introduced before or simultaneously with the process described above to extend the length of the polymer chain before terminal occlusion with alkoxysilane. The chain extender may be, for example, a bifunctional silane. A suitable bifunctional silane may have the following structure: [ka] In the formula, each R 11 These may be the same or different, and may be linear, branched, or cyclic, but are non-functional groups in that they are non-reactive with the -OH group or hydrolyzable group of the silanol-terminated polydiorganosiloxane starting material. Therefore, each R 11 The group is selected from alkyl groups, alkenyl groups, alkynyl groups, or aryl groups such as phenyl, which have 1 to 10 carbon atoms. One alternative example is R 11The group may be either an alkyl group or an alkenyl group, or there may be one alkyl group and one alkenyl group per molecule. The alkenyl group may be selected from linear or branched alkenyl groups such as vinyl, propenyl, and hexenyl groups, for example, and the alkyl group may have 1 to 10 carbon atoms such as methyl, ethyl, or isopropyl. Further alternative examples include R 11 It is a ring-shaped R bonded to Si atoms at two positions. 111 It may be replaced by this.

[0031] Each group R 12 The groups may be the same or different, and can react with a hydroxyl group or a hydrolyzable group. 12 Examples include alkoxy, acetoxy, oxime, hydroxy, and / or acetamide groups. Alternatively, each R 12 R is either an alkoxy group or an acetamide group. 12 If is an alkoxy group, then an alkoxy group containing 1 to 10 carbon atoms, such as methoxy, ethoxy, propoxy, isopropyl, butoxy, and t-butoxy groups. Specific examples of suitable difunctional silane chain extenders in this specification include alkenylalkyldialkoxysilanes such as vinylmethyldimethoxysilane, vinylethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylethyldiethoxysilane; alkenylalkyldioxymosilanes such as vinylmethyldioxymosilane, vinylethyldioxymosilane, vinylmethyldioxymosilane, and vinylethyldioxymosilane; alkenylalkyldiacetoxysilanes such as vinylmethyldiacetoxysilane, vinylethyldiacetoxysilane, vinylmethyldiacetoxysilane, and vinylethyldiacetoxysilane; and alkenylalkyldihydroxysilanes such as vinylmethyldihydroxysilane, vinylethyldihydroxysilane, vinylmethyldihydroxysilane, and vinylethyldihydroxysilane.

[0032] R 12If is an acetamide, the disilane may be a dialkyldiacetamidosilane or an alkylalkenyldiacetamidosilane. Such diacetamidosilanes are known chain extension materials for low modulus sealant formulations, for example, as described in U.S. Patents 5,017628 and 3,996184. The diacetamidosilane may have, for example, the following structure: [ka] (In the formula, each R 13 They may be the same or different, and may be the same as R as defined above, or each R 13 (These may be the same or different, and may contain an alkyl group having 1 to 6 carbon atoms or 1 to 4 carbon atoms). 14 Furthermore, may be the same or different, and may be the same as R as defined above, and may contain an alkyl group having 1 to 6 carbon atoms or 1 to 4 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms or 2 to 4 carbon atoms, or vinyl. During use, diacetamidosilane may be selected from one or more of the following: N,N'-(dimethylsilylene)bis[N-methylacetamide] N,N'-(dimethylsilylene)bis[N-ethylacetamide] N,N'-(diethylsilylene)bis[N-methylacetamide] N,N'-(diethylsilylene)bis[N-ethylacetamide] N,N'-(dimethylsilylene)bis[N-propylacetamide] N,N'-(diethylsilylene)bis[N-propylacetamide] N,N'-(dipropylsilylene)bis[N-methylacetamide] N,N'-(dipropylsilylene)bis[N-ethylacetamide] N,N'-(methylvinylsilylene)bis[N-ethylacetamide] N,N'-(ethylvinylsilylene)bis[N-ethylacetamide] N,N'-(propylvinylsilylene)bis[N-ethylacetamide] N,N'-(methylvinylsilylene)bis[N-methylacetamide] N,N'-(ethylvinylsilylene)bis[N-methylacetamide] and / or N,N'-(propylvinylsilylene)bis[N-methylacetamide]. Alternatively, the dialkyldiacetamidosilane may be a dialkyldiacetamidosilane selected from N,N'-(dimethylsilylene)bis[N-ethylacetamide] and / or N,N'-(dimethylsilylene)bis[N-methylacetamide]. Or, the dialkyldiacetamidosilane is N,N'-(dimethylsilylene)bis[N-ethylacetamide].

[0033] If present, the chain extender is present in an amount of 0.01 to 5% by weight, or 0.05 to 1% by weight, of the composition.

[0034] When the above process is carried out, based on the weight of the final mixture, it may include (for example, in the absence of additional steps to produce the final sealant or similar composition): (ai) Silanol-terminated polydiorganosiloxane starting material in an amount of 40% to 99.5% by weight of the component, or 60 to 99.5% by weight of the starting material, or 70 to 99.5% by weight of the component, or 80 to 99.5% by weight of the starting material, or 90 to 99.5% by weight of the starting material, or 95 to 99.5% by weight of the starting material; (aii) One or more polyalkoxysilanes with the following structures [ka] (In the formula, b is 0, 1, or 2, R 2 R is an alkyl group which may be linear or branched and have 1 to 15 carbon atoms. 1 is any suitable group, namely, R 2(This may include monovalent hydrocarbon groups such as cycloalkyl groups; alkenyl groups, aryl groups; aralkyl groups; and groups obtained by replacing all or part of the hydrogen atoms in the aforementioned organic groups with halogens) in an amount of approximately 0.5 to 60% by weight of the starting material, or 0.5 to 40% by weight of the starting material, 0.5 to 30% by weight of the starting material, 0.5 to 20% by weight of the starting material, 0.5 to 10% by weight of the component, or 0.5 to 5% by weight of the component, or 0.25 to 2.5% by weight of the starting material (aiii) A terminal-bound catalyst comprising one or more linear, branched, or cyclic molecules containing at least one amidine group, guanidine group, or derivatives thereof, or mixtures thereof, in an amount of 0.0005 to 0.75 wt% of the starting material. The total wt% of the starting components is understood to be 100 wt%.

[0035] Neutralization of end-stop catalysts in the final product has been a significant problem in prior art processes. However, given the low end-stop catalyst content in the process of the present invention, it has been determined that removal of the end-stop catalyst at the end of the reaction is not necessary. Neutralization may be carried out by physical removal of the end-stop catalyst, chemical neutralization (e.g., acid / base reaction), chemiadsorption (e.g., adsorption or metal ion sequestering), or other standard embodiments of product purification and removal of the end-stop catalyst. Furthermore, although some amidines and guanidines are known to have a very strong odor, it has been found that this is not a significant problem in current processes given the amount of end-stop catalyst present. A further advantage of this disclosure is that the need for a neutralization step can be eliminated by the level of end-stop catalyst addition, even if it is not removed.

[0036] In one embodiment, typically, a silanol-terminated polydiorganosiloxane starting material (ai) is introduced into a suitable mixer and stirred, then one or more polyalkoxysilanes (aii) are added, and the resulting mixture is mixed again. Step (i) may use any suitable mixing time, for example, 10 to 30 minutes or 10 to 20 minutes. Optionally, the mixing in step (i) may be carried out at a high temperature of about 100°C or less, for example, 30 to 100°C or 50 to 80°C. A terminal-blocking catalyst may be introduced before, simultaneously with, or after the addition of one or more polyalkoxysilanes, if deemed necessary.

[0037] If desired, the resulting alkoxy-end-bound polydiorganosiloxane polymer reaction final product may be isolated from by-products and end-binding catalysts. Alternatively, equimolar amounts of polymer (ai) and polyalkoxysilane (aii) starting material may be used in the reaction process so as not to contain excess polyalkoxysilane (aii) starting material. Similarly, if desired, any excess polyalkoxysilane (aii) may be added to the reaction mixture with the intention of using it as a crosslinking agent (c) or as part of crosslinking agent (c) in the preparation of the polydiorganosiloxane elastomer composition.

[0038] If it is desirable for the polymer to be chain-extended, a chain-extension process step is also performed. Typically, in this case, the chain extender is added in the first step instead of one or more polyalkoxysilanes, and then, after the chain-extension process with the end-sealing catalyst as described above is considered complete, the polyalkoxysilane is introduced into the mixture with the intention of end-sealing the chain-extended polymer. Mixing can be done in any suitable type of mixer, such as a speed mixer or a Turello mixer. Alternatively, if the silanes are different, the chain-extending silane and the end-sealing silane may be added at the same time. Alternatively, if they are the same silane, the chain-extending silane and the end-sealing silane may be added separately.

[0039] Similarly, as previously shown, as long as the alkoxy-end-blocked polymer is utilized within 3 to 7 days or less after its formation, unlike most prior art methodologies, neutralization of the final product is not required.

[0040] The resulting alkoxy-end-blocked polymer reaction final product may be collected and stored for future use within 3 to 7 days of production, but preferably it is used immediately as part of a process to prepare a polydiorganosiloxane elastomer composition comprising: (a) The alkoxy-end sealed polydiorganosiloxane prepared as described above, i.e., the final product of the alkoxy-end sealed polymer reaction, (b) Fillers, (c) Crosslinking agent, (d) condensation curing catalyst; Furthermore, optionally, (e) Adhesion promoter.

[0041] It should be noted that the crosslinking agent may be supplied with the end-bound polymer (a) in the final product of the end-bound reaction as an excess of unreacted polyalkoxysilane that can be used as a crosslinking agent in the composition. Alternatively, if the end-bound reaction is completed using polyalkoxysilane, the crosslinking agent may be added. Alternatively, if polyalkoxysilane is used to complete the end-bound reaction, the crosslinking agent may be added, otherwise the crosslinking agent may be a mixture of two, partially in excess and partially newly added at this stage.

[0042] The alkoxy-terminated polydiorganosiloxane (a) is typically present in the composition in an amount of 40–80% by weight of the polydiorganosiloxane elastomer composition, or about 40–65% by weight of the sealant composition.

[0043] The above composition is suitable as a sealant elastomer composition and may be designed to form a product that has a low modulus of elasticity upon curing and / or is non-contaminating in that plasticizers and / or fillers (sometimes referred to as processing aids) do not leak out and do not contaminate adjacent substrates such as concrete blocks or other building materials.

[0044] Typically, when a low modulus sealant composition is desired, the polymer produced by the process described herein is chain-extended as described above so that the alkoxy-end-sealed polymer (a) has a high molecular weight / chain length.

[0045] The filler (b) may contain reinforcing fillers and / or non-reinforcing fillers, such as one or more pulverized reinforcing fillers, fumed silica, colloidal silica, and / or precipitated silica, and / or other fillers such as precipitated calcium carbonate and pulverized calcium carbonate, if desired. Typically, the surface area of ​​the filler (b) is measured according to the BET method in accordance with ISO 9277:2010, and is at least 15 m² in the case of precipitated calcium carbonate. 2 / g, or 15-50m in the case of precipitated calcium carbonate. 2 / g, or 15-25m 2 The surface area is / g. Silica-reinforced fillers typically have a surface area of ​​at least 50 m² / g. In one embodiment, filler (b) is precipitated calcium carbonate, precipitated silica, and / or fumed silica, or precipitated calcium carbonate. In the case of high surface area fumed silica and / or high surface area precipitated silica, these are measured using the BET method in accordance with ISO 9277:2010 and have a surface area of ​​75-400 m² / g. 2 The surface area per g, or 100-300 m using the BET method in accordance with ISO 9277:2010. 2 It may have a surface area of ​​ / g.

[0046] Typically, the reinforcing filler (b) is present in the composition in an amount of about 5–45% by weight, or about 5–30% by weight, or about 5–25% by weight, depending on the selected filler.

[0047] For example, the filler (b) can be made hydrophobic by hydrophobic treatment with one or more fatty acids, such as stearic acid or fatty acid esters such as stearate, or with organosilanes, organosiloxanes, or organosilazanes, such as hexaalkyldisilazanes or short-chain siloxane diols, thereby making it easier to handle and obtain a homogeneous mixture with other adhesive components. Surface treatment of the filler makes it easily wettable with alkoxy-terminated polydiorganosiloxane (a). These surface-modified fillers do not aggregate and can be uniformly incorporated into the basic component alkoxy-terminated polydiorganosiloxane (a). This improves the mechanical properties of the uncured composition at room temperature. The filler may be pre-treated or, if mixed with alkoxy-terminated polydiorganosiloxane (a), may be treated in situ.

[0048] The sealant composition also includes a condensation curing catalyst (d). Any suitable condensation curing catalyst (d) can be used. The above-mentioned condensation curing catalyst may include, for example, one or more tin-based catalysts such as tin triflate, organotin curing catalysts, such as triethyltin tartrate, tin octanoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate, tin butyrate, carbomethoxyphenyl tin trisberate, isobutyltin triseroate, and diorganosin salts, particularly diorganosin dicarboxylate compounds, such as dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate, dimethyltin bisneodecanoate, dibutyltin dibenzoate, stannous octanoate, dibutyltin bis(2,4-pentanedionate), dimethyltin dineodecanoate (DMTDN), and dibutyltin dioctoate.

[0049] Alternatively, the condensation curing catalyst (d) may be, for example, a catalyst of the general formula Ti[OR 22 ]4 or Zr[OR 22 ]4(In the formula, each R 22 The catalyst may include titanate and / or zirconate catalysts (which may be identical or different, and which represent monovalent primary, secondary, or tertiary aliphatic hydrocarbon groups containing 1 to 10 carbon atoms, which may be linear or branched). Optionally, the titanate and / or zirconate may contain partially unsaturated groups. 22 Examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, and branched secondary alkyl groups, such as 2,4-dimethyl-3-pentyl. Alternatively, each R 22 If they are the same, R 22 The catalyst is an isopropyl group, a branched secondary alkyl group, or a tertiary alkyl group, particularly a tertiary butyl group. As an alternative, the catalyst is a titanate. Examples of suitable titanates include tetra-n-butyl titanate, tetra-t-butyl titanate, titanium tetrabutoxide, and tetraisopropyl titanate. Examples of suitable zirconates include tetra-n-propyl zirconate, tetra-n-butyl zirconate, and zirconium diethyl citrate.

[0050] Alternatively, the titanate and / or zirconate may be chelated. Chelation may be carried out by any suitable chelating agent, such as alkylacetylacetonates, e.g., methyl or ethylacetylacetonate. Alternatively, the titanate may be a monoalkoxy titanate that yields three chelating agents, e.g., 2-propanolate, trisisooctadecanoate titanate, or diisopropoxy-bisethylacetoacetate titanate.

[0051] The condensation curing catalyst (d) is typically present in the composition in an amount of 0.25 to 4.0% by weight, or 0.25 to 3% by weight, or 0.3% to 2.5% by weight. The polydiorganosiloxane elastomer composition may be a one-part composition in which all components of the composition are stored together, or a two-part composition in which the components are stored in two parts before use to prevent premature curing.

[0052] In a preferred embodiment, the polydiorganosiloxane elastomer composition described herein is a partial polydiorganosiloxane elastomer composition, preferably a partial polydiorganosiloxane elastomer composition in which the condensation curing catalyst (d) is a tin-based condensation curing catalyst.

[0053] The separate addition of crosslinking agent (c) to the above polydiorganosiloxane elastomer composition during its preparation is optional. This is because, although crosslinking agent (c) is an essential component in the above polydiorganosiloxane elastomer composition, Structure used in the above end-seal reaction [ka] (In the formula, R 2 , R 1 This is because b may be the same as one or more of the polyalkoxysilanes described above. In this case, it is possible to introduce a sufficiently large amount of polyalkoxysilane into the reaction mixture for terminal closure of the silanol polymer during the terminal closure reaction, which does not require an additional crosslinking agent (c) when preparing the polydiorganosiloxane elastomer composition. However, if deemed necessary, an additional crosslinking agent may be added when preparing the polydiorganosiloxane elastomer composition.

[0054] When a certain amount of crosslinking agent (c) is added during the preparation of a polydiorganosiloxane elastomer composition, any suitable crosslinking agent having at least three groups per molecule that can react with the alkoxy-terminated polydiorganosiloxane (a) may be used. Typically, any crosslinking agent (c) to be added may be one or more silanes or siloxanes containing silicon-bonded hydrolyzable groups, e.g., acyloxy groups (e.g., acetoxy, octanoyloxy, and benzoyloxy groups); ketoximino groups (e.g., dimethylketoximo and isobutylketoximino groups); alkoxy groups (e.g., methoxy, ethoxy, isobutoxy, and propoxy groups); and alkenyloxy groups (e.g., isopropenyloxy and 1-ethyl-2-methylvinyloxy groups).

[0055] If a crosslinking agent (c) is required, it may include a siloxane-based crosslinking agent having a linear, branched, or cyclic molecular structure.

[0056] The crosslinking agent (c) has at least three or at least four hydroxyl and / or hydrolyzable groups per molecule that are reactive with the hydroxyl and / or hydrolyzable groups in the alkoxy-terminated polydiorganosiloxane (a). If it is necessary to add the crosslinking agent (c), the crosslinking agent (c) may also be a silane, and if the silane has a total of three silicon-bonded hydroxyl and / or hydrolyzable groups per molecule, the fourth group is preferably a non-hydrolyzable silicon-bonded organic group. These silicon-bonded organic groups are preferably hydrocarbyl groups optionally substituted with halogens such as fluorine and chlorine. Examples of such fourth groups include alkyl groups (e.g., methyl, ethyl, propyl, and butyl groups); cycloalkyl groups (e.g., cyclopentyl and cyclohexyl groups); alkenyl groups (e.g., vinyl and allyl groups); aryl groups (e.g., phenyl and tolyl groups); aralkyl groups (e.g., 2-phenylethyl group); and groups obtained by replacing all or part of the hydrogen atoms in the aforementioned organic groups with halogens. However, preferably, the fourth silicon-bonded organic group is methyl or vinyl.

[0057] Silanes and siloxanes that can be used as crosslinking agents (c) include alkyltrialkoxysilanes such as methyltrimethoxysilane (MTM) and methyltriethoxysilane, alkenyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, and isobutyltrimethoxysilane (iBTM). Other suitable silanes include ethyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, alkoxytrioxymosilane, alkenyltrioxymosilane, 3,3,3-trifluoropropyltrimethoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, ethyltriacetoxysilane, dibutoxydiacetoxysilane, phenyl-tripropionoxysilane, methyltris(methylethylketoximo)silane, vinyltris-methylethylketoximo)silane, methyltris(methylethylketoximino)silane, methyltris(isopropenoxy)silane, vinyltris(isopropenoxy)silane, ethylpolysilicate, n-propyl orthosilicate, ethyl orthosilicate, and / or dimethyltetraacetoxydisiloxane. Alternatively, the crosslinking agent (c) may contain any combination of two or more of the above.

[0058] Alternatively, the crosslinking agent (c) may include a silyl-functionalized molecule containing two or more silyl groups, each silyl group containing at least one -OH group or hydrolyzable group, and the total number of -OH groups and / or hydrolyzable groups per crosslinking agent molecule is at least three. Thus, the disilyl-functionalized molecule contains two silicon atoms, each having at least one hydrolyzable group, and these silicon atoms are separated by an organic or siloxane spacer. Typically, the silyl groups on the disilyl-functionalized molecule may be terminal groups. The spacer may be a polymer chain having a siloxane or organic polymer backbone. In the case of such a siloxane or organic crosslinking agent (c), the molecular structure may be linear, branched, cyclic, or macromolecule. For siloxane polymers, the viscosity of the crosslinking agent (c) was measured using either a Brookfield® rotational viscometer with spindle LV-4 (designed for viscosities in the range of 1,000 to 2,000,000 mPa.s) or a Brookfield® rotational viscometer with spindle LV-1 (designed for viscosities in the range of 15 to 20,000 mPa.s) for viscosities less than 1,000 mPa.s, with the speed (shear rate) adjusted according to the polymer viscosity. The measured viscosity was in the range of 15 to 50,000 MPa·s at 25°C, and the measurements were performed at 25°C.

[0059] For example, if it is necessary to add crosslinking agent (c), the crosslinking agent (c) is a disilyl functional polymer, i.e., a polymer containing two silyl groups, each having at least one hydrolyzable group, for example, the following formula [ka] (In the formula, each R and n may be selected individually as described above.) It may be a polymer as described above. 4 This is an alkylene (divalent hydrocarbon group), or an alkylene group having 1 to 10 carbon atoms, or further 1 to 6 carbon atoms, or a combination of the divalent hydrocarbon group and a divalent siloxane group.

[0060] Each X group may be the same or different, and may be a hydroxyl group or a condensable or hydrolyzable group. The term "hydrolyzable group" means any group bonded to silicon that is hydrolyzed by water at room temperature. The hydrolyzable group X includes a group of formula -OT, where T is an alkyl group such as methyl, ethyl, isopropyl, or octadecyl; an alkenyl group such as allyl or hexenyl; a cyclic group such as cyclohexyl, phenyl, benzyl, or β-phenylethyl; or a hydrocarbon ether group such as 2-methoxyethyl, 2-ethoxyisopropyl, 2-butoxyisobutyl, p-methoxyphenyl, or -(CH2CH2O)2CH3. The most preferred X group is a hydroxyl group or an alkoxy group. Exemplary alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, hexoxyoctadecyloxy, and dialkoxy groups such as 2-ethylhexoxy, methoxymethoxy, or ethoxymethoxy, and alkoxyaryloxy groups such as ethoxyphenoxy. The most preferred alkoxy groups are methoxy or ethoxy groups.

[0061] Preferred disilyl functional polymer crosslinking agents have n=0 or 1, X=OMe, and R 4 This is an alkylene group having 4 to 6 carbon atoms.

[0062] Examples of crosslinking agents for disilyl polymers having silicone or organic polymer chains with alkoxy functional end groups include polydimethylsiloxane having at least one trialkoxy end, in which case the alkoxy group may be a methoxy group or an ethoxy group. Examples include 1,6-bis(trimethoxysilyl)hexane, hexamethoxydisiloxane, hexaethoxydisiloxane, hexa-n-propoxydisiloxane, hexa-n-butoxydisiloxane, octaethoxytrisiloxane, octa-n-butoxytrisiloxane, and decaethoxytetrasiloxane. In one embodiment, the crosslinking agent may be one or more of vinyltrimethoxysilane, methyltrimethoxysilane, and / or vinylmethyldimethoxysilane.

[0063] The composition preferably contains at least a stoichiometric amount of crosslinking agent (c) compared to the alkoxy-terminated polydiorganosiloxane (a), regardless of whether it results from an excess amount from the end-binding reaction, from its addition after the completion of the end-binding reaction, or a combination of both. Therefore, the amount present also depends on the specific properties of the crosslinking agent (c) used, in particular the molecular weight of the selected molecule. Thus, the crosslinking agent is typically present in the composition in an amount of 0.1 to 5% by weight, but potentially in larger amounts.

[0064] If present, component (e) is an adhesion promoter. A suitable adhesion promoter (e) is of formula R 14 h Si(OR 15 ) (4-h) The formula may contain an alkoxysilane (wherein the subscript h is 1, 2, or 3, or h is 3). Each R 14 R is an independently monovalent organic functional group. 14 R may be an epoxy functional group such as a glycidoxypropyl group or (epoxycyclohexyl)ethyl group, an amino functional group such as an aminoethylaminopropyl group or an aminopropyl group, a mercapto functional group such as a methacrylateoxypropyl group or a mercaptopropyl group, or an unsaturated organic group. 15 R is independently an unsubstituted saturated hydrocarbon group of at least one carbon atom. 15 It may have 1 to 4 carbon atoms, or 1 to 2 carbon atoms. 15 These are exemplified by methyl, ethyl, n-propyl, and isopropyl.

[0065] Alternatively, the adhesion promoter may be a polyfunctional material obtained by reacting glycidoxypropyltrimethoxysilane or two or more of the above. For example, a reaction product of alkylalkoxysilane, e.g., trimethoxymethylsilane, aminoalkoxysilane, e.g., 3-aminopropyltrimethoxysilane, and epoxyalkoxysilane, e.g., glycidoxypropyltrimethoxysilane, in a weight ratio of (i):(ii):(iii) of 0.1-6:0.1-5:1.

[0066] Examples of suitable adhesion promoters (e) include, also, structural - [ka] The formula may also include molecules of the following type: (wherein each R' may be the same or different, and is an alkyl group containing 1 to 10 carbon atoms, g is 2 to 10, and q is 2 to 10).

[0067] The polydiorganosiloxane elastomer composition may, if present, contain 0.01% to 2% by weight, or 0.05% to 2% by weight, or 0.1% to 1% by weight of an adhesion promoter, based on the weight of the composition. Preferably, the hydrolysis rate of the adhesion promoter should be slower than that of the crosslinking agent, so as to favor the diffusion of molecules into the substrate rather than their incorporation into the product network.

[0068] Other additives may be used as needed. These include rheological modifiers, stabilizers such as antioxidants, UV and / or light stabilizers, pigments, -OH scavengers (water / water / alcohol) scavengers (typically the same compounds used as silazanes or crosslinking agents), plasticizers and / or fillers (sometimes identified as processing aids), and fungicides and / or biocides. Some additives may be listed in multiple additive lists. In such cases, these additives have the ability to function in all the different applications mentioned.

[0069] Rheology modifiers that can be incorporated into the water-curable composition according to the present invention include those described in European Patent No. 0802233, which are based on silicone organic copolymers, such as polyethers or polyester polyols; waxes such as polyamide waxes; nonionic surfactants selected from the group consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylate, copolymers or ethylene oxide and propylene oxide, and silicone polyether copolymers; and silicone glycols. For some systems, these rheology modifiers, in particular copolymers of ethylene oxide and propylene oxide, and silicone polyether copolymers, can enhance adhesion to substrates, especially plastic substrates.

[0070] Any suitable antioxidant can be used if deemed necessary. Examples include ethylenebis(oxyethylene)bis(3-tert-butyl-4-hydroxy-5(methylhydrocinnamate), 36443-68-2; tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, 6683-19-8; octadecyl[3,5-di-tert-butyl-4-hydroxyhydroxycinnamate, 2082-79-3; N,N-hexamethylene-bis(3, Examples include 5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide, 23128-74-7; 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, C7-9 branched alkyl ester, 125643-61-0; reaction product with N-phenylbenzeneamine and 2,4,4-trimethylpentene, 68411-46-1; and, for example, antioxidants sold under the name Irganox® by BASF.

[0071] UV and / or light stabilizers may include, for example, benzotriazole, ultraviolet absorbers and / or hindered amine light stabilizers (HALS), such as the TINUVIN® product line manufactured by Ciba Specialty Chemicals Inc.

[0072] Pigments are used as needed to color the composition. Any suitable pigment can be used as long as it is compatible with the composition. If present, carbon black functions as both a non-reinforcing filler and a colorant and is present in amounts ranging from 1 to 30% by weight of the composition, or 1 to 20% by weight of the catalyst package composition, or 5 to 20% by weight of the composition, or 7.5 to 20% by weight of the composition.

[0073] Any suitable -OH (water / water / alcohol) scavenger, e.g., orthoformates, molecular sieves, silazanes, e.g., organosilazanes, hexaalkyldisilazanes, e.g., hexamethyldisilazanes, and / or one or more silanes of the following structures may be used: [ka] (In the formula, each R 21 These are alkyl groups that may be the same or different, and contain at least two carbon atoms. j is either 1 or 0. R 20(The scavenger is a substituted or unsubstituted linear or branched monovalent hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or silicon-bonded organic group selected from any one of the above, having at least two carbon atoms, wherein at least one hydrogen atom bonded to the carbon is substituted with a halogen atom, or an organic group having an epoxy group, glycidyl group, acyl group, carboxyl group, ester group, amino group, amide group, (meth)acrylic group, mercapto group, or isocyanate group). If present, the scavenger is typically introduced into the composition in an amount ranging from 0.5 to 3.0% by weight of the total weight of the composition, although this amount may be greater depending on the amount of alcohol byproducts produced and the process used to produce the composition. The captured byproducts are, if possible, intentionally removed from the final sealant composition to achieve stability and prevent pre-curing restoration during storage.

[0074] In one embodiment, the polydiorganosiloxane elastomer composition contains an -OH scavenger.

[0075] Plasticizers and / or fillers (sometimes identified as processing aids) If desired, any suitable plasticizer or filler may be used. These may be any of the plasticizers or fillers specified in British Patent No. 2445821, which is incorporated herein by reference. If used, the plasticizer or filler may be added before, after, or during the preparation of the polymer. However, it does not contribute to or participate in the polymerization process.

[0076] Examples of plasticizers or fillers include silicon-containing liquids, e.g., hexamethyldisiloxane, octamethyltrisiloxane, and other short-chain linear siloxanes, e.g., octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane, etc.), and cyclic siloxanes, e.g., hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane; optionally, for 0.5 to 5000 mPa.s (5000 mPa.s must be tested at 100°C), a glass capillary viscometer (ASTM D-445, IP) is used. Further polydiorganosiloxanes, including aryl-functionalized siloxanes, have viscosities of 0.5–12,500 mPa·s when measured at 25°C using 71). For 5,000–12,500 mPa·s, a Brookfield cone-plate viscometer RV DIII with a cone-plate CP-52 is used at 5 rpm (ASTM D4287).

[0077] Alternatively, plasticizers or fillers may include organic liquids such as butyl acetate, alkanes, alcohols, ketones, esters, ethers, glycols, glycol ethers, hydrocarbons, hydrofluorocarbons, or any other material that can dilute the composition without adversely affecting any of the component materials. Examples of hydrocarbons include isododecane, isohexadecane, Isopar® L (C11-C13), Isopar® H (C11-C12), hydrogenated polydecene, mineral oil, particularly hydrogenated mineral oil or white oil, liquid polyisobutene, isoparaffinic oil, or petroleum jelly. Examples of ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3-ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaplate, and octyl palmitate. Further organic diluents include fats, oils, fatty acids, and aliphatic alcohols. Mixtures of diluents can also be used.

[0078] If necessary, biocides may be further used in the composition. Note that the term "biocide" includes fungicides, fungicides, and algaecides, among others. Suitable examples of useful biocides that may be used in the compositions described herein include, for example: Carbamates, such as methyl-N-benzimidazole-2-ylcarbamate (carbendazim) and other suitable carbamates, such as 10,10'-oxybisphenoxacin, 2-(4-thiazolyl)-benzimidazole, Examples of suitable combinations with UV stabilizers include N-(fluorodichloromethylthio)phthalimide, diiodomethyl p-tolylsulfone, 2,6-di(tert-butyl)-p-cresol, 3-iodo-2-propinyl (propinyl) butylcarbamate (IIPBC), zinc 2-pyridinethiol-1-oxide, triazolyl compounds, and isothiazolinones, such as 4,5-dichloro-2-(n-octyl)-4-isothiazolinone-3-one (DCOIT), 2-(n-octyl)4-isothiazolinone-3-one (OIT), and n-butyl-1,2-benzoisothiazolinone-3-one (BBIT). Other biocides include, for example, zinc pyridinethione, 1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazole-1-ylmethyl)pentan-3-ol and / or 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole.

[0079] The fungicide and / or biocide may preferably be present in an amount of 0 to 0.3% by weight of the polydiorganosiloxane elastomer composition, and may be present in an encapsulated form as necessary, as described in European Patent No. 2106418.

[0080] Generally, polymer (a) is prepared as described above and at least partially completed before the addition of other components. Typically, the end-sealing reaction is completed before the addition of other components of the polydiorganosiloxane elastomer composition. Furthermore, any desired neutralization step and / or end-sealing catalyst removal step, although not necessary for short-term storage, is typically performed before the addition of other components of the polydiorganosiloxane elastomer composition.

[0081] If desired, the alkoxy-end-bound polymer from the final product of the alkoxy-end-bound polydiorganosiloxane polymer reaction may be used as component (a) in the polydiorganosiloxane elastomer composition together with other components introduced into the composition in any preferred order. As previously discussed, all or part of the polyalkoxysilane excess from the end-bound reaction can be used as a crosslinking agent (c), and therefore, a further crosslinking agent (c) is optional, as long as a sufficient amount of crosslinking agent (polyalkoxysilane excess) is available in the final polydiorganosiloxane elastomer composition for the composition to cure into an elastomer product.

[0082] The first component added to the final reaction product (a) of the alkoxy-terminated polydiorganosiloxane polymer is, for example, a filler (b) for effectively forming a base containing the alkoxy-terminated polydiorganosiloxane (a) and the filler (b). Other components may then be added in any preferred order, for example, an additional crosslinking agent (c) as needed, followed by a condensation curing catalyst (d), followed by an adhesion promoter (e) as needed, along with the addition of other optional additional components as needed. Alternatively, for example, to stabilize the composition during storage, an adhesion promoter (if present), an additional crosslinking agent (if needed), and a catalyst may be added first, followed by the filler, and finally a -OH (water / water / alcohol) scavenger.

[0083] The processes described herein are used to produce alkoxy-end sealed polydiorganosiloxane polymers. The alkoxy-end sealed polydiorganosiloxane polymers produced by the processes described herein can be incorporated into polydiorganosiloxane elastomer compositions. These compositions are preferably room-temperature curable compositions, meaning they cure at room temperature without heating, but curing can be accelerated by heating where appropriate.

[0084] Polydiorganosiloxane elastomer compositions prepared from alkoxy-terminated polydiorganosiloxane polymers produced by the processes described herein may be designed to provide low modulus and high elongation sealant, adhesive, and / or coating compositions. Low modulus silicone sealant compositions are preferably "gun-applicable," i.e., have a suitable extrusion capacity, i.e., minimum extrusion rate, of 10 ml / min, or 10 to 1000 mL / min, or 100 to 1000 mL / min, as measured by ASTMC1183-04.

[0085] The components in the polydiorganosiloxane elastomer composition and their amounts may be selected to impart mobility to the cured sealant material. Mobility is greater than 25% or in the range of 25% to 50% as measured by ASTMC719-13.

[0086] The polydiorganosiloxane elastomer composition described above is (i) Space / gap filling applications, (ii) Sealing applications such as sealing the edges of lap joints in construction membranes, or (iii) Sealing penetration applications, for example, sealing vents in construction membranes, (iv) Bonding at least two substrates together, (v) A gun-applicable sealant composition used for a laminated layer between two substrates to produce a laminate of a first substrate, a sealant product, and a second substrate.

[0087] In the case of (v) above, when used as layers in a laminate, the resulting laminated structure is not limited to these three layers. Additional layers of cured sealant and substrate may be applied. The layers of the gun-applicable polydiorganosiloxane elastomer compositions described above in the laminate may be continuous or discontinuous.

[0088] Polydiorganosiloxane elastomer compositions prepared from alkoxy-terminated polydiorganosiloxane polymers produced by the processes described herein may be applied to any suitable substrate. Suitable substrates may include, but are not limited to, glass; concrete; brick; decorative plaster; metals such as aluminum, copper, gold, nickel, silicon, silver, stainless steel alloys, and titanium; ceramic materials; epoxy, polycarbonate, poly(butylene terephthalate) resins, polyamide resins, and blends thereof, such as blends of polyamide resins with syndiotactic polystyrene, including acrylonitrile-butadiene-styrene, styrene-modified poly(phenylene oxide), poly(phenylene sulfide), vinyl esters, polyphthalamides, and polyimides, commercially available from The Dow Chemical Company in Midland, Michigan, USA; cellulose substrates such as paper, cloth, and wood; and combinations thereof. If two or more substrates are used, the substrates do not need to be made of the same material. For example, it is possible to form laminates of plastic and metal substrates or wood and plastic substrates.

[0089] In the case of a polydiorganosiloxane elastomer composition prepared from an alkoxy-terminated polydiorganosiloxane polymer produced by the process described herein, the polydiorganosiloxane elastomer composition may be used as a silicone sealant composition, in a method of filling the space between two substrates to form a seal between them, a) To provide the polydiorganosiloxane elastomer composition described above, b) Applying the polydiorganosiloxane elastomer composition to a first substrate and bringing a second substrate into contact with the polydiorganosiloxane elastomer composition applied to the first substrate, or c) A method is provided which includes filling the space formed by the arrangement of the first substrate and the second substrate with the polydiorganosiloxane elastomer composition and curing the polydiorganosiloxane elastomer composition.

[0090] As an alternative, a polydiorganosiloxane elastomer composition prepared from an alkoxy-terminated polydiorganosiloxane polymer produced by the process described herein may be a self-leveling sealant composition, for example, a self-leveling highway sealant. A self-leveling sealant composition is "self-leveling" when it is extruded from a storage container into a horizontal joint; that is, the sealant will flow under sufficient gravity to provide close contact between the sealant and the sides of the joint space. This allows for maximum adhesion of the sealant to the joint surface. Self-leveling also eliminates the need to work the sealant with tools after it has been placed into the joint, as is required for sealants designed for use in both horizontal and vertical joints. Thus, the sealant flows well enough to fill cracks upon application. If the sealant has sufficient flow under gravity, it will form close contact with the sides of the irregular crack wall and create a good bond. However, there is no need to work the sealant with tools after it has been pushed into the crack in order to apply mechanical force to make it contact the crack sidewall.

[0091] The self-leveling compositions described herein are useful as sealants possessing a unique combination of properties necessary for their function in sealing asphalt pavements. Asphalt pavement materials are used to form asphalt highways by stacking materials of considerable thickness, such as 20.32 cm, and to repair deteriorated concrete highways by covering them with layers of thickness, such as 10.16 cm. Asphalt overlays are susceptible to a phenomenon known as reflective cracking, in which cracks are formed in the asphalt overlay due to the movement of the underlying concrete at joints present in the concrete. These reflective cracks need to be sealed to prevent water from entering the cracks, as water freezing and expanding in these cracks will further damage the asphalt pavement.

[0092] For any reason, for example, to form an effective seal against a crack exposed to movement due to thermal expansion and contraction, the sealing material must be bonded to the interface of the crack sidewall, and this sealing material must not lose its bonding force when the crack compresses and expands. In the case of asphalt pavement, the sealant must not exert enough strain on the asphalt at the interface to cause the asphalt itself to break; that is, the elastic modulus of the sealant must be sufficiently low so that the stress applied to the bond line is well below the yield strength of the asphalt.

[0093] In such cases, the modulus of elasticity of the hardened material is designed to be sufficiently low so as not to exert enough force on the asphalt to cause cohesive failure. When the hardened material is subjected to tension, the level of stress caused by the tension decreases over time, and even in cases of high elongation, the joint is not exposed to high stress levels.

[0094] Alternatively, polydiorganosiloxane elastomer compositions prepared from alkoxy-terminated polydiorganosiloxane polymers produced by the processes described herein may be used as elastomer coating compositions, for example, as barrier coatings for building materials or as weather-resistant coatings for roofs, and the compositions may have a viscosity similar to that of paints, thereby allowing application by, for example, a brush, roller, or spray gun. The coating compositions described herein may be designed, when applied to a substrate, to provide the substrate with long-term protection from, for example, the penetration of air and water under normal movement conditions caused by, for example, seasonal thermal expansion and / or contraction, ultraviolet rays, and weather. [Examples]

[0095] Unless otherwise specified, all viscosity measurements were performed using either a Brookfield® rotational viscometer with spindle LV-4 (designed for viscosities in the range of 1,000 to 2,000,000 mPa.s) or a Brookfield® rotational viscometer with spindle LV-1 (designed for viscosities in the range of 15 to 20,000 mPa.s) for viscosities below 1,000 mPa.s, with the rate (shear rate) adjusted according to the polymer viscosity, and measurements were performed at 25°C.

[0096] Example 1: I put the following into the Max100 speedmixer cup: (i) 40 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 42 mPa·s and an average of 3.7 wt% of Si-OH groups per molecule, and (ii) 47 g of methyltrimethoxysilane. Next, 0.6 g of 1,8-diazabicyclo[5.4.0]undeca-7-ene (DBU) was added, and the mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C for 18 hours.

[0097] After 18 hours, the resulting product was complete. 29 Si NMR and1 The final reaction product of methyldimethoxy-terminated polydimethylsiloxane was obtained with a conversion rate of >99.6% when measured by 1H NMR. The silanol signal disappeared. 29 Si NMR (80 MHz, CDCl3) δ-12 and 1 ¹H NMR (400 MHz, CDCl3) δ 0.85) and the appearance of the corresponding methyldimethoxysilyl terminal blockade ( 29 Si NMR (80 MHz, CDCl3) δ-48 and 1 The conversion rate was measured by observing 1H NMR (400 MHz, CDCl3) δ3.48).

[0098] Comparative Example 1: I put the following into the Max100 speedmixer cup: (i) 40 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 42 mPa·s and an average of 3.7 wt% of Si-OH groups per molecule, and (ii) 47 g of methyltrimethoxysilane.

[0099] The resulting mixture was mixed at 2000 rpm for 20 seconds three times, and then left to stand at 23°C for one week. 1 H and 29 Analysis of the mixture using Si NMR revealed no evidence of any reaction. The final reaction product contained only unreacted starting materials.

[0100] Example 2 I prepared the following in the Max40 speedmixer cup: (i) 10 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 42 mPa·s and an average of 3.7 wt% of Si-OH groups per molecule, and (ii) 5.9 g of methyltrimethoxysilane. Next, 0.05 g of DBU was added, and the mixture was mixed at 2000 rpm for 20 seconds three times. The resulting reaction mixture was then left to stand at 23°C. The reaction mixture was analyzed at 2 and 24 hours by NMR using the polydimethylsiloxane skeleton signal as an internal standard. 1 ¹H NMR (400 MHz, CDCl3) δ 3.48, 0.06). By comparing the relative amount of alkoxysilane terminal sealing groups with that of the polydimethylsiloxane skeleton, it was determined that the reaction proceeded with a conversion rate of >99.6% in 2 hours, yielding the methyldimethoxy-terminated polydimethylsiloxane product.

[0101] Comparative Example 2 I put the following into the Max100 speedmixer cup: (i) 10 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 42 mPa·s and an average of 3.7 wt% of Si-OH groups per molecule, and (ii) 5.9 g of methyltrimethoxysilane. Next, 0.05 g of 2-ethylhexanoic acid (2-EHA) and 0.05 g of DBU were added (i.e., 2-EHA was used as a catalyst and DBU as a co-catalyst), and the mixture was mixed at 2000 rpm for 20 seconds three times. The reaction mixture was analyzed at 2 and 24 hours by NMR using the polydimethylsiloxane skeleton signal as an internal standard. 1 ¹H NMR (400 MHz, CDCl3) δ 3.48, 0.06). By comparing the relative amount of alkoxysilane terminal sealing groups with that of the polydimethylsiloxane skeleton, it was determined that the reaction proceeded with a conversion rate of 90% in 2 hours, yielding a methyldimethoxy-terminated polydimethylsiloxane product.

[0102] This represents a lower conversion rate than that measured in Example 2.

[0103] Comparative Example 3 I put the following into the Max100 speedmixer cup: (i) 10 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 42 mPa·s and an average of 3.7 wt% of Si-OH groups per molecule, and (ii) 5.9 g of methyltrimethoxysilane. Next, 0.017 g of barium oxide was added, and the mixture was mixed at 2000 rpm for 20 seconds x 3 times. Then, the resulting mixture was left to stand at 23°C. 1 The reaction was analyzed by NMR at 2 hours and 24 hours using 1H NMR (400 MHz, CDCl3). NMR analysis showed that approximately 21% of the reaction was converted to the alkoxysilane-terminated product at 2 hours, but by 24 hours, the reaction appeared turbid. 1 1H NMR revealed a complex mixture of unidentified products. Furthermore, although methyltrimethoxysilane was added in excess, the silane starting material was not observed after 24 hours, suggesting further undesirable reactions and decomposition.

[0104] Example 3 I prepared the following in the Max300 speedmixer cup: (i) 250 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 56,000 mPa.s and an average of 0.05 wt% of Si-OH groups per molecule, and (ii) 4.3 g of methyltrimethoxysilane. The mixture was stirred, and then 0.001 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was added. The mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C for 18 hours. After 18 hours, the reaction was complete. 1 The final reaction product of methyldimethoxy-terminated polydimethylsiloxane was obtained with a conversion rate of >99.6% when measured by 1H NMR (400 MHz, CDCl3).

[0105] Comparative Example 4 I put the following into the Max100 speedmixer cup: (j) 10 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 42 mPa·s and an average of 3.7 wt% Si-OH groups per molecule, and (ii) 5.9 g of methyltrimethoxysilane. Next, 0.36 g of a Pt solution (1.3 wt% platinum in dimethylvinylsiloxy-terminated dimethylsiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added, and the mixture was mixed at 2000 rpm for 20 seconds × 3 times. Then, the resulting mixture was left at 23 °C, 29 and analyzed by NMR at 96 hours using Si NMR (80 MHz, CDCl3). The reaction showed a conversion rate of approximately 0% to the alkoxysilane-terminated product by NMR analysis.

[0106] Comparative Example 5 The following were charged into a Max100 speedmixer cup: (j) 40 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 56,000 mPa·s and an average of 0.05 wt% Si-OH groups per molecule, and (ii) 0.69 g of methyltrimethoxysilane. 0.04 g of a 0.4 M lithium trimethylsilanolate solution in toluene was added. The mixture was mixed at 2000 rpm for 20 seconds × 3 times. Then, the resulting mixture was left at 23 °C, 29 and analyzed by NMR at 24 hours using Si NMR (80 MHz, CDCl3). The reaction showed a conversion rate of approximately 0% to the alkoxysilane-terminated product by NMR analysis.

[0107] Example 4 The following were charged into a Max100 SpeedMixer cup: (k) 40 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 56,000 mPa·s and an average of 0.05 wt% Si-OH groups per molecule, and (ii) 1.65 g of 1,6-bis(trimethoxysilyl)hexane. The mixture was stirred, and then 0.0002 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was added. The mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C for 18 hours. After 18 hours, the product was complete. 1 1H NMR (400 MHz, CDCl3) and 29 The final reaction product, methyldimethoxy-terminated polydimethylsiloxane, was obtained with a conversion rate of >99.6% when measured by Si NMR (80 MHz, CDCl3).

[0108] Example 5 I put the following into the Max100 SpeedMixer cup: (j) 40 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 56,000 mPa.s and an average of 0.05 wt% Si-OH groups per molecule, and (ii) 0.79 g of vinyltrimethoxysilane. The mixture was stirred, and then 0.0002 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was added. The mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C for 2 hours. After 2 hours, the product was complete. 1 1H NMR (400 MHz, CDCl3) and 29 The final reaction product, methyldimethoxy-terminated polydimethylsiloxane, was obtained with a conversion rate of >99.6% when measured by Si NMR (80 MHz, CDCl3).

[0109] Example 6 I put the following into the Max300 SpeedMixer cup: 250 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of (m) 56,000 mPa.s and an average of 0.05 wt% Si-OH groups per molecule, and (ii) 4.3 g of methyltrimethoxysilane. The mixture was mixed at 2000 rpm for 20 seconds three times. The initial viscosity was measured using an ARES cone and plate rheometer. Then, 0.0011 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was added, and the mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C. The viscosity was measured at different time points using an ARES cone and plate rheometer, and the viscosity of the obtained material is shown in Table 1 below. [Table 1]

[0110] As shown, this reaction mixture can be stored at room temperature for 168 hours without change, and for 336 hours with only slight decomposition.

[0111] Example 7 I put the following into the Max300 SpeedMixer cup: (n) 250 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 56,000 mPa.s and an average of 0.05 wt% Si-OH groups per molecule, and (ii) 4.3 g of methyltrimethoxysilane. The mixture was mixed at 2000 rpm for 20 seconds three times. The initial viscosity was measured using an ARES cone and plate rheometer. Next, 0.0110 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was added, and the mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C. The viscosity was measured at different time points using an ARES cone and plate rheometer. The viscosities of the materials are shown in Table 2 below. [Table 2]

[0112] As shown, the reaction mixture can be stored at room temperature for 72 hours without decomposition.

[0113] Example 8 I put the following into the Max300 SpeedMixer cup: (i) 250 g of dimethylsilanol-terminated polydimethylsiloxane having a viscosity of 56,000 mPa.s and an average of 0.05 wt% of Si-OH groups per molecule, and (ii) 4.3 g of methyltrimethoxysilane. The mixture was mixed at 2000 rpm for 20 seconds three times. The initial viscosity was measured using an ARES cone and plate rheometer. Next, 0.1100 g of 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) was added, and the mixture was mixed at 2000 rpm for 20 seconds three times. The resulting mixture was then left to stand at 23°C. The viscosity was measured at different time points using an ARES cone and plate rheometer. The viscosity of the materials is shown in Table 3 below. [Table 3]

[0114] As shown, the reaction mixture stored at room temperature for 72 hours already shows significant degradation.

[0115] Examples 9-15 In the following embodiments, various silanes were used to prepare end-bound polymers to be produced according to the disclosure as the first step in the preparation of sealant compositions. In Examples 9-15, dimethylsilanol-terminated polydimethylsiloxanes having a viscosity of 56,000 mPa·s and an average of 0.05 wt% Si-OH groups per molecule were mixed with possible combinations of end-bound silanes and catalysts. The catalyst used was a 2% solution of triazabicyclodecene (TBD) in toluene. The mixture was stirred in a SpeedMixer at 2000 rpm for 20 seconds, then heated to a temperature of 50°C and maintained at that temperature for 60 minutes to react, at which point the resulting mixture was sampled. 1 Analysis by 1H NMR determined that the reaction was complete. The materials used are shown in Table 4 below. [Table 4]

[0116] The polymer used in Table 1 was a dimethylsilanol-terminated polydimethylsiloxane with a viscosity of 56,000 mPa·s at 25°C and an average of 3.7% by weight of Si-OH groups per molecule. In this case, the catalyst was provided in a toluene solution. Later, it was found that it was optimal for the catalyst to be provided in a solution of another starting material, usually a polyalkoxysilane.

[0117] Sealant formulations were prepared using the alkoxy-end sealed polydiorganosiloxane polymer reaction final products obtained from the preparations described herein and related to Examples 4 to 10 in Table 1, by taking the final product of the alkoxy-end sealed polydiorganosiloxane polymer reaction and adding the components shown in Table 5 below. [Table 5]

[0118] In Table 5, DBTDL is the tin-based catalyst dibutyltin dilaurate. The adhesion promoter (AP) used was aminopropylaminoethyltrimethoxysilane. The HMDZ was hexamethyldisilazane, used as a scavenger, and the filler used was CAB-O-SIL LM-150 fumed silica from Cabot Corporation.

[0119] In this series of examples, sealant compositions were first prepared by adding an adhesion promoter and a tin catalyst to the final product of an alkoxy-terminated polydiorganosiloxane polymer reaction containing a polymer and an excess of polyalkoxysilane for use as a crosslinking agent. These components were then mixed in a SpeedMixer at 2000 rpm for 20 seconds. Next, a filler was introduced into the mixture, and the resulting composition was mixed at 2000 rpm for 40 seconds. Subsequently, a stabilizer (HMDZ) was added, and the resulting mixture was mixed again at 2000 rpm for 20 seconds. The sealant compositions were then stored for future use. Different compositions were tested for their physical properties, and the results are shown in Table 6 below. [Table 6]

[0120] In Table 6, RHEO was a visual assessment of whether the final product provided a non-sag or fluid composition. The term "good" used for Rheo in Table 6 indicates that the composition was non-sag.

[0121] Skin-over time (SOT) and non-adhesion time (TFT) were measured according to ASTM C679-15.

[0122] 24-hour storage stability was a visual test to determine whether the sealant composition gelled within the first 24 hours after process completion. This can occur if the polymer end-sealing process is not fully completed before the introduction of the tin catalyst. Stable materials do not change from their initial rheology and, specifically, do not gel. Polymers used in this tin chemistry that are not fully sealed before formulation will gel in packaging within a short period. In Table 6, "good" indicates that the composition has not gelled after 24 hours. Test samples were evaluated for rheology using a spatula.

[0123] A 24-hour curing evaluation was used to assess whether the cured elastomer had hardened and formed into a well-formed elastomer. This test involved drawing down a 100 mil slab of sealant and allowing it to cure for 24 hours. The "curing evaluation" involved peeling and pulling the slab while observing its mechanical properties. If the elastomer product "peeled" and was elastic, it passed the evaluation and was recorded as "good" in Table 6. Materials that did not pass remained in a paste-like state and were therefore recorded as "uncured."

Claims

1. A process for preparing alkoxy-terminated polydiorganosiloxanes from silanol-terminated polydiorganosiloxane starting materials, (i) The silanol-terminated polydiorganosiloxane starting material is obtained from one or more polyalkoxysilane starting materials having the following structures 【Chemistry 1】 (wherein b is 0, 1, or 2, R ２ R is a linear or branched alkyl group having 1 to 15 carbon atoms. １ (This group is selected from linear or branched alkyl groups having 1 to 15 carbon atoms; cycloalkyl groups; alkenyl groups, aryl groups; aralkyl groups; and groups obtained by replacing all or part of the hydrogen atoms of the aforementioned organic groups with halogens.) The process involves reacting in the presence of one or more end-bound catalyst starting materials comprising linear, branched, or cyclic molecules, each containing at least one amidine group, guanidine group, or derivatives of the amidine group and / or guanidine group, or mixtures thereof, in an amount of 0.0005 to 0.75% by weight of the starting material composition. A process carried out using only the silanol-terminated polydiorganosiloxane starting material, the polyalkoxysilane starting material, and the terminal-terminated catalyst starting material.

2. The end-sealed catalyst starting material contains one or more of the following groups (1) to (4), including a linear, branched, or cyclic silicon-containing molecule or a linear, branched, or cyclic organic molecule. 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (where each R ４ , R ５ , R ６ , R ７ , and R ８ may be the same or different and are selected from hydrogen, an alkyl group, a cycloalkyl group, a phenyl group, an aralkyl group, or R ４ and R ５ , or R ６ and R ５ , or R ７ and R ５ , or R ８ and R ４ together form an alkylene group, which is part of a ring structure and which alkylene group may or may not be interrupted by an oxygen or nitrogen atom), a process for preparing an alkoxy-terminated polydiorganosiloxane from the silanol-terminated polydiorganosiloxane starting material according to claim 1.

3. A process for preparing an alkoxy-terminated polydiorganosiloxane from a silanol-terminated polydiorganosiloxane starting material according to claim 1, wherein the terminally sealed catalyst starting material comprises one or more of the following: 1,1,3,3-tetramethylguanidine, 2-[3-(trimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, 2-[3-(methyldimethoxysilyl)propyl]-1,1,3,3-tetramethylguanidine, triazabicyclodecene (1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, and 1,8-diazabicyclo[5.4.0]undeca-7-ene.

4. A process for preparing an alkoxy-terminated polydiorganosiloxane from a silanol-terminated polydiorganosiloxane starting material according to any one of claims 1, 2, or 3, wherein the alkoxy-terminated polydiorganosiloxane is not stabilized, not neutralized, or neither stabilized nor neutralized at the completion of the process, and / or the terminally sealed catalyst starting material is not removed at the end of the process.

5. A process for preparing an alkoxy-ended polydiorganosiloxane from a silanol-ended polydiorganosiloxane starting material according to any one of claims 1, 2, or 3, wherein the end-stopping catalyst starting material is introduced into the reaction environment either as a solid, as a solution in a compatible silicone or organic solvent, or added to or within one of the polyalkoxysilane starting materials used to alkoxy-end-stop the silanol-ended polydiorganosiloxane.

6. A process for preparing an alkoxy-terminated polydiorganosiloxane from a silanol-terminated polydiorganosiloxane starting material according to any one of claims 1, 2, or 3, wherein the process is carried out at a temperature of 30 to 100°C.

7. A process for preparing an alkoxy-terminated polydiorganosiloxane from a silanol-terminated polydiorganosiloxane starting material according to any one of claims 1, 2, or 3, wherein the polyalkoxysilane starting material is provided in excess so that unreacted polyalkoxysilane starting material is available to function as a crosslinking agent when used to prepare a sealant composition.

8. The following ingredients: (a) Final reaction product of an alkoxy-terminated polydiorganosiloxane polymer prepared according to the process described in any one of claims 1, 2, or 3, (b) Fillers, and (d) Condensation curing catalyst, (c) Crosslinking agents, and / or A method for preparing a curable polydiorganosiloxane elastomer composition, comprising the step of mixing (e) with an adhesion promoter, or without (c) and (e).

9. A method for preparing a curable polydiorganosiloxane elastomer composition according to claim 8, further comprising adding an -OH scavenger to the curable polydiorganosiloxane elastomer composition.

10. A method for preparing a curable polydiorganosiloxane elastomer composition according to claim 8 or 9, wherein the composition is a one-component composition and the curing catalyst (d) is a tin-based catalyst.

11. A method for preparing a silicone elastomer, comprising the step of curing a curable polydiorganosiloxane elastomer composition prepared according to the method of any one of claims 8 to 10.

12. Use of alkoxy-terminated polydiorganosiloxanes prepared according to the process described in any one of claims 1 to 7 in sealants in the fields of facades, insulating glass, window construction, automobiles, solar, or buildings, or as elastomer coating compositions.

13. The use according to claim 12, wherein the elastomer coating composition is used in a barrier coating for building materials or as a weather-resistant coating for roofs.

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