Synthesis and Use of Carbamate-Functionalized Alkoxysilalkylene Silane Compounds

Abstract

A carbamate-functional alkoxysilalkylene silane compound, and methods for its preparation and use are provided. This compound has the formula (R 1 2)N-C(=O)O-Si(R 2 2)-D-Si(OR 4 )3, wherein R 1 may be hydrogen, methyl, or ethyl, R 2 may be methyl, R 4 may be methyl, and in each case of D, is a linear or branched alkylene group such as -CH2-CH2- and -CH(CH3)-. This compound may be used to cap the silanol moieties of silanol-functional polyorganosiloxanes to produce polyalkoxy-functional polyorganosiloxanes. The polyalkoxy-functional polyorganosiloxanes may be used as crosslinking agents in moisture-curable room temperature vulcanizing (RTV) silicone compositions.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 392,299, filed on July 26, 2022, under 35 U.S.C. § 119(e). U.S. Provisional Patent Application No. 63 / 392,299 is hereby incorporated by reference in its entirety.

[0002] There are provided carbamate - functional alkoxysilalkylene silane compounds, and methods for their preparation and use. The compounds can react with polyorganosiloxanes having silanol moieties to form polyalkoxy - functional polyorganosiloxanes, which are useful in condensation - reaction curable compositions.

[0003] Introduction Polyalkoxy - functional polydiorganosiloxanes are useful in moisture - curable polyorganosiloxane compositions. Polyalkoxy - functional polydiorganosiloxanes can be synthesized, for example, as described in U.S. Pat. Nos. 10968317, 11098163, 11168181, and 11161939, or International Publication No. 2020 - 0231755, by end - capping vinyl - functional polyorganosiloxanes with polyalkoxy - functional hydrogen siloxane oligomers via hydrosilylation reactions. However, this end - capping method has the disadvantages of being relatively costly and there being a relatively small number of commercially available vinyl - functional polyorganosiloxanes, resulting in limited selection of expensive polyalkoxy - functional polydiorganosiloxane products.

Summary of the Invention

[0004] There are provided carbamate - functional alkoxysilalkylene silane compounds. Methods for the preparation and use of the above compounds are also provided. The present compounds can be used in silylation reactions for capping the silanol moieties of polyorganosiloxanes. The resulting polyalkoxy-functional polyorganosiloxanes are useful in condensation reaction-curable polyorganosiloxane compositions.

DETAILED DESCRIPTION OF THE INVENTION

[0005] The compounds introduced above have the following formula

[0006]

CHEMICAL

[0007] In the formula of the present compound, each R 1 may be the same or different. The alkyl groups of R 1 have 1 to 6 carbon atoms and are exemplified by methyl, ethyl, propyl (including n-propyl and / or isopropyl), butyl (including n-butyl, t-butyl, sec-butyl, and isobutyl), pentyl (including n-pentyl and branched-chain saturated hydrocarbon groups having 5 carbon atoms), and hexyl (including n-hexyl and branched-chain saturated hydrocarbon groups having 6 carbon atoms). Alternatively, two instances of R 1 may be joined together to form a cyclic secondary amine moiety having a nitrogen atom as shown in the formula of the present compound. Alternatively, each R 1may be independently selected from the group consisting of hydrogen and alkyl groups having 1 to 4 carbon atoms. Alternatively, each R 1 may be selected from the group consisting of hydrogen, methyl, and ethyl.

[0008] In the formula of this compound, each R 2 may be the same or different. Each R 2 is independently selected from the group consisting of alkyl groups and aryl groups. The alkyl group may have 1 to 6 carbon atoms, and the alkyl group of R 1 is as described above. Suitable aryl groups for R 2 may have 6 to 12 carbon atoms and are exemplified by phenyl, tolyl, xylyl, and naphthyl, or phenyl. Alternatively, each R 2 may be an alkyl group having 1 to 6 carbon atoms. Alternatively, each R 2 may be methyl or ethyl. Alternatively, each R 2 may be methyl.

[0009] In the formula of this compound, D is an alkylene group and may have 2 to 20 carbon atoms, or 2 to 10 carbon atoms, or 2 to 8 carbon atoms, or 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Examples include

[0010]

Chemical Structure

[0011]

Chemical Structure

[0012]

Chemical Structure

[0013]

Chemical

[0014] In the formula of this compound, each R 4 may be the same or different. Each R 4 is an independently selected alkyl group. The alkyl group may have 1 to 6 carbon atoms, and the alkyl group of R 2 is as described above. Alternatively, each R 4 may be an alkyl group having 1 to 4 carbon atoms. Alternatively, each R 4 may be methyl or ethyl. Alternatively, each R 4 may be methyl.

[0015] Method for producing the compound The above-mentioned compound is 1) Under the conditions for carrying out the reaction C) Carbamate salt D) Hydridosilane of the formula ClSiR 2 2H (wherein R 2 is as described above), and Optionally H) Combine the starting materials containing a solvent Thereby E) Carbamate-functional hydridosilane of the formula R 1 2NC(=O)O-SiR 2 2H (wherein R 1 and R 2 are as described above), and J) Form a reaction product containing by-products 2) Under the conditions for carrying out the hydrosilylation reaction, E) A carbamate-functional hydridosilane, F) A compound of the formula R 3 Si(OR 4 )3 (wherein R 3 is an alkenyl group and R 4 is as described above) an alkenyl-functional alkoxysilane, G) A hydrosilylation reaction catalyst, Optionally H) combining starting materials including a solvent, Thereby, I) forming a reaction product comprising the above-mentioned carbamate-functional alkoxysilalkylene silane compound, may be prepared by a method comprising.

[0016] The carbamate salt used in step 1) of the above method which is starting material C) may be commercially available. For example, ammonium carbamate of the formula H2N-C(=O)OH·NH3 is available from Sigma Aldrich Inc., St. Louis, Missouri, USA.

[0017] Alternatively, the method for preparing this compound may include an optional step for forming a carbamate salt. In an optional additional step, starting material A) R 1 2NH, R 1 NH2, or a combination thereof (wherein R 1An amine having a formula selected from the group consisting of) as described above may be used. Suitable amines are known in the art and are commercially available. For example, the amine may be a dialkylamine such as diethylamine (HN(CH2CH3)2) or dimethylamine (HN(CH3)2). Dialkylamines are commercially available from various suppliers such as Sigma Aldrich Inc. in St. Louis, Missouri, USA. Alternatively, the amine may be a monoalkylamine, for example, propylamine (H2NCH2CH2CH3) or butylamine (H2NCH2CH2CH2CH3). Alternatively, the amine may be a cyclic secondary amine. Alternatively, a combination of a dialkylamine and a monomalkylamine may be used.

[0018] Starting material B) is carbon dioxide of the formula CO2, which is known in the art and is commercially available. For example, gaseous CO2 may be purchased from various suppliers such as Air Products and Chemicals in Allentown, Pennsylvania, USA. Solid CO2 (cardice) may also be purchased from various suppliers such as EZPro Delivery.

[0019] Starting material H) is a solvent that may optionally be used in the method. Solvents that can be used herein serve to fluidize the starting materials and do not essentially react with those starting materials. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility refers to the solvent being sufficient to dissolve and / or disperse the starting materials. Volatility refers to the vapor pressure of the solvent. Solvents used to prepare the carbamate salts may include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, or xylene; aliphatic hydrocarbons such as heptane, hexane, or octane; halogenated hydrocarbons such as dichloromethane or chloroform; or combinations of two or more of these. Such solvents are known in the art and are commercially available.

[0020] The optional step cited above for forming the carbamate salt may be carried out by any convenient means such as adding the amine and, if present, the solvent to the reaction vessel and bubbling gaseous CO2 into the vessel, or adding phosgene to the reaction vessel containing the amine and, if present, the solvent. The headspace in the reaction vessel may be maintained under inert conditions such as an inert gas (e.g., nitrogen) during the formation of the carbamate salt. The formed carbamate salt may have the formula R 1 2NH2 + R 1 2NC(=O)O - (wherein R 1 is as described above). In this method, forming the carbamate salt according to the optional step may be carried out before step 1). B) The amount of carbon dioxide is not critical, but it may be in molar excess with respect to the amine in A).

[0021] In step 1) of this method, the starting materials comprising the above-mentioned C) carbamate salt and D) hydridosilane chloride of the formula ClSiR 2 2H (wherein R 2 is as described above) are combined under conditions under which a reaction between the carbamate salt and chlorine occurs. The hydridosilane chloride is known in the art and may be prepared by known methods such as the Direct Process. Examples of hydridosilane chlorides include dimethylchlorosilane (Me2HSiCl) and phenylmethylchlorosilane (PhMeHSiCl), which are commercially available from Sigma Aldrich Inc.

[0022] In step 1), an additional solvent may be added. The solvent in step 1), if used, may be the same as or different from the solvent used to form the carbamate salt. The hydridosilane and the solvent may optionally be combined, for example, by mixing, before adding the hydridosilane to the carbamate salt in the reaction solution described above. Step 1) produces a reaction product containing a carbamate-functional hydridosilane and a by-product. The carbamate-functional hydridosilane may have the formula R 1 2NC(=O)O-SiR 2 2H (wherein R 1 and R 2 are as described above).

[0023] Step 1) may be carried out by mixing starting materials comprising C) a carbamate salt and D) a hydridosilane (and H) a solvent, if present). The mixing may be carried out at RT or while heating to a temperature at which the carbamate is not decomposed, for example, up to 150 °C. Alternatively, step 1) may be carried out while cooling. Step 1) may be carried out under inert drying conditions. Step 1) produces a reaction product containing E) a carbamate-functional hydridosilane and a by-product. The method may optionally further comprise recovering E) the carbamate-functional hydridosilane and, if used, all or part of H) the solvent and / or any by-products that may form, for example, an alkylammonium chloride of the formula R 1 4N + Cl - (wherein R 1 is as described above) by purifying the reaction product by any convenient means such as filtration, distillation and / or stripping.

[0024] The carbamate-functional hydridosilane E) produced as described above may have the formula R 1 2NC(=O)O-SiR 2 2H, wherein R 1 and R 2is as described above. The carbamate-functional hydridosilane is used in step 2) of the above-described method, and step 2) combines starting materials including E) a carbamate-functional hydridosilane, F) an alkenyl-functional alkoxysilane, G) a hydrosilylation reaction catalyst, and optionally H) a solvent under conditions for carrying out a hydrosilylation reaction.

[0025] The starting material F) is an alkenyl-functional alkoxysilane which may have the formula R 3 Si(OR 4 )3 (wherein R 3 is an alkenyl group and R 4 is as described above). Alkenyl-functional alkoxysilanes are known in the art and are commercially available. Examples include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, and hexenyltriethoxysilane, all of which are commercially available, for example, from Gelest, Inc., Morrisville, Pennsylvania, USA.

[0026] In the above-described method, the amounts of starting materials E) and F) are not critical, but starting materials E) and F) can be used in a weight ratio of (E) / F) of 1 / 1 to 1 / 5, or 1 / 1 to 1 / 3.

[0027] The starting material G) is a hydrosilylation reaction catalyst. This catalyst will promote the reaction between the alkenyl group in F) alkenyl-functional alkoxysilane and the silicon-bonded hydrogen atom in E) carbamate-functional hydridosilane. The catalyst contains a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation reaction catalyst may be a platinum group metal or a compound or complex of a platinum group metal. For example, the hydrosilylation reaction catalyst may be chloridotris(triphenylphosphine)rhodium(I) (Wilkinson catalyst), a rhodium diphosphine chelate such as [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an organopolysiloxane, for example, a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex with platinum (Karstedt catalyst), or a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby catalyst), etc. Alternatively, the compound or complex may be microencapsulated in a matrix or core-shell structure. The hydrosilylation reaction catalyst is known in the art, for example, as described in International Publication No. 2021 / 081822 and the references cited therein. The hydrosilylation reaction catalyst is commercially available. For example, SYL-OFF (trademark) 4000 Catalyst and SYL-OFF (trademark) 2700 are available from Dow Silicones Corporation, Midland, Michigan, USA.

[0028] G) The amount of the hydrosilylation reaction catalyst is an amount sufficient to catalyze the hydrosilylation reaction of the silyl hydride moiety of starting material E) and the alkenyl group of starting material F). The amount depends on various factors including the reaction conditions and the types of starting materials E) and F) chosen. However, the amount may be sufficient to provide a platinum group metal in an amount of at least 5 ppm, or at least 50 ppm, or at least 100 ppm, or at least 200 ppm, or at least 400 ppm based on the combined weight of starting materials E) and F). At the same time, the amount of the hydrosilylation reaction catalyst G) may be at most 10,000 ppm, or at most 5,000 ppm, or at most 2,000 ppm, or at most 1,000 ppm, or at most 600 ppm on the same basis.

[0029] Starting material H) is the solvent described above and may be the same as or different from the solvent used in step 1) and / or any optional steps for forming the carbamate salt. One or more of the starting materials described above for use in step 2) may be dissolved or dispersed in the solvent before being combined in step 2). For example, the hydrosilylation reaction catalyst may be dissolved in a hydrocarbon solvent such as toluene before use in step 2). The amount of the solvent used in step 2) is not critical and may be, for example, 0 to 95% by weight, or more than 0% by weight and up to 90% by weight based on the combined weight of starting materials E), F), G), and H).

[0030] Step 2) may be carried out by any convenient means such as mixing and heating. The same reaction vessel as in Step 1) may be used. Alternatively, different reaction vessels may be used. The vessel may be purged with an inert gas such as nitrogen. The starting materials may be added in any order. Alternatively, (E) the carbamate-functional hydridosilane and (H) the solvent may be added to the reaction vessel. Thereafter, a portion of (F) the alkenyl-functional alkoxysilane may be added, and the contents of the vessel may be mixed. The hydrosilylation reaction catalyst, which is starting material (G), may be dissolved in (H) the solvent. A portion of the resulting catalyst / solvent solution may be added to the reaction vessel while mixing. Step 2) may be carried out at room temperature. Alternatively, in Step 2), the contents of the reaction vessel may be heated at a temperature up to 150 °C for a time sufficient to complete the reaction, or at 70 °C for up to 18 hours. Thereafter, one or more additional portions of (F) the alkenyl-functional alkoxysilane may be added, and the catalyst / solvent solution may be added while mixing and heating. During the addition, volatile substances may be removed by any convenient means such as stripping, at room temperature, or while heating, and optionally under reduced pressure.

[0031] Step 2) produces a hydrosilylation reaction product comprising (I) the above-mentioned carbamate-functional alkoxysilalkylenesilane compound. The method may optionally further comprise one or more additional steps. For example, the (I) compound may be recovered from the hydrosilylation reaction product by any convenient means such as filtration, stripping and / or distillation, optionally with heating and / or under reduced pressure.

[0032] The above method is illustrated in Scheme 1 and Examples 1 and 2 below in this specification. Scheme 1 - Exemplary method for forming a compound Optional steps and Step 1):

[0033]

Chemical formula

[0034] [Chemical]

[0035] The hydrosilylation reaction product produced by the above method comprises a combination of compounds having linear and branched linkers (β - adducts and α - adducts respectively) represented by D in the formula of the compounds shown above herein.

[0036] Alternatively, the compounds shown by the formula above herein are 1) Under the conditions for carrying out the hydrosilylation reaction, F) An alkenyl - functional alkoxysilane of the formula R 3 Si(OR 4 )3 (wherein R 3 is an alkenyl group and R 4 is as described above), D) A hydridochlorosilane of the formula ClSiR 2 2H (wherein R 2 is as described above), G) A hydrosilylation reaction catalyst, and Optionally H) a solvent are combined as starting materials, whereby E’) A hydrosilylation reaction product containing chlorodialkyl((trialkoxysilyl)alkylene)silane of the formula ClSiR 2 2 - D - Si(OR 4 )3 (wherein R 2 , D and R 4 are as described above) is formed, 2) Under the conditions for carrying out the reaction, E’) Chlorodialkyl((trialkoxysilyl)alkylene)silane, C) A carbamate salt, and Optionally H) a solvent are combined as starting materials, whereby I) The above - mentioned carbamate - functional alkoxysilalalkylenesilane compound, and forming a reaction product comprising the by-product J’), may be prepared by an alternative method.

[0037] In this alternative method, C) the carbamate salt may be commercially available or may be prepared in an optional step in the same manner as described above herein. When used in this alternative method, the optional step may be carried out before or after step 1). However, step 1) of this alternative method comprises combining starting materials comprising F) an alkenyl-functional alkoxysilane, D) a hydridochlorosilane, G) a hydrosilylation reaction catalyst, and optionally H) a solvent, under conditions for carrying out the hydrosilylation reaction, each of which is as described above herein. Step 1) may be carried out in a reaction vessel different from that in which the optional step of forming the above-described carbamate salt is used. The starting materials may be added to the vessel in any order. Step 1) may comprise mixing and heating the starting materials. Alternatively, H) the solvent and F) the alkenyl-functional alkoxysilane may be combined in the reaction vessel while mixing. The hydridochlorosilane may be added, followed by addition of the catalyst / solvent solution (prepared as described above). The vessel contents may be mixed while heating for a time sufficient to carry out the hydrosilylation reaction, for example up to 72 hours, optionally at, for example, 30 °C. Alternatively, the reaction mixture may be cooled to control the exothermic hydrosilylation reaction. The resulting hydrosilylation reaction product comprises E’) chlorodialkyl((trialkoxysilyl)alkylene)silane. The chlorodialkyl((trialkoxysilyl)alkylene)silane may comprise ClSiR 2 2-D-Si(OR 4 )3, wherein R 2 , D and R 4 are as described above. This may be a mixture having both linear and branched linkers D. The method may further optionally comprise recovering the chlorodialkyl((trialkoxysilyl)alkylene)silane from the hydrosilylation reaction product by any convenient means such as filtration, stripping, and / or distillation under heating and / or reduced pressure.

[0038] Step 2) of this alternative method involves combining starting materials including the E’) chlorodialkyl((trialkoxysilyl)alkylene)silane prepared as described above, C) the carbamate salt described above, and optionally H) a solvent, under the conditions for carrying out the reaction. The solvent, if present, may be the same as or different from the solvent used in step 1) and / or any optional steps. Step 2) may be carried out in the same reaction vessel as used in step 1) or in a different reaction vessel. Step 2) may be carried out, for example, by mixing the carbamate salt and the solvent (such as benzene) in a reaction vessel. The vessel may be purged with an inert gas, such as nitrogen. The chlorodialkyl((trialkoxysilyl)alkylene)silane may be added, for example, weighed into the reaction vessel intermittently or continuously at room temperature until all is added. The reaction vessel may be heated or cooled to control the exothermic hydrosilylation reaction. The resulting mixture may be stirred at room temperature for a certain period of time, for example, up to 18 hours, to complete the reaction. The reaction product of step 2) contains I) a carbamate-functional alkoxysilalkylene silane compound and K) by-products. This method may further include one or more additional steps, such as recovering the compound from the reaction product by any convenient means such as filtration, stripping, and / or distillation (optionally under reduced pressure) at room temperature or elevated temperature.

[0039] This alternative method is illustrated below in Scheme 2 and in Examples 1, 4, and 5 herein. Scheme 2 - Exemplary method for producing a compound Optional steps:

[0040]

Chemical formula

[0041]

Chemical formula

[0042] [Chemistry]

[0043] The reaction products generated by the above alternative methods include combinations of compounds having linear and branched linkers (β - adducts and α - adducts respectively) represented by D in the formula of the compounds shown above in this specification.

[0044] Preparing polyalkoxy - functionalized polyorganosiloxanes using the compound The above - mentioned compound is useful in a silylation reaction for capping silanol moieties. A method for capping the silanol moieties of a polyorganosiloxane includes combining, under conditions for carrying out the silylation reaction, starting materials comprising I) a compound of the above formula and II) a polyorganosiloxane having a silanol moiety. This method may further include preparing I) the compound by carrying out the above - mentioned method prior to step 1). This method produces a reaction product comprising a polyalkoxy - functionalized polyorganosiloxane.

[0045] The polyorganosiloxane II) having a silanol moiety is not particularly limited as long as II) the polyorganosiloxane has at least one silicon - bonded (HO 1 / 2 ) group capable of a capping reaction with the carbamate functional group of the compound of I) per molecule. The polyorganosiloxane may be linear, branched, cyclic or resinous. The polyorganosiloxane has the unit formula (R 5 3SiO 1 / 2 ) a (R 5 2SiO 2 / 2 ) b (R 5 SiO 3 / 2 ) c (SiO 4 / 2 ) d (HO 1 / 2 ) emay contain, wherein each R 5 is independently selected from the group consisting of monovalent hydrocarbyl groups (e.g., alkyl, alkenyl, and aryl) and monovalent halogenated hydrocarbyl groups (e.g., haloalkyl, haloalkenyl, and haloaryl), and the subscripts a, b, c, d, and e represent the average number of each unit per molecule, where a≧0, b≧0, c≧0, d≧0, and e≧1, and 2≦(a + b + c + d)≦10,000. Alternatively, the subscripts may have values such that 2≦(a + b + c + d)≦2,000, or 2≦(a + b + c + d)≦1,000. The alkyl groups suitable for R 5 are as described and exemplified above for R 2 . The aryl groups suitable for R 5 are as described and exemplified above for R 2 . The alkenyl groups suitable for R 5 are as described and exemplified above for R 3 . The monovalent halogenated hydrocarbyl group is a monovalent hydrocarbyl group as described above except that at least one hydrogen atom is formally replaced by a halogen atom. For example, the haloalkyl group includes chloromethyl and fluoromethyl. Alternatively, each R 5 may be an alkyl group such as methyl or ethyl, or an aryl group such as phenyl. Alternatively, each R 5 may be selected from methyl and phenyl. Alternatively, each R 5 may be methyl.

[0046] Alternatively, II) The polyorganosiloxane having a silanol moiety may be a polydiorganosiloxane, for example, the following formula

[0047]

Chemical formula

[0048] Polydiorganosiloxanes having a suitable silanol moiety are known in the art and are commercially available. For example, polydiorganosiloxane resins having various silanol contents are available from The Dow Chemical Company, Midland, Michigan, USA, as described, for example, in Silicone resins and intermediates Selection guide at Silicone Resins and Intermediates Selection Guide (dow.com). Polydiorganosiloxanes having a silanol moiety are also available from The Dow Chemical Company, Midland, Michigan, USA, under the trade name XIAMETER™ OHX Polymers. Examples are described, for example, in XIAMETER Brand Sealant Formulation Materials for North America (dow.com).

[0049] When the silanol moiety of a polyorganosiloxane is capped with this compound, a polyalkoxy-functionalized polyorganosiloxane is produced. For example, the capped polyorganosiloxane has the unit formula (R 5 3SiO 1 / 2 ) a (R 5 2SiO 2 / 2 ) b (R 5 SiO 3 / 2 ) c (SiO 4 / 2 ) d R 6 e and may contain, where R 6 is a group of the formula

[0050]

Chemical formula

[0051] When a bis-hydroxyl-terminated polydiorganosiloxane is capped, the resulting polyalkoxy-functionalized polyorganosiloxane has the formula

[0052]

Chemical formula

Examples

[0053] The following examples are provided to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the present invention described in the claims. The starting materials used in these examples are listed in Table 1.

[0054] [Table 1] Synthesis of Example 1 - O - Dimethylsilyl - N,N - Diethylcarbamate

[0055] [Chemical formula]

[0056] To a dry 250 mL round - bottom flask cooled in an ice bath, while stirring under a positive N2 pressure, dichloromethane (100 mL) and diethylamine (16.9 mL, 12.0 g, 164 mmol, 2.0 equivalents) were added through a rubber septum. Solid CO2 was carefully added to this mixture until the solution was saturated, and then a solution of dimethylchlorosilane (10.0 mL, 8.52 g, 90.0 mmol, 1.1 equivalents) in dichloromethane (10 mL) was added via syringe over 10 minutes. CO2 was added periodically over the next 30 minutes, and then the mixture was warmed to room temperature. The mixture was quickly filtered through a disposable frit, and dichloromethane was removed under reduced pressure at ambient temperature. The residue was dissolved in hexane and filtered through a disposable frit. Hexane was removed under reduced pressure to obtain a crystalline white solid (11.94 g, 68.1 mmol, 83%). 1 The presence of O - Dimethylsilyl - N,N - Diethylcarbamate was confirmed by 1H NMR analysis. Synthesis of Example 2 - Dimethyl(2 - (Trimethoxysilyl)ethyl)silyl Diethylcarbamate (ETM - Carbamate - NEt2)

[0057] [Chemical formula]

[0058] The following procedure was carried out in a dried nitrogen-purged glove box. To a dried 40 mL vial, O-dimethylsilyl-N,N-diethylcarbamate (2.60 g, 14.8 mmol) and dry toluene (25 mL) were added. Vinyltrimethoxysilane (1.25 mL, 8.15 mmol, 0.55 eq) was added to this solution, and the mixture was stirred (magnetic stirrer). A toluene solution of Karstedt catalyst (“Pt solution”, 2.5 wt% Pt, 10.4 μL) was added. The mixture was stirred at 70 °C for 3 h, and the progress of the reaction was monitored by gas chromatography. Then, a second portion of vinyltrimethoxysilane (1.25 mL, 8.15 mmol, 55 eq) was added, and the mixture was stirred at 70 °C for 18 h. An additional volume of Pt solution (10.4 μL) was added, and the mixture was stirred at 70 °C for 6 h. An additional volume of Pt solution (10.4 μL) was added, and the mixture was stirred at 70 °C for 18 h. Volatiles were removed at room temperature under reduced pressure. 1 H NMR, 13 C NMR, and GC showed a clean reaction forming an approximately 9:1 mixture of the β / α hydrosilylation product (dimethyl(2-(trimethoxysilyl)ethyl)silyldiethylcarbamate), with approximately 15 - 25% unreacted dimethylhydridosilyldiethylcarbamate. Synthesis of Preparation Example 3-chlorodimethyl((trimethoxysilyl)ethyl)silane

[0059]

Chemical formula

[0060] The following procedure was carried out in a dried nitrogen-purged glove box. To a dried 250 mL round-bottom flask were added dry toluene (100 mL) and vinyltrimethoxysilane (8.3 mL, 8.0 g, 54 mmol). To the stirred solution was added dimethylchlorosilane (6.6 mL, 5.6 g, 59 mmol, 1.1 eq), followed by a toluene solution of Karstedt catalyst (2.5 wt% Pt, 22.5 μL). The mixture was stirred at 30 °C for 72 h and then filtered through a pad of alumina. Toluene was removed under reduced pressure at ambient temperature. 1 H and 13 C NMR spectroscopy and GC showed no residual vinyltrimethoxysilane or dimethylchlorosilane, that the product contained about 14 wt% toluene, and that it was a mixture of β-addition product (86%) and α-addition product (14%). The mass of the product was 15.0 g (12.6 g, 51.9 mmol, 96% at 84 wt%). Synthesis of Example 4 - Dimethyl(2-(trimethoxysilyl)ethyl)silyldimethylcarbamate (ETM-carbamate-NMe2)

[0061]

Chemical formula

[0062] The following procedure was carried out in a dried nitrogen-purged glove box. To a stirred solution of dimethylammonium dimethylcarbamate (1.4 mL, 11.0 mmol, 1.3 eq) in dry benzene (20 mL) in a dried 40 mL vial was added, at ambient temperature, undiluted chlorodimethyl(2-(trimethoxysilyl)ethyl)silane (2.5 mL, 8.44 mmol) prepared as described in Example 3 dropwise over about 2 minutes. The mixture was stirred for 18 h. The mixture was filtered and the filtrate was placed under high vacuum to give a light brown liquid. The liquid was diluted with hexane (8 mL) and filtered through a 0.45 μm PTFE filter. The filtrate was placed under high vacuum to give a colorless liquid, 1By \(^1\)H NMR, it was confirmed that dimethyl(2-(trimethoxysilyl)ethyl)silyldimethylcarbamate exists as a mixture of β - addition product and α - addition product. Example 5 - Synthesis of dimethyl(2-(trimethoxysilyl)ethyl)silylcarbamate (ETM - carbamate - NH2)

[0063]

Chemical formula

[0064] The following procedure was carried out in a dry nitrogen - purged glove box. In an 80 - mL glass bottle, a suspension of ammonium carbamate (1.002 g, 12.8 mmol, 1.5 eq) in dry benzene (20 mL) was vigorously stirred at ambient temperature. To this, through a syringe, 84% - pure chlorodimethyl(2-(trimethoxysilyl)ethyl)silane (about 2.5 mL, 2.44 g, 2.05 g at 84 wt%, 8.44 mmol) prepared in Example 3 was added dropwise over 2 minutes. After stirring at ambient temperature for 1 hour, the mixture was filtered through a glass frit. The filtrate was placed under high vacuum to obtain a light - brown oily substance. 1 By \(^1\)H NMR, the presence of dimethyl(2-(trimethoxysilyl)ethyl)silylcarbamate (1.70 g, 6.34 mmol, 75%) was confirmed. Example 6 - Capping of hydroxyl - terminated polydimethylsiloxane

[0065]

Chemical formula

[0066] Into a dental cup, PDMS - OH and the capping agent prepared as described above in one of Examples 2, 4, and 5 were introduced. After mixing for 5 minutes with a high - speed mixer, the reaction mixture was maintained at room temperature in a sealed container or under high vacuum. The progress of the reaction was monitored by \(^1\)H NMR by the disappearance of the SiOH moiety. 1 When the reaction was complete, the formation of bis - trialkoxy - terminated PDMS was 29It was confirmed by Si NMR. The viscosity of the capped polydimethylsiloxane was measured by an ARES rheometer (25 mm parallel cone and plate, cone angle 0.0999 radians, gap 0.0508 mm, the test is a constant rate sweep from 0.1 to 10 1 / s at 10 points / 10).

[0067]

Table 2

Industrial Applicability

[0068] The above examples show that the carbamate-functional alkoxysilylalkylene silane compounds can be successfully prepared by the methods described herein. The examples further show that the compounds can be successfully used to cap the silanol moieties of polyorganosiloxanes. These examples show that by using the carbamate-functional polyalkoxysilylalkylene silane compounds of the present invention to cap various commercially available silanol-functional polyorganosiloxanes, a wide variety of polyalkoxy-functional polyorganosiloxanes can be prepared, which is due to the ready availability of various polyorganosiloxanes having silanol moieties (e.g., which can be linear, branched, or resinous). The carbamate-functional alkoxysilylalkylene silane compounds undergo a silylation reaction to cap the silanol moieties and have one or more of the following advantages. The reaction proceeds at room temperature without the addition of a catalyst with no increase in viscosity or a relatively low increase in viscosity. Also, the product can be transparent (not cloudy).

[0069] Definition and Usage of Terms Unless otherwise indicated by the context of this specification, all amounts, ratios, and percentages herein are by weight, the articles "a," "an," and "the" each refer to one or more, and the singular forms include the plural forms. The "Summary of the Invention" and "Abstract" are incorporated herein by reference. The terms "comprising" or "comprise" are used herein in their broadest sense and mean the concepts of "including," "include," "consisting essentially of," and "consisting of," and encompass it. The use of "for example," "e.g.," "such as," and "including" for listing examples is not limited to only the listed examples. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples.

[0070] "Yield" means the molar amount of the carbamate-functional alkoxysilylalkylene silane compound produced / the molar amount of the carbamate-functional alkoxysilylalkylene silane compound possible based on the amount of the limiting reagent. "Selectivity" means the ratio of the linear isomer / branched-chain isomer of the carbamate-functional alkoxysilylalkylene silane compound (the isomers have the same molecular weight).

[0071] The abbreviations used herein have the definitions in Table 4.

[0072] [Table 3]

[0073] Test Method The GC test method used in this application was carried out as follows. Chromatograms were recorded using two methods. (1) The chromatography equipment consisted of a Hewlett Packard 5890 Series II GC equipped with a flame ionization detector and a Hewlett Packard 6890 Series Autoinjector. Separation was carried out using a 30 m HP-5 column at a helium flow rate of 78 mL / min and a column flow rate of 1.05 mL / min. The sample was prepared as 100 μL in 1 mL of dichloromethane. Using an injector temperature of 180 °C and a detector temperature of 300 °C, a 2 μL injection volume was used and data was collected for 36.33 minutes. The oven method consisted of holding an initial temperature of 40 °C for 1 minute, then increasing to 150 °C at 5 °C / min, then increasing to 275 °C at 15 °C / min, and finally holding the final temperature of 275 °C for 5 minutes.) (2). An Agilent Technologies 7896A GC system equipped with a 7693 autosampler and connected to a 5975C mass spectrometer. Column: Agilent DB-5MS (phenyl-arylene, 30 m × 250 μm × 0.25 μm). Inlet temperature: 250 °C. Oven program: 50 °C for 1 minute, 10 °C / min to 275 °C, 275 °C for 5 minutes. Total run time: 28.5 minutes. The mass spectrometer was operated in chemical ionization mode / cation mode using methane as the reagent gas. Mass range: 50 - 1000. Solvent delay: 3.5 minutes.

[0074] The NMR test method used in this application was carried out as follows. (Proton ( 1 H) and 13 C nuclear magnetic resonance (NMR) spectra were recorded on an Agilent 500-MR or Varian NMR spectrometer operating at 500 MHz. Carbon ( 13 C) and silicon ( 29 Si) NMR spectra were recorded on an Agilent 500 MHz DD2 system equipped with a 16 mm silicon-free AutoZ probe. Peak frequencies were recorded in ppm. 1The H sample was run using 100 μL of the sample in 1 mL of deuterated chloroform (CDCl3) or benzene (C6D6), while 29 the Si and 13 C samples were run using 2 mL of the sample in 3 mL of deuterated chloroform containing Cr(acac)3.) 1 The 1H NMR spectra were referenced to the residual protons in the deuterated solvent as an internal standard. 13 The 13C NMR spectra were referenced to the deuterated solvent as an internal standard.

Claims

1. A carbamate-functional alkoxysilalkylene silane compound containing the following formula, 【Chemical 1】 wherein, Each R １ is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, provided that two cases of R １ may be bonded together to form a cyclic secondary amine moiety, Each R ２ is independently selected from the group consisting of an alkyl group and an aryl group, D is an alkylene group, Each R ４ is a carbamate-functional alkoxysilalkylene silane compound that is an alkyl group having 1 to 6 carbon atoms selected independently.

2. Each R １ is the compound according to claim 1, selected from the group consisting of hydrogen, methyl, and ethyl.

3. Each R ２ is methyl, the compound according to claim 1 or 2.

4. each D is, 【Chemical 2】 The compound according to any one of claims 1 to 3, selected from the group consisting of.

5. Each R ４ is methyl, and the compound according to any one of claims 1 to 4.

6. A method for preparing a carbamate-functional alkoxysilalkylene silane compound according to any one of claims 1 to 5, wherein the method comprises: 1) Under the conditions for carrying out the reaction, C) A carbamate salt, and D) Compound of the formula ClSiR ２ ２ H (wherein R ２ is as described above), and combining starting materials containing hydridochlorosilane thereby, E) formula R １ ２ NC(=O)O - SiR ２ ２ H (wherein R １ and R ２ are as described above) to form a reaction product containing a carbamate-functional hydridosilane. 2) Under the conditions for carrying out the hydrosilylation reaction, E) A carbamate-functional hydridosilane, F) Formula R ３ Si(OR ４ ) ３ (wherein R ３ is an alkenyl group and R ４ is as described above) alkenyl-functional alkoxysilane, G) A hydrosilylation reaction catalyst, Optionally H) Combining starting materials containing a solvent, thereby, I) Forming a hydrosilylation reaction product containing a carbamate-functional alkoxysilalkylene silane compound, and J) By-products.

7. Each R １ The method according to claim 6, wherein R is a methyl group or an ethyl group.

8. A method for preparing a carbamate-functional alkoxysilalkylene silane compound according to any one of claims 1 to 5, wherein the method comprises: 1) Under the conditions for carrying out the hydrosilylation reaction, F) Formula R ３ Si(OR ４ ) ３ (wherein, R ３ is an alkenyl group and R ４ is as described above) alkenyl-functional alkoxysilane, D) hydridochlorosilane of the formula ClSiR ２ ２ H (wherein R ２ is as described above), G) A hydrosilylation reaction catalyst, and Optionally H) Combining starting materials containing a solvent, thereby, E') type ClSiR ２ ２ -D-Si(OR ４ ) ３ (wherein, R ２ , D and R ４ are as described above) to form a hydrosilylation reaction product containing chlorodialkyl((trialkoxysilyl)alkylene)silane 2) Under the conditions for carrying out the reaction, E') Chlorodialkyl((trialkoxysilyl)alkylene)silane, C) A carbamate salt, and Optionally H) Combining starting materials containing a solvent, thereby, I) Forming a reaction product containing a carbamate-functional alkoxysilalkylene silane compound, and J') By-products.

9. Each R １ is a hydrogen atom, the method according to claim 8.

10. A method for preparing a polyalkoxy-functional polyorganosiloxane, wherein the method comprises: i) Implementing the method according to any one of claims 6 to 9, thereby forming I) the carbamate-functional alkoxysilalkylene silane compound, and ii) Under the conditions for carrying out the capping reaction, I) Combining a carbamate-functional alkoxysilalkylene silane compound, and II) Starting materials containing a polyorganosiloxane having a silanol moiety.

11. A method for preparing a polyalkoxy-functional polyorganosiloxane, wherein the method comprises: 1) Under the conditions for carrying out the capping reaction, I) A carbamate-functional alkoxysilalkylene silane compound according to any one of claims 1 to 5, and II) A method comprising combining starting materials comprising a polyorganosiloxane having a silanol moiety. **Claim 12** II) The polyorganosiloxane has the formula [Chemical Formula 3] is a bis-hydroxyl-terminated polydiorganosiloxane, wherein each R ５ is independently selected from the group consisting of an alkyl group, an alkenyl group, and an aryl group, and the subscript x represents the degree of polymerization and has an average value of from 1 to 2,000, the method according to claim 10 or 11. **Claim 13** The method according to claim 12, wherein the bis-hydroxyl-terminated polydiorganosiloxane is bis-hydroxyl-terminated polydimethylsiloxane. **Claim 14** A polyalkoxy-functional polyorganosiloxane prepared by the method according to claim 12, wherein the polyalkoxy-functional polyorganosiloxane has the following formula 【Chemical Formula 4】 (wherein the subscripted letters x and R ５ , R ２ , D, and R ４ are as described above) and a polyalkoxy-functional polyorganosiloxane. **Claim 15** Use of the polyalkoxy-functional polyorganosiloxane according to claim 14 in a condensation reaction-curable polyorganosiloxane composition.

Images