Branched organosilanol compounds and methods for their preparation and use

Abstract

Branched organosilanol compounds and methods for their preparation are provided. The branched organosilanol compounds can be used as raw materials in methods for preparing functionalized polymers.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 017689, filed April 30, 2020. U.S. Provisional Patent Application No. 63 / 017689 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention relates generally to organosilicon compounds. More specifically, the present invention relates to a method for preparing branched organosilanol compounds and the branched organosilanol compounds prepared by the method. Furthermore, the present invention relates to methods of using the branched organosilanol compounds. More specifically, the present invention relates to methods for preparing functionalized polymers, such as functionalized polyorganosiloxanes and / or silicone-organic hybrid copolymers, using branched organosilanols as raw materials. [Background technology]

[0003] Organosilicon compounds are known in the art and are utilized in a wide variety of end uses and environments.For example, polyorganosiloxanes are used in many industrial, home care, and personal care formulations.The use of hybrid materials with both silicone and organic functionality in such formulations is increasing, and as a result, such hybrid materials can exhibit a combination of benefits that have previously been associated only with silicone materials or organic materials.However, many methods for preparing hybrid materials require functional organosilicon compounds, which are often difficult to synthesize and / or use.In particular, traditional methods for preparing specific functional organosilicon compounds are often incompatible with many silicone materials (for example, through promoting silicone rearrangement, non-selective reactions, decomposition, hydrolysis of functional groups, etc.), resulting in reduced yield and purity, limiting the general applicability of such methods. Summary of the Invention

[0004] A branched organosilanol compound is provided. The branched organosilanol compound comprises

[0005] [ka] and (IV) a formula selected from the group consisting of a combination of any two or more of (I), (II), and (III), wherein each R, each R', and each R" is an independently selected monovalent hydrocarbyl group, each R'" is independently selected from the group consisting of R and OR", and each D is an independently selected divalent hydrocarbyl group.

[0006] Also provided is a method for preparing the branched organosilanol compounds described above, the method comprising: (A) The initial organosilicon compound and (B) water are reacted with (C) (C-1) [(CH 12 (C-1) IrX]2, wherein each X is an independently selected halogen atom, and (C-2) in the presence of a catalyst selected from the group consisting of Pd / C, thereby preparing an organosilanol compound; The initial organosilicon compound (A) is

[0007] [ka] and (A-4) having a formula selected from the group consisting of a combination of two or more of (A-1), (A-2), and (A-3), wherein R, R', R'', and R''' are defined above. [Brief explanation of the drawings]

[0008] [Figure 1] Gas chromatography of PrT EHM converter and PrT EHM silanol. [Figure 2] 1H NMR spectrum of PrT EHM silanol. [Figure 3] 29Si NMR spectrum of PrT EHM silanol. [Figure 4] FIG. 10 is a comparison of PrT EHM converters and PrT EHM silanols in 1H NMR. [Figure 5] FIG. 29Si NMR comparison of PrT EHM converters and PrT EHM silanols. [Figure 6] 1H NMR spectrum of PrT EHM silanol. [Figure 7] 29Si NMR spectrum of PrT EHM silanol. [Figure 8] FIG. 10 is a comparison of PrT EHM converters and PrT EHM silanols in 1H NMR. [Figure 9] FIG. 29Si NMR comparison of PrT EHM converters and PrT EHM silanols. [Figure 10] FIG. 11 is a gas chromatography diagram of the reaction products of PrT EHM converter and water in the presence of [Ru(p-cymene)Cl]. DETAILED DESCRIPTION OF THE INVENTION

[0009] The method for preparing branched organosilanol compounds comprises reacting (A) an initial organosilicon compound with (B) water in the presence of (C) a catalyst. Catalyst (C) is (C1) [(CH 12 )IrX]2, where each X is independently selected from the group consisting of Cl, Br, and I, and (C2)Pd / C.

[0010] Initial organosilicon compounds (A) The initial organosilicon compound (A) is

[0011] [ka] and (A-4) a combination of two or more of (A-1), (A-2), and (A-3), wherein each R, each R', and each R" is an independently selected monovalent hydrocarbyl group, each R"' is independently selected from the group consisting of R and OR", and each D is an independently selected divalent hydrocarbyl group. Examples of suitable monovalent hydrocarbyl groups for R, R', and R" include alkyl, alkenyl, and aryl groups. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl. Alternatively, each R may be an alkyl group of 1 to 18 carbon atoms or an aryl group of 6 to 18 carbon atoms. Alternatively, each R' may be an alkyl group of 1 to 18 carbon atoms. Alternatively, each R" may be an alkyl group of 1 to 6 carbon atoms. Alternatively, each R may be an alkyl group such as methyl, ethyl, or propyl, or may be methyl. Alternatively, each R' may be methyl, ethyl, or propyl, or may be propyl. Alternatively, each R" may be methyl or ethyl, or may be methyl. Alternatively, at least two R'" per molecule may be OR", or each R'" may be OR". Alternatively, each R'" may be methoxy or ethoxy.

[0012] Suitable divalent hydrocarbon groups for D include alkylene groups such as propylene, butylene, or hexylene, such as ethylene (-CH2-CH2-), -CH2-CH2-CH2-, or -CH(CH3)CH2-), arylene groups such as phenylene, or

[0013] [ka] Alternatively, D may be an alkylene group of 2 to 6 carbon atoms, such as ethylene or propylene.

[0014] Alternatively, the initial organosilicon compound (A-1) can be of the formula:

[0015] [ka] and may be abbreviated as PrT EHM Converter.

[0016] Alternatively, the initial organosilicon compound (A-2) is a compound of the formula

[0017] [ka] may have

[0018] Alternatively, the initial organosilicon compound (A-3) is a compound of the formula

[0019] [ka] may have

[0020] The initial organosilicon compound (A) can be utilized in any form, for example, neat (i.e., without a carrier vehicle such as a solvent and / or diluent) or can be disposed in a carrier vehicle such as a solvent or diluent. The carrier vehicle, if present, can comprise an organic solvent (e.g., an aromatic hydrocarbon such as benzene, toluene, and / or xylene; an aliphatic hydrocarbon such as heptane, hexane, and / or octane; a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, and / or chloroform; an ether such as diethyl ether and / or tetrahydrofuran), a silicone fluid, or a combination thereof. Alternatively, the method can be carried out in the presence of a carrier vehicle comprising a polar component such as an ether, acetonitrile, dimethylformamide, dimethyl sulfoxide, or a combination thereof. Alternatively, the carrier vehicle can comprise a halogenated hydrocarbon such as those described above. In general, the carrier vehicle and / or the halogenated hydrocarbon in particular can be purified and / or treated to reduce or remove any hydrochloric acid (HCl) derived therefrom. It is understood that the initial organosilicon compound (A) can be combined with the support vehicle before, during, or after combining the water (B) and catalyst (C).

[0021] Alternatively, the above-described method for making branched organosilanol compounds may be carried out in the absence of a carrier vehicle reactive with the initial organosilicon compound (A) and / or catalyst (C). For example, the method may include stripping a mixture of the initial organosilicon compound (A) with volatile materials and / or solvents (e.g., water and / or reactive solvents). Techniques for stripping the initial organosilicon compound (A) are known in the art and may include heating, drying, application of reduced pressure / vacuum, azeotroping with solvents, utilizing molecular sieves, and combinations thereof.

[0022] The initial organosilicon compound (A) can be utilized in any amount selected by one skilled in the art, depending on various factors, such as the particular catalyst (C) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of initial organosilicon compound (A) converted and / or organosilanol compound prepared). The initial organosilicon compound (A) may be synthesized using known methods, such as those disclosed in U.S. Pat. No. 6,265,518 and European Patent No. 1013653(A2).

[0023] Water (B) Water (B) is generally not limited, and can be neat (i.e., free of carrier vehicles / solvents) and / or highly purified (i.e., free of or substantially free of mineral matter and / or other impurities). For example, water (B) may or may not be treated prior to reaction with the initial organosilicon compound (A). Examples of treatments that can be used to purify water include distillation, filtration, deionization, and combinations of two or more thereof; thus, water (B) may be deionized, distilled, and / or filtered. Alternatively, water (B) may be untreated (e.g., tap water, i.e., water supplied from a water system, or well water, used without further purification). Alternatively, water (B) may be purified prior to reaction with the initial organosilicon compound (A). Alternatively, water (B) may be used as a mixture (e.g., solution or suspension) including a carrier vehicle / solvent, such as any of those listed above for the initial organosilicon compound (A).

[0024] Water (B) can be utilized in any amount selected by one skilled in the art, depending on various factors, such as the particular catalyst (C) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of initial organosilicon compound (A) converted and / or organosilanol compound prepared).

[0025] The relative amounts of initial organosilicon compound (A) and water (B) utilized may vary based, for example, on the particular initial organosilicon compound (A) selected, the particular catalyst (C) selected, and the reaction parameters employed. As will be appreciated by those skilled in the art, hydrolysis of the initial organosilicon compound (A) with water (B) occurs at a molar ratio (A):(B) of 1:1 to 1:1.5. However, an excess of one of these may be utilized to completely consume one of the initial organosilicon compound (A) or water (B), e.g., to simplify purification of the reaction product that is formed. For example, in certain embodiments, water (B) is utilized in relative excess to maximize the conversion of the initial organosilicon compound (A) to the organosilanol compound.

[0026] Catalyst (C) As mentioned above, the catalyst (C) is (C-1) [(CH 12 )IrX]2, where each X is independently selected from the group consisting of chlorine (Cl), bromine (Br), and iodine (I), and (C2)Pd / C. Alternatively, each X may be Cl. Alternatively, the catalyst (C2)Pd / C may be utilized.

[0027] Methods for preparing catalysts (C1) and (C2) are well known in the art, and the catalysts and / or compounds used to prepare them are commercially available from various suppliers. Thus, catalyst (C) may be prepared as part of the process or may be otherwise obtained (i.e., as a prepared compound). The catalyst (C) preparation may be formed before the reaction of the initial organosilicon compound (A) with water (B), or in situ (i.e., during the reaction of (A) with (B)).

[0028] Catalyst (C) may be utilized in any form, for example, neat (i.e., in the absence of a solvent, carrier vehicle, or diluent) or may be disposed in a carrier vehicle such as a solvent or dispersant (e.g., any of those listed above for the initial organosilicon compound (A)). Alternatively, catalyst (C) may be utilized in a form free of carrier vehicle / volatile materials that react with water and / or the initial organosilicon compound (A) and / or catalyst (C) itself (i.e., until combined with the initial organosilicon compound (A) and / or water (B)). For example, the method may include stripping volatile materials and / or solvents (e.g., water and / or organic solvents) from catalyst (C). Techniques for stripping catalyst (C) are known in the art and may include heating, drying, application of reduced pressure / vacuum, azeotroping with a solvent, utilizing an adsorbent such as a molecular sieve, and combinations thereof.

[0029] The catalyst (C) can be utilized in any amount selected by those skilled in the art, depending on various factors, such as the specific catalyst (C) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of the initial organosilicon compound (A) and water (B)). The molar ratio of catalyst (C) to the initial organosilicon compound (A) and / or water (B) utilized in the reaction can affect the rate and / or amount of hydrolysis in preparing the organosilanol compound. Thus, the amount of catalyst (C) relative to (A) and / or (B), as well as the molar ratio therebetween, can vary. Typically, these relative amounts and molar ratios are selected to maximize the hydrolysis of the initial organosilicon compound (A) to the organosilanol compound while minimizing the amount of catalyst (C) used (e.g., to improve the economic efficiency of the reaction and / or to improve the ease of purification of the reaction product formed).

[0030] Alternatively, catalyst (C) may be utilized in the reaction in an amount of 0.001 to 10 mol %, based on the total amount of initial organosilicon compound (A) utilized. For example, catalyst (C) may be used in an amount of 0.005 to 10, alternatively 0.005 to 5, alternatively 0.01 to 5 mol %, based on the total amount of initial organosilicon compound (A) utilized.

[0031] The reaction of the initial organosilicon compound (A) with water (B) to prepare the organosilanol compound is carried out in a vessel or reactor. As described below, when the reaction is carried out at elevated or reduced temperatures, the vessel or reactor may be heated or cooled in any suitable manner, for example, via a jacket, mantle, exchanger, bath, and / or coil.

[0032] Ingredients (A), (B), and (C), and the optional carrier vehicle, may be provided to a vessel together or separately, or may be disposed within the vessel in any order of addition and in any combination. For example, ingredients including (B) and (C) may be added to a vessel containing ingredients including (A) and the optional carrier vehicle. In such embodiments, ingredients including (B) and (C) may be first combined prior to addition, or may be added sequentially to the vessel (e.g., (C) followed by (B)). In general, references herein to a "reaction mixture" generally refer to a mixture including ingredients (A), (B), and (C) (e.g., as obtained by combining ingredients as described above). Of course, if utilized, a carrier vehicle may also be included in the reaction mixture.

[0033] The method may further include stirring the reaction mixture. Stirring may further mix and contact the raw materials (A), (B), and (C), for example, when combined in a reaction mixture. Such contact may be performed independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or alternatively), and other conditions may be used. Other conditions may be adapted to promote contact between the initial organosilicon compound (A) and water (B), and thus reaction (i.e., hydrolysis), to form the organosilanol compound. Other conditions may be effective to increase the reaction yield or to minimize the amount of certain reaction by-products included in the reaction product along with the organosilanol compound.

[0034] Alternatively, the reaction of the initial organosilicon compound (A) with water (B) can be carried out in the presence of a carrier vehicle or solvent, such as one or more of those described above. For example, a portion of the carrier vehicle or solvent can be added to or otherwise combined with the initial organosilicon compound (A), water (B), and / or catalyst (C) (i.e., if present), individually, together with the mixture of raw materials (A), (B), and / or (C), or with the reaction mixture as a whole. The total amount of carrier vehicle / solvent present in the reaction mixture will be selected by one skilled in the art based, for example, on the particular initial organosilicon compound (A) selected, the particular catalyst (C) selected, and the reaction parameters employed.

[0035] The reaction may be carried out at a low temperature. The low temperature is selected and controlled depending on the specific organosilicon compound (A), the specific catalyst (C), the specific organosilanol compound being prepared, and combinations thereof. Therefore, the low temperature can be easily selected by one skilled in the art in light of the selected reaction conditions and parameters and the description herein. The low temperature may be from -78°C to below ambient temperature, for example, from -30°C to 25°C, alternatively from -15°C to 25°C, alternatively from -10°C to 25°C, alternatively from -10°C to 20°C, or alternatively from -5°C to 20°C. Alternatively, the reaction may be carried out at a temperature of about 0°C ± 5°C (e.g., by using ice and / or a circulator or chiller using a 0°C set point). Alternatively, the reaction may be carried out at RT.

[0036] It should be understood that the reaction temperature may also vary from the ranges stated above. Similarly, it should be understood that reaction parameters may be modified during the reaction of the initial organosilicon compound (A) with water (B). For example, temperature, pressure, and other parameters may be independently selected or modified during the reaction. Any of these parameters may independently be ambient parameters (e.g., RT and / or atmospheric pressure) and / or non-ambient parameters (e.g., low or high temperature and / or reduced or elevated pressure). Any parameter may also be dynamically modified, i.e., changed in real time during the process, or static (e.g., during the duration of the reaction or any portion thereof).

[0037] The time for which the reaction of the initial organosilicon (A) with water (B) to prepare the organosilanol compound is carried out is a function of various factors, including the scale, reaction parameters and conditions, and the selection of specific raw materials. The time for which the reaction is carried out may be from 0 to 48 hours, for example, from 1 minute to 48 hours. On a relatively large scale (e.g., >1, or >5, or >10, or >50, or >100 kg), the reaction may be carried out for a time period of 1 to 48, or 2 to 36, or 4 to 24, or 6, 12, 18, 24, 36, or 48 hours, as readily determined by one skilled in the art (e.g., by monitoring the conversion of the initial organosilicon compound (A) and / or the formation of the organosilanol compound, such as via chromatography and / or spectroscopy). On a relatively small scale (e.g., gram scale, or <10, or <5, or <1 kg), the reaction may be carried out for a time of from 1 minute to 4 hours, such as from 1 minute to 1 hour, 5 to 30 minutes, or 10, 15, or 20 minutes.

[0038] The initial organosilicon compound (A) is reacted with water (B) to form a reaction product containing a branched organosilanol compound. During the course of the reaction, the amount of organosilanol compound increases and the amounts of (A) and (B) decrease in the reaction mixture containing the initial organosilicon compound (A), water (B), catalyst (C), and carrier vehicle (if present). When the reaction is complete (e.g., one of the initial organosilicon compound (A) or water (B) is consumed, or no additional organosilanol compound is prepared), the reaction mixture can be referred to as a reaction product containing an organosilanol compound. Thus, the reaction product typically includes any remaining amounts of raw materials (A), (B), and (C), and solvent (if present), as well as their decomposition and / or reaction products (e.g., materials not previously removed by distillation, stripping, etc.).

[0039] The above-described methods may further include recovering (e.g., isolating and / or purifying) the organosilanol compound from the reaction product. As used herein, recovering the organosilanol compound is typically defined as increasing the relative concentration of the organosilanol compound (e.g., in the reaction product or a purified version thereof) compared to other compounds combined with it. Thus, as understood in the art, recovery may include removing other compounds from such a combination (i.e., reducing the amount of impurities combined with the organosilanol compound in the reaction product), and / or removing the organosilanol compound itself from the combination. Any suitable technique and / or protocol for isolation may be utilized. Examples of suitable isolation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, and combinations of two or more thereof. As will be understood by those skilled in the art, any of these techniques may be used in combination (e.g., sequentially) with any other technique to recover the organosilanol compound.

[0040] Alternatively, isolating the organosilanol compound may include distilling and / or stripping volatile materials from the reaction product. When a support vehicle is utilized, volatile materials may be distilled and / or stripped from the reaction mixture containing the organosilanol compound. Isolating the organosilanol compound may include filtering the reaction product to remove residual amounts of catalyst (C) and / or solids formed therefrom. In either case (e.g., after removing volatile materials and / or solids via stripping / distillation and / or filtration), the reaction product may be referred to as recovered organosilanol compound.

[0041] The method may further include purifying the organosilanol compound. Any suitable technique for purification may be utilized. Purification of the organosilanol compound may involve distillation to either remove the organosilanol compound (e.g., as a distillate) or strip other compounds / components therefrom (i.e., leaving the organosilanol compound in the pot as a high-boiling component of the reaction mixture or purified reaction mixture). As will be understood by those skilled in the art, distillation of the reaction product or purified reaction product to purify and / or isolate the organosilanol compound may be carried out at elevated temperatures and reduced pressures. The elevated temperatures and reduced pressures are independently selected and readily determined by those skilled in the art depending on various factors, such as the specific raw materials used, the specific organosilanol compound being prepared, and other isolation / purification techniques utilized. Alternatively, purifying the organosilanol compound may be defined as purifying the recovered organosilanol compound (e.g., purification is carried out subsequent to isolation of the organosilanol compound).

[0042] The above-described method produces a branched organosilanol compound. The branched organosilanol compound is

[0043] [ka] and (IV) a formula selected from the group consisting of a combination of any two or more of (I), (II), and (III), wherein R, R', R'', R''', and D are defined above.

[0044] Alternatively, the branched organosilanol compound may have the formula (I): Alternatively, the branched organosilanol compound may have the formula (I-1):

[0045] [ka] [wherein Me represents methyl and Pr represents propyl], and the abbreviation thereof may be PrT EHM-OH (or PrT EHM silanol).

[0046] Alternatively, the branched organosilanol compound may comprise a combination of formula (II) and formula (III). The compound of formula (II) is represented by (II-1):

[0047] [ka] The compound of formula (III) may be (III-1)

[0048] [ka] where Me represents methyl.

[0049] How to use The above-mentioned organic silanol compound can be used to functionalize polymer.For example, in the method for preparing silicone hybrid copolymer, the modification method can include using the above-mentioned organic silanol compound to functionalize organic compound, and then reacting the functionalized organic polymer with polyorganosiloxane, for example, by condensation reaction.Alternatively, the above-mentioned organic silanol compound can be used to functionalize polyorganosiloxane, and then reacting the functionalized silicone compound with organic polymer, for example, by condensation reaction.

[0050] Alternatively, the above-described organosilanol compounds may be used to functionalize polyorganosiloxanes, such as polyorganosiloxanes having silicon-bonded hydrogen atoms or silicon-bonded alkoxy groups. In the method for preparing a functionalized polymer, the modification method may include reacting the above-described organosilanol compound with a raw material selected from the group consisting of polyorganosiloxanes having groups capable of reacting with the silanol moieties of the organosilanol compound and / or one or more raw materials for preparing silicone-organic hybrid copolymers, wherein the one or more raw materials have groups capable of reacting with the silanol moieties of the organosilanol compound. [Example]

[0051] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the claims.

[0052] In Example 1, PrT EHM-OH was prepared from PrT EHM converter using [Ir(COD)Cl] catalyst as follows: A three-necked round-bottom (RB) flask was charged with PrT EHM converter (10 g) and a 25 mM solution of [Ir(COD)Cl] in toluene (0.57 mL). The system was purged with N and heated to 40°C. Water (0.4 g) was added dropwise to the reaction mixture over 20 minutes with stirring. After the addition, the reaction mixture was stirred at 40°C for 30 minutes and then stripped under vacuum. The residue was analyzed by GC, and the results are shown in Figure 1. The residue also contained: 29 Si NMR and 1 The results are reported in Figures 2 to 5.

[0053] In Example 2, PrT EHM-OH was prepared from PrT EHM converter using a Pd / C catalyst as follows. Tetrahydrofuran (THF) (13 mL), PrT EHM converter (11.86 g, 20 mmol), and Pd / C (5 wt %, 0.1 mol %, 42 mg, powdered form) were added to a 50 mL three-neck 14 / 20 flask. The flask was stirred under nitrogen. Water (0.47 mL, 26 mmol) was then added via syringe over 5 minutes. Bubbling was observed. GCMS was performed at multiple time points after the addition of water. After 161 minutes, the reaction was worked up by filtration through a pad of Celite, removal of the solvent, and drying under high vacuum. The results are shown in Figures 6-9.

[0054] In Example 3, an attempt was made to prepare PrT EHM-OH from PrT EHM converter using dichloro(p-cymene) ruthenium dimer catalyst as follows. A three-necked round-bottom flask was charged with PrT EHM converter (20 g) and a solution of [Ru(p-cymene)Cl] in THF (7.5 mM, 3.8 mL). The system was purged with N and heated to 70 °C. Water (0.79 g) was added dropwise to the reaction mixture while stirring. Compared to the reactions in Examples 1 and 2 described above, gas evolution was much slower. One hour after two-thirds of the water had been added, the reaction mixture was analyzed by GC. Instead of dehydrogenative coupling between Si-H and HO, hydrolysis of Si-OMe appeared to be the main reaction. The results are shown in Figure 10. [Industrial Applicability]

[0055] The examples and comparative examples demonstrate that novel branched organosilanol compounds can be prepared using the Ir- and Pd-catalyzed methods described herein.

[0056] Definitions and Use of Terms The Summary and Abstract are incorporated herein by reference. Table 1 shows the abbreviations used herein.

[0057] [Table 1]

[0058] NMR. Proton ( 1 H NMR spectra were recorded on an Agilent 400-MR NMR spectrometer (mi-MR-05) operating at 400 MHz. 29 Si) NMR spectra were recorded on an Agilent 500 MHz DD2 (mi-MR-06) system equipped with a 16 mm silicon-free AutoZ probe. Peak frequencies are reported in ppm. 100 μL of sample in 1 mL of deuterated chloroform (CDCl3) was used. 1Obtain the H sample by dissolving 2 mL of the sample in 3 mL of deuterated chloroform containing Cr(acac)3. 29 Si samples were obtained.

[0059] GC. The chromatography equipment was a Hewlett Packard 5890 Series II GC equipped with a flame ionization detector and a Hewlett Packard 6890 Series Autoinjector. Separation was performed using a 30 m HP-5 column with a helium flow rate of 78 mL / min and a column flow rate of 1.05 mL / min. Samples were prepared as 100 μL in 1 mL of dichloromethane. The injection temperature was 180 °C and the detector temperature was 300 °C, with a 2 μL injection volume and data collection time of 36.33 minutes. The oven method included an initial temperature of 40 °C held for 1 minute, followed by a ramp rate of 5 °C / min to 150 °C, a ramp rate of 15 °C / min to 275 °C, and a final temperature of 275 °C held for 5 minutes. Samples were prepared by diluting 100 μL of material into 1 mL of dichloromethane.

[0060] All amounts, ratios, and percentages are by weight unless otherwise indicated. The articles "a," "an," and "the" each refer to one or more, unless the context of the specification dictates otherwise. The disclosure of ranges includes the range itself and any subsumed within that range, as well as the endpoints. For example, disclosure of a range of 1 to 18 includes not only the range 1 to 18, but also 1, 2, 3, 4, 6, 12, and 18 individually, and any other number subsumed within that range. Furthermore, disclosure of a range of 1 to 18 includes subsets such as 1 to 10, 1 to 6, 1 to 4, 1 to 2, 6 to 18, 6 to 12, and 12 to 18, as well as any other subset subsumed within that range. Similarly, disclosure of a Markush group includes the group as a whole, as well as any individual elements and subgroups subsumed therein. For example, disclosure of the Markush groups Cl, Br, and I includes its members individual Br, the subgroups Cl and Br, and any other individual members and subgroups contained therein.

Claims

1. An organosilanol compound, 【Chemical 1】 wherein each R, each R', and each R" is an independently selected monovalent hydrocarbyl group; each R'" is independently selected from the group consisting of R and OR", and each D is an independently selected divalent hydrocarbyl group.

2. 2. The compound of claim 1, wherein each R is an alkyl group of 1 to 18 carbon atoms or an aryl group of 6 to 18 carbon atoms, each R' is an alkyl group of 1 to 18 carbon atoms, each R'' is an alkyl group of 1 to 6 carbon atoms, and at least two R''' per molecule are OR''.

3. 3. The compound of claim 1 or 2, wherein each R''' is OR''.

4. 4. The compound of any one of claims 1 to 3, wherein each R is selected from the group consisting of methyl and phenyl, each R' is selected from the group consisting of methyl, ethyl, and propyl, each R" is selected from the group consisting of methyl and ethyl, and each R'" is selected from the group consisting of methoxy and ethoxy.

5. The compound of any one of claims 1 to 4, wherein the compound has formula (I):

6. The compound has the formula (I-1): 【Chemistry 2】 6. The compound of claim 5, having the formula: wherein Me represents methyl and Pr represents propyl.

7. The compound of formula (II) 【Chemistry 3】 (II-1), and said compound of formula (III) is 【Chemistry 4】 (III-1), wherein Me represents methyl.

8. A method for preparing the organosilanol compound of any one of claims 1 to 7, said method comprising: (A) an initial organosilicon compound and (B) water are reacted with (C) (C-1) [(C ８ H １２ ) IrX] ２ wherein each X is independently selected from the group consisting of Cl, Br, and I; and (C-2) reacting in the presence of a catalyst selected from Pd / C, thereby preparing the organosilanol compound; The initial organosilicon compound (A) is 【Chemistry 5】 wherein D, R, R', R'', and R''' are defined as above.

9. (A-1) is a compound represented by the formula: 【Chemistry 6】 9. The method of claim 8, wherein Me represents methyl and Pr represents propyl.

10. (A-2) is a compound represented by the formula 【Chemistry 7】 9. The method of claim 8, wherein Me represents methyl.

11. (A-3) is a compound represented by the formula 【Chemistry 8】 9. The method of claim 8, wherein Me represents methyl.

12. 12. The method of any one of claims 8-11, wherein the initial organosilicon compound (A) is reacted with water (B) to form a reaction product comprising the organosilanol compound, the method further comprising separating the organosilanol compound from the reaction product.

13. Use of the organosilanol compounds according to any one of claims 1 to 7 for functionalizing polymers.

14. 10. A method for preparing a functionalized polymer, comprising reacting the organosilanol compound of any one of claims 1 to 7 with a raw material selected from the group consisting of one or more raw materials for preparing polyorganosiloxanes and / or silicone-organic hybrid copolymers having groups capable of reacting with the silanol moieties of the organosilanol compound, wherein the one or more raw materials have groups capable of reacting with the silanol moieties of the organosilanol compound.

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