Preparation of polyfunctional organosilicon compounds

Abstract

A method for preparing polyfunctional organosilicon compounds is provided. The method comprises reacting (A) an organosilanol compound containing functional moieties selected from alkoxysilyl and acryloxy moieties with (B) a hydridosilane compound having at least two hydrolyzable groups in the presence of (C) an acetate salt. Polyfunctional organosilicon compounds prepared by this method are also provided.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 046,591, filed on 30 June 2020, the contents of which are incorporated herein by reference.

[0002] The present invention generally relates to organosilicon compounds, and more specifically to methods for preparing polyfunctional organosilicon compounds, polyfunctional organosilicon compounds prepared using the same, and functionalized siloxanes prepared therefrom. [Background technology]

[0003] Organosilicon materials are well-known in the art and are used in countless end-uses and environments. For example, organopolysiloxanes are used in many industrial, home care, and personal care formulations. The use of hybrid materials possessing both silicone and organic functionalities in such formulations is increasing, and as a result, such hybrid materials can offer a combination of benefits previously associated only with silicone or organic materials. However, many methods for preparing hybrid materials require functional organosilicon compounds, which are often difficult to synthesize and / or utilize. Furthermore, many conventional organosilicon materials have limited functionality available in the preparation of hybrid materials. Specifically, conventional methods for preparing certain functional organosilicon compounds are often incompatible with many silicone materials (e.g., through enhanced silicone rearrangement, non-selective reactions, decomposition, hydrolysis of functional groups, etc.), resulting in reduced yield and purity, and limiting the overall applicability of such methods. [Overview of the project]

[0004] This disclosure provides a method for preparing a polyfunctional organosilicon compound. The method comprises reacting (A) an organosilanol compound and (B) a hydridosilane compound in the presence of (C) an acetate to prepare a polyfunctional organosilicon compound. The organosilanol compound (A) comprises a functional moiety selected from an alkoxysilyl moiety and an acrylooxy moiety, and the hydridosilane compound (B) comprises at least two hydrolyzable groups.

[0005] Polyfunctional organosilicon compounds prepared by this method are also provided. The polyfunctional organosilicon compounds have the following general formula: [ka] (In the formula, each Y independently comprises a functional moiety selected from an alkoxysilyl moiety and an acrylicoxy moiety, and each R is an independently selected hydrocarbyl group, and each R 5 (where is an independently selected hydrocarbyl group, and each subscript a is independently 0, 1, or 2, and subscript c is 2 or 3). [Modes for carrying out the invention]

[0006] Methods for preparing polyfunctional organosilicon compounds are provided herein. The prepared polyfunctional organosilicon compounds comprise two different types of functional groups, each containing at least one hydrosilylated group, and are therefore useful in the preparation of functionalized siloxane compounds, and in compositions and methods for preparing curable compositions (e.g., as capping agents, etc.) and various components thereof, such as those based on one or more silicones as starting materials, reagents, building blocks, functionalized compounds, etc.

[0007] This method involves reacting (A) an organosilanol compound with (B) a hydridosilane compound in the presence of (C) an acetate. This method prepares a polyfunctional organosilicon compound via a condensation-type addition reaction ("the reaction"), which will be understood from the description herein. In particular, the organosilanol compound (A), the hydridosilane compound (B), and the acetate (C), along with any additional components that may be used in this method, are described below in order and may be referred to herein collectively as "components" of this method (i.e., "component (A)", "component (B)", "component (C)", etc., respectively), or similarly as "starting materials", "components", and / or "reagents" (A), (B), and / or (C), etc.

[0008] As described above, component (A) is an organosilicon compound, i.e., an organosilicon compound having at least one silicon-bonded hydroxyl group (i.e., a Si-OH group, a silanol group, etc.). The organosilicon compound (A) also includes a functional moiety, which is selected from an alkoxysilyl moiety and an acrylooxy moiety, as will be described in more detail below.

[0009] Typically, organosilanol compounds (A) have the following general formula: [ka] (wherein Y is a functional moiety selected from an alkoxysilyl moiety and an acrylooxy moiety, each R is an independently selected hydrocarbyl group, and the subscript a is 0, 1, or 2). If the functional moiety Y is an alkoxysilyl moiety, component (A) may be further defined as an alkoxysilyl functional organosilano compound. Similarly, if the functional moiety Y is an acrylooxy moiety, component (A) may be further defined as an acrylooxy functional organosilano compound.

[0010] With respect to the general formula of component (A) above, each R is an independently selected hydrocarbyl group. Preferred hydrocarbyl groups may be substituted or unsubstituted. With respect to such hydrocarbyl groups, the term “substituted” refers to a hydrocarbon moiety in which one or more hydrogen atoms are replaced by atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, or bromine), or carbon atoms in the hydrocarbon chain are replaced by atoms other than carbon (i.e., R may contain one or more heteroatoms (oxygen, sulfur, nitrogen, etc.) in the carbon chain), or both. Thus, since R may contain or may be a hydrocarbon moiety having one or more substituents in and / or on its carbon chain / main chain (i.e., attached to and / or integral to its carbon chain / main chain), it will be understood that R may contain or may be an ether, ester, etc.

[0011] In general, suitable hydrocarbyl groups for R can be linear, branched, cyclic, or combinations thereof. Linear and branched hydrocarbyl groups can be saturated or unsaturated independently. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can be monocyclic or polycyclic independently. An example of a combination of linear and cyclic hydrocarbyl groups is the aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, variants, and combinations thereof. 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, for example, 6 to 18 carbon atoms. Suitable examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable examples of monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include alkyl halides, aryl groups, and combinations thereof. Examples of alkyl halides include the alkyl groups mentioned above in which one or more hydrogen atoms are substituted with halogen atoms such as F or Cl.Specific examples of alkyl halides include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, as well as their derivatives. Examples of aryl halides include the aryl groups mentioned above, in which one or more hydrogen atoms are substituted with halogen atoms such as F or Cl. Specific examples of aryl halides include chlorobenzyl and fluorobenzyl groups. Typically, each R is an independently selected substituted or unsubstituted hydrocarbyl group. For example, in some embodiments, each R is independently selected from unsubstituted hydrocarbyl groups, such as linear or unbranched unsubstituted hydrocarbyl groups. In some such embodiments, each R is independently selected from unsubstituted hydrocarbyl groups having 1 to 18 carbon atoms, for example, 1 to 12, or 1 to 10, or 1 to 6 carbon atoms.

[0012] Each R may be the same as or different from any other R in the organic silanol compound (A). In a particular embodiment, each R is the same. In other embodiments, at least one R is different from at least one other R in the organic silanol compound (A). In a particular embodiment, each R is independently selected from alkyl groups, such as a methyl group, an ethyl group, etc. In a particular embodiment, each R is methyl.

[0013] Furthermore, with respect to the general formula of component (A) above, the functional moiety Y is selected from an alkoxysilyl moiety and an acrylooxy moiety. In other words, the functional moiety Y includes at least one independently selected alkoxysilyl substituent or acrylooxy substituent. The alkoxysilyl substituent or acrylooxy substituent of the functional moiety Y may be directly (e.g., via a covalent bond) or indirectly (e.g., via a divalent linking group) bonded to the silicon atom shown in the general formula of the organosilanol compound (A) above (i.e., the siloxane backbone of the organosilanol compound (A)). In certain embodiments, the alkoxysilyl or acrylooxy substituent of the functional moiety Y is directly bonded to the siloxane backbone of the organosilanol compound (A) such that Y itself represents an alkoxysilyl or acrylooxy group, as shown below. In other embodiments, the alkoxysilyl or acrylooxy substituent of the functional moiety Y is indirectly bonded to the siloxane backbone of the organosilanol compound (A), for example, via a linking group.

[0014] For example, in some embodiments, the functional part Y is given by formula R 1 -D-(wherein, R 1 The compound comprises an alkoxysilyl group or an acrylooxy group, as will be described in more detail below, and D is a linking group. More specifically, in such embodiments, the linking group D is an independently selected divalent linking group, which may be linear or branched, and may be substituted or unsubstituted. Typically, the linking group D is selected from divalent substituted or unsubstituted hydrocarbon groups. For example, in some embodiments, the linking group D is of the formula -(CH2) m - (wherein the formula, the subscript m is 1 to 16, or 1 to 6) comprises a hydrocarbon moiety. In these or other embodiments, the linking group D may include a substituted hydrocarbon, i.e., a hydrocarbon group having a main chain having at least one heteroatom (e.g., O, N, S, etc.). For example, in some embodiments, the linking group D is a hydrocarbon having a main chain containing an ether moiety.

[0015] Generally, R 1is independently selected from an alkoxysilyl group and an acryloxy group. These groups are not particularly limited and are exemplified by the following general and specific examples. Thus, alternative alkoxysilyl groups and / or acryloxy groups can be readily envisioned by those skilled in the art in view of the description herein.

[0016] In certain embodiments, R 1 is an alkoxysilyl group such that the functional moiety Y is an alkoxysilyl moiety, and component (A) can be further defined as the alkoxysilyl-functional organic silanol compound (A) introduced above. In such embodiments, R 1 typically has the following formula:

Chemical formula

[0017] The alkoxysilyl group R 1 can be further defined as a mono-, di-, or trialkoxysilyl group, i.e., when the subscript b is 1, 2, or 3, respectively. Typically, the subscript b is 2 or 3 such that the alkoxysilyl group R 1 contains at least two alkoxy groups represented by the above partial formula R 2 O-. In such embodiments, each R 2 can be the same as or different from any other R 1 in the alkoxysilyl group R 2 .

[0018] R 2 , and when present, R 3 (i.e., when the subscript b is 1 or 2), examples of suitable hydrocarbyl groups generally include those described above for R. Typically, each R 2 and R3 The alkyl group R is independently selected from alkyl groups such as methyl and ethyl groups. In such cases, the alkoxysilyl group R 1 It can be defined as a trialkoxysilyl, dialkoxyalkylsilyl, or alkoxyldialkylsilyl group, i.e., subscript b is 3, 2, or 1, respectively.

[0019] In a particular embodiment, each R 2 is methyl or ethyl. In these or other embodiments, each R 3 is methyl or ethyl. In certain embodiments, the alkoxysilyl group R 1 Each R inside 2 and R 3 is methyl. For example, in a particular embodiment, R 1 The subscript b is 3, and each R is a trimethoxysilyl group (for example, (CH3O)3Si-), 2 is methyl. Similarly, in other embodiments, R 1 The subscript b is 3, and each R is a triethoxysilyl group (for example, (CH3CH2O)3Si-), and 2 is ethyl. In some embodiments, R 1 The subscript b is 2, and each R is a trimethoxysilyl group (for example, (CH3CH2O)3Si-). 2 is methyl, and R 2 It is methyl.

[0020] In a particular embodiment, R 1 In such embodiments, R is an acrylicoxy group such that the functional moiety Y is an acrylicoxy moiety, and component (A) can be further defined as the acrylicoxy-functional organosilanol compound (A) described above. 1 Typically, this is expressed by the following formula: [ka] (In the formula, R 4 R is an acrylic oxy group having an independently selected hydrocarbyl group or H.4 Examples of suitable hydrocarbyl groups include those described above for R. For example, R 4 This may include, or could be, substituted or unsubstituted hydrocarbyl groups having 1 to 4 carbon atoms.

[0021] In a particular embodiment, the acrylic oxy group R 1 R can be defined as an acrylate group, 4 In other embodiments, R 4 R is selected from substituted or unsubstituted hydrocarbyl groups such as any of those described above. In some such embodiments, the acrylic oxy group R 1 R can be defined as an alkyl acrylate group, 4 is an alkyl group. Examples of such alkyl groups include methyl, ethyl, propyl (n-propyl, isopropyl), and butyl (e.g., n-butyl, sec-butyl, iso-butyl, t-butyl) groups. In certain embodiments, the acrylic oxy group R 1 R can be defined as a methacrylate group, 4 It is methyl.

[0022] Regarding the general formula of component (A) above, the subscript a of the organic silanol compound (A) is 0, 1, or 2. For example, in a particular embodiment, the subscript a is 0, and the organic silanol compound (A) is given by the following formula: [ka] The formula has the following characteristics (wherein each R and Y is as described above). In some such embodiments, each R is methyl, such that the organosilanol compound (A) has the formula YSi(CH3)2OH (wherein Y is as described above).

[0023] In other embodiments, subscript a is 1, and the organosilanol compound (A) is of the following formula: [ka] The formula has the following characteristics (wherein each R and Y is as described above). In some such embodiments, each R is methyl, such that the organosilanol compound (A) has the formula YSi(CH3)2OSi(CH3)2OH (wherein Y is as described above).

[0024] In yet another embodiment, the subscript a is 2, and the organosilanol compound (A) is given by the following formula: [ka] The formula has the following characteristics (wherein each R and Y is as described above). In some such embodiments, each R is methyl, such that the organosilanol compound (A) has the formula YSi(CH3)2OSi(CH3)2OSi(CH3)2OH (wherein Y is as described above).

[0025] The organic silanol compound (A) may be in any form, for example, undiluted (i.e., without solvent, carrier vehicle, diluent, etc.), or supplied in a carrier vehicle such as a solvent or dispersant. If present, the carrier vehicle may include organic solvents (e.g., aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; etc.; ethers such as diethyl ether and tetrahydrofuran), silicone fluids, or combinations thereof. In certain embodiments, the organic silanol compound (A) is used in the absence of a carrier vehicle. In some such embodiments, the organic silanol compound (A) is used in the absence of water and carrier vehicle / volatile substances that react with the organic silanol compound (A) and / or hydridosilane compound (B). For example, in certain embodiments, the method may include stripping a volatile substance and / or solvent (e.g., an organic solvent, water, etc.) from the organic silanol compound (A). Techniques for stripping from the organic silanol compound (A) are known in the art and may include distillation, heating, application of reduced pressure / vacuum, azeotropic mixing with a solvent, use of molecular sieves, and combinations thereof.

[0026] The organosilanol compound (A) may be used in any amount selected by those skilled in the art, which may vary depending on, for example, a specific hydridosilane compound (B) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of components (A) and / or (B) to be reacted and / or the polyfunctional organosilicon compound prepared).

[0027] In certain embodiments, the method involves utilizing two or more organic silanol compounds (A), such as two, three, four, or more organic silanol compounds (A). In such embodiments, each organic silanol compound (A) is independently selected and may be the same as or different from any other organic silanol compound (A) in terms of, for example, the siloxane backbone, functional moiety Y, substituent R, etc.

[0028] For example, in a particular embodiment, the organic silanol compound (A) comprises a mixture of compounds, where the functional part Y is the same as the above formula R 1 The compounds have -D-, and these compounds are distinct from each other with respect to the divalent linking group D. In some such embodiments, each D is a linear or branched hydrocarbon group, and the organic silanol compound (A) is a compound having a linear or branched group ratio of 50:50, or 65:35, or >90:10, or >95:5 (linear:branched). In certain such embodiments, each linking group D is a linear hydrocarbon group in component (A) having the general formula of the organic silanol compound (A) above, in an amount of at least 70 mol%, or at least 75 mol%, or at least 80 mol%, or at least 85 mol%, or at least 90 mol%, or at least 95 mol% of the molecule utilized.

[0029] The organosilanol compound (A) may be provided, or otherwise obtained “as is,” i.e., ready for the reaction to prepare the polyfunctional organosilicon compound, or alternatively, prepared as part of the present method. For example, in some embodiments, the present method further includes preparing the organosilanol compound (A).

[0030] As those skilled in the art will understand, the condensation of the Si-OH group and the Si-Cl group may occur directly or indirectly by first hydrolysis of the Si-Cl group to the Si-OH group and then condensation of the two Si-OH groups. Thus, the preparation of the organosilanol compound (A) is given by the following formula: [ka] It should be understood that this can be carried out by hydrolysis of halogen-functional organosilicon compounds, such as chlorine-functional organosilicon compounds having (wherein R, Y, and subscript a are as described above with respect to organosilicon compound (A)). Therefore, although the silanol functional group (i.e., its Si-OH group) has been described herein with respect to organosilicon compound (A), it should also be understood that under certain conditions, the aforementioned chlorine-functional organosilicon compounds may react themselves with one or more hydrolysis reaction products of component (B), as shown below, which themselves contain one or more Si-OH groups. In such cases, organosilicon compound (A) itself does not become a silanol (i.e., a Si-OH functional group) in the method. Therefore, the term "organosilicanol" as used with respect to organosilicon compound (A) should be understood not to be limiting, but to include halogen-functional organosilicon compounds that are readily converted to the corresponding organosilicon compounds under hydrolysis conditions.

[0031] As described above, component (B) is a hydridosilane compound, i.e., a silicon compound having at least one silicon-bonded hydrogen atom (i.e., a Si-H group) per molecule. Hydroidosilane compound (B) also typically contains at least two hydrolyzable groups (i.e., two silicon-bonded groups that can be hydrolyzed, for example, during a condensation reaction).

[0032] Typically, hydridosilane compounds (B) have the following general formula: [ka] (In the formula, each Z is an independently selected hydrolyzable group, and each R 5 (where is an independently selected hydrocarbyl group, and the subscript c is 2 or 3).

[0033] In a particular embodiment, the subscript c is 2, and the hydridosilane compound (B) is given by the following formula: [ka] (In the formula, each Z and R 5 The compound has the following characteristics (as described herein). In other embodiments, the subscript c is 3, and the hydridosilane compound (B) is of the following formula: [ka] (wherein each Z is as described herein)

[0034] Each hydrolyzable group Z is independently selected and may be the same as or different from any other hydrolyzable group Z in the hydridosilane compound (B). In certain embodiments, each hydrolyzable group Z is the same. In other embodiments, at least one hydrolyzable group Z is different from at least one other hydrolyzable group Z in the hydridosilane compound (B). Suitable hydrolyzable groups for the hydridosilane compound (B) are not limited and may be any group that can promote the condensation between the silanol group of the organosilanol compound (A) and the hydridosilane compound (B).

[0035] In certain embodiments, each hydrolyzable group Z is independently selected from halogens (e.g., chlorine, bromine, etc.), alkoxy groups (e.g., methoxy, ethoxy, propoxy, butoxy, phenoxy, etc.), carboxyl groups (e.g., acetoxy), oxime groups (e.g., -ONC(CH2CH3)2), and aminooxy groups (e.g., -ON(CH2CH3)2). In certain embodiments, each hydrolyzable group Z is a halogen. In certain embodiments, each hydrolyzable group Z is chlorine.

[0036] In some embodiments, each hydrolyzable group Z is selected with particular consideration to a specific functional moiety Y utilized in the organosilanol compound (A). For example, in certain embodiments, compound (A) is the alkoxysilyl functional organosilanol compound (A) described above, and hydridosilane compound (B) does not contain an alkoxysilyl group (i.e., each hydrolyzable group Z is non-alkoxy, such as a halogen).

[0037] If present (i.e., as described above, the subscript c is 2), substituent R of hydridosilane compound (B) 5 is a hydrocarbyl group. Preferred hydrocarbyl groups may be substituted or unsubstituted, and are exemplified by the above hydrocarbyl groups with respect to substituent R of the above organosilanol compound (A). Typically, R 5 R is selected from alkyl groups such as methyl and ethyl groups. For example, in a particular embodiment, R 5 It is methyl. However, aryl, alkaryl, and other types of hydrocarbyl groups are also R 5 It can be used as such. In addition, R 5 As described above, the selected hydrocarbyl group may be substituted internally, terminally, and / or pendantly on the hydrocarbon chain.

[0038] In a particular embodiment, each hydrolyzable group Z is Cl, and R 5 If present, it is methyl. In such embodiments, the hydridosilane compound (B) is exemplified by dichloromethylsilane (i.e., subscript c is 2) and trichlorosilane (i.e., subscript c is 3).

[0039] The hydridosilane compound (B) may be used in any form, for example, undiluted (i.e., without solvent, carrier vehicle, diluent, etc.), or supplied in a carrier vehicle such as a solvent or dispersant. The carrier vehicle, if present, may include organic solvents (e.g., aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; etc.; ethers such as diethyl ether and tetrahydrofuran), silicone fluids, or combinations thereof.

[0040] In some embodiments, the hydridosilane compound (B) is utilized in the absence of water and a carrier vehicle / volatile substance that react with the organosilanol compound (A) and / or the hydridosilane compound (B). For example, in certain embodiments, the method may include stripping the volatile substance and / or solvent (e.g., water, a reactive solvent, etc.) from the hydridosilane compound (B). Techniques for stripping from the hydridosilane compound (B) are known in the art and may include heating, drying, application of reduced pressure / vacuum, azeotropic mixing with a solvent, use of molecular sieves, and combinations thereof.

[0041] In certain embodiments, the method involves utilizing two or more hydridosilane compounds (B), such as two, three, or four or more hydridosilane compounds (B). In such embodiments, each hydridosilane compound (B) is independently selected and may be the same as or different from any other hydridosilane compound (B) with respect to, for example, hydrolyzable groups Z, the number of hydrolyzable groups Z (i.e., as represented by the subscript c), etc.

[0042] The hydridosilane compound (B) may be used in any amount selected by those skilled in the art, which may vary depending on, for example, a specific organosilanol compound (A) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of component (A) to be converted and / or the polyfunctional organosilicon compound prepared).

[0043] The relative amounts of the organic silanol compound (A) and hydridosilane compound (B) used may vary depending on, for example, the specific organic silanol compound (A) selected, the specific hydridosilane compound (B) selected, and the reaction parameters employed. As will be understood by those skilled in the art, the theoretical maximum molar ratio of the reaction of components (A) and (B) (i.e., the stoichiometric ratio of the complete reaction) depends on the subscript c, i.e., the number of hydrolyzable groups Z. For example, if the subscript c is 2 (i.e., the hydridosilane compound (B) has 2 hydrolyzable groups Z), components (A) and (B) may react in a molar ratio of 2:1 (A):(B). Similarly, if the subscript c is 3 (i.e., the hydridosilane compound (B) has 3 hydrolyzable groups Z), components (A) and (B) may react in a molar ratio of 3:1 (A):(B).

[0044] Regardless of the specific theoretical maximum molar ratio of the reaction, typically, one of the components is utilized in excess to completely consume either component (A) or (B), for example, to simplify the purification of the reaction product formed. Thus, in certain embodiments, the organosilanol compound (A) and the hydridosilane compound (B) react in a molar ratio of (A):(B) of 10:1 to 1:10, e.g., 8:1 to 1:8, or 6:1 to 1:6, or 4:1 to 1:4. In certain embodiments, the organosilanol compound (A) is utilized in relative excess (i.e., stoichiometric excess, e.g., when the molar equivalent ratio of (A) to (B) is greater than subscript c) to maximize the conversion rate of component (B) to the polyfunctional organosilicon compound. In such embodiments, the organic silanol compound (A) and the hydridosilane compound (B) react in a molar ratio of 6:1 to greater than 2:1, for example, 5:1 to greater than 2:1, or 4:1 to greater than 2:1, or 3:1 to greater than 2:1 (A):(B). In certain such embodiments, the organic silanol compound (A) and the hydridosilane compound (B) react in a molar ratio of 3.5:1 to greater than 3.01:1 (A):(B) (for example, when the subscript c is 3 such that the hydridosilane compound (B) has 3 hydrolyzable groups Z), or when the molar ratio of 2.5:1 to 2.01:1 (A):(B) (for example, when the subscript c is 2 such that the hydridosilane compound (B) has 2 hydrolyzable groups Z).

[0045] In other embodiments, the hydridosilane compound (B) is used in relative excess (i.e., stoichiometric excess, e.g., when the molar equivalent ratio of (A) to (B) is less than subscript c) to maximize the conversion rate of component (A) to the polyfunctional organosilicon compound. In such embodiments, the organosilanol compound (A) and the hydridosilane compound (B) react in a stoichiometric ratio of (A):(B) of 1:1 or less. For example, in some embodiments, the organosilanol compound (A) and the hydridosilane compound (B) react in a molar ratio of (A):(B) of 3:1 or less (e.g., when subscript c is 3 such that the hydridosilane compound (B) has 3 hydrolyzable groups Z), or in a molar ratio of (A):(B) of 2:1 or less (e.g., when subscript c is 2 such that the hydridosilane compound (B) has 2 hydrolyzable groups Z).

[0046] It will be understood that ratios outside these ranges may also be used. For example, in a particular embodiment, if, for example, an organic silanol compound (A) is used as a support (i.e., solvent, diluent, etc.) during the reaction, the organic silanol compound (A) may be used in a large excess (e.g., 10 or more, or 15 or more, or 20 or more, the molar amount of the hydridosilane compound (B)). In another embodiment, if, for example, a hydridosilane compound (B) is used as a support (i.e., solvent, diluent, etc.) during the reaction, the hydridosilane compound (B) may be used in excess of component (A) or in a large excess (e.g., 10 or more, 15 or more, or 20 or more, the molar amount of the organic silanol compound (A)).

[0047] As described above, component (C) is a complex containing an acetate, i.e., an acetate anion. The acetate (C) is not particularly limited in any other way.

[0048] As will be understood by those skilled in the art, acetates generally contain a counterion (e.g., a cation, or a combination of cations), which can be selected from organic cations (e.g., quaternary ammonium cations such as imidazolium, pyridinium, and pyrrolidinium cations, sulfonium cations, phosphonium cations, etc.), inorganic cations (e.g., metal cations), and combinations thereof. Specific examples of suitable cations include alkali metal cations (e.g., lithium (Li), sodium (Na), potassium (K), etc.) and alkaline earth metal cations (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), barium (Ba), etc.).

[0049] In certain embodiments, the acetate (C) is a salt of the general formula [R 6 C(O)O] - [M] + (In the formula, R 6 The complex includes a substituted or unsubstituted methyl group, where M is an alkali metal.

[0050] Subexpression [R 6 C(O)O] - The portion indicated by may be defined as acetate (i.e., acetate ion, acetate anion, etc.), or otherwise called acetate, and it will be understood that this term generally encompasses the conjugate base of acetate. However, substituent R in this specification 6 Considering the description, the acetate of acetate (C) may be a higher-order carboxylate anion (e.g., propionate, butyrate, etc.) or another acetate derivative (e.g., fluoroacetate, dichloroacetate, etc.), and these together constitute the substituent R in the above general formula. 6 It should be understood that this falls within the range of substituted or unsubstituted methyl groups represented by [the specified symbol].

[0051] For example, in a particular embodiment, the salt complex of component (C) is given by formula [H3CC(O)O] - [M] +(wherein M is as described herein) R 6 is an unsubstituted methyl group. In other embodiments, substituent R 6 is the formula (R 7 )3C-(in the formula, each R 7 This is a substituted methyl group having H, a halogen (e.g., F, Cl, Br, etc.), and a hydrocarbyl group (selected independently from these).

[0052] R 7 Suitable hydrocarbyl groups include any of the above-mentioned substituents R of the organosilanol compound (A). Typically, R 7 The hydrocarbyl group is selected from alkyl groups such as methyl and ethyl groups, and aryl groups such as phenyl and benzyl groups. For example, in certain embodiments, at least one R may be defined as a salt complex of component (C) further or alternatively as a propionate ion. 7 It can be methyl. However, aryl, alkaryl, and other types of hydrocarbyl groups are also R 7 It can be used as such.

[0053] In a particular embodiment, each R 7 R is independently selected from H, F, Cl, an unsubstituted alkyl group having 1 to 4 carbon atoms, and a phenyl group. In some such embodiments, R 7 At least two of them are H. In certain embodiments, R 6 As described above, each R is an unsubstituted methyl group. 7 H is H.

[0054] The alkali metal M is not particularly limited and may include, or could include, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), or combinations thereof (for example, when the acetate (C) is a mixed salt containing two or more cations). In certain embodiments, M includes sodium and / or potassium (K). In certain embodiments, M is sodium, so that the acetate (C) may be further defined as a sodium acetate compound. In certain embodiments, the acetate (C) may alternatively include sodium acetate, for example, a complex having the chemical formula NaCO2CH3, usually abbreviated as NaOAc.

[0055] In general, with respect to acetate(C), it will be understood that compounds containing an average of two or more acetate ions in a given complex, such as polyacetates in which polycationic and / or crosslinked counterions are utilized, may also be used. For example, certain alkali metal diacetates (e.g., sodium diacetate) and / or alkaline earth metal acetates (e.g., calcium diacetate, also simply called calcium acetate) may also be used in this method. Similarly, in certain embodiments, this method involves utilizing two or more acetate(C), such as two, three, or four or more acetate(C) compounds. In such embodiments, each acetate(C) is selected independently and may be the same as or different from any other acetate(C) with respect to, for example, acetate anions, countercations, etc.

[0056] Methods for preparing acetate (C) are well known in the art, and specific compounds described and / or represented by the above formula, as well as compounds used to prepare them, are commercially available from various suppliers. Therefore, acetate (C) may be prepared as part of the present method, or otherwise, may be obtained (i.e., as a prepared compound). Similarly, preparations of acetate (C) may be formed before the reaction of components (A) and (B), or in situ (i.e., during the reaction of components (A) and (B)).

[0057] Acetate (C) may be used in any form, for example, undiluted (i.e., without solvent, carrier vehicle, diluent, etc.), or supplied in a carrier vehicle such as a solvent or dispersant (e.g., any of those described above with respect to the organic silanol compound (A)). In some embodiments, acetate (C) is used in the absence of water and carrier vehicle / volatile substances (e.g., anhydrous) to react with the organic silanol compound (A), the hydridosilane compound (B), and / or acetate (C) itself (i.e., until combined with components (A) and (B)). For example, in certain embodiments, the method may include stripping the volatile substances and / or solvent (e.g., water, organic solvent, etc.) from acetate (C). Techniques for stripping acetate (C) are known in the art and may include heating, drying, application of reduced pressure / vacuum, azeotrope with a solvent, use of molecular sieves, and combinations thereof.

[0058] Acetate (C) may be used in any amount that a person skilled in the art would select, which will vary depending, for example, the specific acetate (C) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of component (A) and component (B)). Generally, the molar ratio of acetate (C) to component (B) used in the reaction affects the reaction rate and / or amount of component (A) and component (B), thereby enabling the preparation of polyfunctional organosilicon compounds. Therefore, the amount of acetate (C) compared to component (A) and / or component (B), and the molar ratio between them, can vary. Typically, these relative amounts and molar ratios are selected to maximize the coupling of component (A) and component (B), and / or the complete conversion of one or both components, for example, to improve the economic efficiency of the reaction or to simplify the purification of the reaction products formed.

[0059] The reactions used to prepare polyfunctional organosilicon compounds are not limited to a specific mechanism and / or type, but under the conditions employed in this method, it is assumed that component (B) and component (C) react to prepare an acetoxyhydridosilane intermediate, for example, via in situ condensation between the acetate anion of component (C) and the silicon atom of component (B), facilitated by one or more hydrolyzable groups (e.g., substituent Z as described above). As will be understood by those skilled in the art, the theoretical maximum molar ratio of the reaction between component (B) and component (C) (i.e., the stoichiometric ratio of the complete reaction) depends on the number of subscripts c, i.e., hydrolyzable groups Z, of the hydridosilane compound (B). For example, if the subscript c is 2 (i.e., the hydridosilane compound (B) has 2 hydrolyzable groups Z), then component (B) and component (C) may react in a molar ratio of 2:1 (C):(B). Similarly, if the subscript c is 3 (i.e., the hydridosilane compound (B) has three hydrolyzable groups Z), then components (A) and (B) can react in a molar ratio of (C):(B) of 3:1.

[0060] As just one example to explain the formation of the acetoxyhydridosilane intermediate, the hydridosilane compound (B) is dichloromethylsilane (i.e., the subscript c is 2, R 5 In embodiments where (a) is methyl and each Z is Cl, and the acetate (C) is sodium acetate (i.e., NaOAc), the acetoxyhydridosilane intermediate has the general formula (AcO) c’ (Cl) 2-c’ It should be understood that the intermediate has SiHCH3 (wherein the formula, the subscript c' is 1 or 2 in each molecule corresponding to this formula). However, those skilled in the art will also understand that the average value of the subscript c' of the entire acetoxyhydridosilane intermediate may be influenced by the relative amounts of components (B) and (C) used. For example, if a stoichiometric excess of component (C) is used in the exemplary embodiment described above, the average value of the subscript c' of the entire acetoxyhydridosilane intermediate may approach 2, which is the theoretical maximum value based on the stoichiometric maximum molar ratio of components (B) and (C) for the desired reaction (i.e., the stoichiometric ratio of the complete reaction).

[0061] As can be understood from the above explanation, acetate (C) is typically used stoichiometrically equivalent to or in excess of hydridosilane compound (B) to maximize the conversion rate of component (B) to the acetoxyhydridosilane intermediate. Thus, hydridosilane compound (B) and acetate (C) are typically used in a molar ratio of (B):(C) of 1:2 or less when the subscript c is 2 (i.e., hydridosilane compound (B) has two hydrolyzable groups Z), or in a molar ratio of (B):(C) of 1:3 or less when the subscript c is 3 (i.e., hydridosilane compound (B) has three hydrolyzable groups Z). For example, in some embodiments, acetate (C) is used in an amount sufficient to provide a relative molar ratio of (B):(C) of less than 1:1 to 1:10 with respect to hydridosilane compound (B). For example, in certain embodiments, the hydridosilane compound (B) and acetate (C) are used in molar ratios of (B):(C) of 1:2 to 1:10, for example, 1:2 to 1:5, or less than 1:2 to 1:5, or less than 1:2 to 1:4, or 1:2.1 to 1:3.1. It will be understood that ratios outside these ranges may also be used. For example, in certain embodiments, acetate (C) is used in large excess (for example, 10 times, 15 times, or 20 times the molar amount of the hydridosilane compound (B)).

[0062] In certain embodiments, the specific types and relative amounts of components (A), (B), and (C) are selected such that the reactivity of certain by-products of the reaction is minimized or otherwise reduced with respect to the reactants and / or reaction products. For example, in certain embodiments, the hydrolyzable group Z of the hydridosilane compound (B) is chlorine, such that the overall condensation of the silanol of component (A) and the hydridosilane compound (B) (i.e., directly and / or via an acetoxyhydridosilane intermediate) produces HCl as a by-product. In such embodiments, the acetate salt (C) may be used in an amount selected to prepare a buffer system in the reaction mixture (e.g., more than the stoichiometric amount required to prepare the acetoxyhydridosilane intermediate), thereby reducing the reactivity of HCl with components (A) and / or (B) by forming a chloride salt (e.g., NaCl) and a conjugate acid (e.g., AcOH) of the acetate anion.

[0063] In certain embodiments, the method comprises reacting components (A) and (B) in the presence of a reaction inhibitor (D). The reaction inhibitor (D) is not limited and may include any compound or composition that can prevent, suppress or otherwise inhibit reactions other than the desired and / or required reactions for the preparation of polyfunctional organosilicon compounds. For example, in some embodiments, if the organosilanol compound (A) is an acrylic oxy functional group, the reaction inhibitor (D) includes or is a polymerization inhibitor.

[0064] Polymerization inhibitors are, but are not limited to, radical scavengers, antioxidants, light stabilizers, or ultraviolet absorbers, or combinations thereof, or any one thereof. Such compounds are known in the art and are generally chemical compounds or moieties that can inactivate free radicals by interacting with them, for example, by removing free radicals through the formation of covalent bonds with them, or include such compounds. Polymerization inhibitors may also, or alternatively, be polymerization retarders, i.e., compounds that reduce the initiation and / or propagation rate of radical polymerization. For example, in some embodiments, the polymerization inhibitor is, or contains, oxygen gas. Generally, polymerization inhibitors are used to prevent and / or suppress the formation of by-products that may be formed through the radical polymerization of organosilanol compounds (A) and / or polyfunctional organosilicon compounds (e.g., including acrylooxy moieties).

[0065] In certain embodiments, the polymerization inhibitor includes or is a phenol compound, a quinone compound or hydroquinone compound, an N-oxyl compound, a phenothiazine compound, a hindered amine compound, or a combination thereof.

[0066] Examples of phenolic compounds include phenols, alkylphenols, aminophenols (e.g., p-aminophenol), nitrosophenols, and alkoxyphenols. Specific examples of such phenolic compounds include o-, m-, and p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol, or 2,2'-Methylenebis(6-tert-butyl-4-methylphenol), 4,4'-Oxybiphenyl, 3,4-Methylenedioxydiphenol (sesamol), 3,4-Dimethylphenol, Pyrocatechol(1,2-Dihydroxybenzene), 2-(1'-Methylcyclohexa-1'-yl)-4,6-Dimethylphenol, 2-or 4-(1'-Phenyleth-1'-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-Tris-tert-butylpheno Al, 2,6-di-tert-butylphenol, nonylphenol, octylphenol, 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3',5,5'-tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol, 2-methoxy -4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate or pentaerythrityltetrakis[p-(3,5-di-tert-butyl-4-hydroxyphenyl) [Propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-sec-butyl-2,4-dinitrophenol, octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, hexadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, octyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 3-thia-1,5-pentanediol bis[(3',5'- [Di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate], 1,9-nonanediol bis[(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 1,7-heptanediamine 3,1-methanediaminebis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 1,1-methanediaminebis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionamide], 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid hydrazide, 3-(3',5'-dimethyl-4'-hydroxyphenyl)propionic acid hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1'-methylcyclohex-1'-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)s Rufid, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris-[1'-(3Δ,5″-di-tert-butyl-4″-hydroxyphen-1″-yl)methyl-1'-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl)butane and tert-butylcatechol, p-nitrosophenol, p- Nitroso-o-cresol, methoxyphenol (guaiacol, pyrocatechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanilla Examples include 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetovanillone), eugenol, dihydroeugenol, isoeugenol, tocopherol, for example, α-, β-, γ-, δ-, and ε-tocopherol, tocol, α-tocopherolhydroquinone, and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran).

[0067] Suitable quinones and hydroquinones include hydroquinone, hydroquinone monomethyl ether (4-methoxyphenol), methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 4-methylpyrocatechol, tert-butylhydroquinone, 3-methylpyrocatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, tetramethyl-p-benzoquinone, diethyl-1,4-cyclohexanedione 2,5-dicarboxylate, phenyl-p-benzoquinone, 2,5-dimethyl-3-benzyl-p-benzoquinone, 2-isopropyl-5-methyl-p- Benzoquinone (thymoquinone), 2,6-diisopropyl-p-benzoquinone, 2,5-dimethyl-3-hydroxy-p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Envelin, tetrahydroxy-p-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2-amino-5-methyl-p-benzoquinone, 2,5-bisphenylamino-1,4-benzoquinone, 5,8-dihydroxy-1,4-naphthoquinone, 2-anilino- This includes 1,4-naphthoquinone, anthraquinone, N,N-dimethylindoaniline, N,N-diphenyl-p-benzoquinone diimine, 1,4-benzoquinone dioxime, coerulignone, 3,3'-di-tert-butyl-5,5'-dimethyldiphenoquinone, p-rosolic acid (aurine), 2,6-di-tert-butyl-4-benzylidenebenzoquinone, 2,5-di-tert-amylhydroquinone, and others.

[0068] Suitable N-oxyl compounds (i.e., nitroxyl group or N-oxyl group) include compounds having at least one NO● group, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4,4',4' '-Tris(2,2,6,6-tetramethylpiperidine-N-oxyl) phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsilyloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ylsebacate, 1-oxyl-2,2,6,6- Tetramethylpiperidine-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl (4-tert-butyl) benzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperizidine-4-yl) succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) 1,10-decandioate , bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) n-butylmalonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) hexahydroterephthalate, N,N'-bis(1-oxyl-2,2,6,Examples include 6-tetramethylpiperidine-4-yl)adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)dodecylsuccinimide, 2,4,6-tris[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl]triazine, N,N'-bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)-N,N'-bisformyl-1,6-diaminohexane, and 4,4'-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazine-3-one).

[0069] Other compounds suitable for use as polymerization inhibitors or polymerization inhibitors include phenothiazine (PTZ) and compounds having a similar structure, such as phenoxazine, promazine, N,N'-dimethylphenazine, carbazole, N-ethylcarbazole, N-benzylphenothiazine, N-(1-phenylethyl)phenothiazine, and N-alkylated phenothiazine derivatives such as N-benzylphenothiazine and N-(1-phenylethyl)phenothiazine. Naturally, the polymerization inhibitor may contain any number of specific compounds, each of which may be selected independently and may be the same as or different from any other compound in the polymerization inhibitor.

[0070] In certain embodiments, the reaction inhibitor (D) includes, or is a polymerization inhibitor selected from (2,2,6,6-tetramethylpiperidine-1-yl)oxyl (TEMPO), 4-hydroxy(2,2,6,6-tetramethylpiperidine-1-yl)oxyl (4HT), bis(2,2,6,6-tetramethylpiperidine-1-yl)oxyl sebacate (Bis-TEMPO), polymer-bound TEMPO, and combinations thereof.

[0071] When used, reaction inhibitor (D) may be added to the reaction as a separate component, or it may be mixed with another component (e.g., an organic silanol compound (A)) before the reaction of components (A) and (B). Reaction inhibitor (D) may be used in any amount selected by those skilled in the art, depending on, for example, a specific reaction inhibitor (D) selected, the reaction parameters employed, and the scale of the reaction (e.g., the total amount of components (A) and / or (B), the atmosphere of the reaction, the temperature and / or pressure of the reaction, etc.). In certain embodiments, reaction inhibitor (D) is present in the reaction in amounts of 50 to 2000 ppm, for example, 50, or 100, or 250, or 500, or 1000, or 1500, or 2000 ppm. However, those skilled in the art will readily understand that amounts outside these ranges and exemplary amounts may also be used, for example, when the scale and / or conditions of the reaction require additional amounts of reaction inhibitor (D).

[0072] The reaction inhibitor (D) may be used at any time in this method, including before, during, and after the reaction of components (A) and (B). In addition, the reaction inhibitor (D) may be used auxiliaryly in this method, for example in a vacuum trap, distillation and / or receiving pot, in addition to its use within the reaction itself. Furthermore, oxygen may be added to the reaction as a separate component (for example, in place of or in addition to a separate reaction inhibitor (D) selected from the above compounds) in addition to or as a substitute for the above amounts. In such cases, oxygen may be introduced into the reaction in the form of oxygen gas in the presence of another gas (e.g., in the form of air), which is optional. If used, the amount of oxygen gas should be selected so that the gas phase above the reaction mixture remains below the explosion limit.

[0073] The components used in this method (i.e., the organosilanol compound (A), the hydridosilane compound (B), the acetate (C), and / or the reaction inhibitor (D) (if used)) may be provided "as is," that is, ready for the reaction to prepare the polyfunctional organosilicon compound. Alternatively, one or more, or all, of components (A), (B), (C), and / or (D) may be formed before or during the reaction. In some embodiments, as described above, the method includes preparing the organosilanol compound (A). In these or other embodiments, the method further includes preparing the hydridosilane compound (B). In these or other embodiments, the method further includes preparing the acetate (C).

[0074] As described above, this method typically involves indirectly reacting component (B) with an organosilanol compound (A) via an acetoxyhydridosilane intermediate, which may be pre-formed (e.g., in a reactive premixture) and / or formed in situ from the hydridosilane compound (B) and acetate (C). In this form, the specific conditions used are variable but generally selected to promote the condensation of components (B) and (C) for the preparation of the acetoxyhydridosilane intermediate, and the condensation of component (A) with the acetoxyhydridosilane intermediate for the preparation of a polyfunctional organosilicon compound. Furthermore, the reaction is typically carried out under conditions that minimize hydrolysis of the organosilanol compound (A) and / or the hydridosilane compound (B), otherwise undesirable side reactions may occur. In particular, the reaction is typically carried out under anhydrous or substantially anhydrous conditions without the use of stoichiometric amounts of acid or base to promote either condensation reaction. For example, the use of acetate (C) provides the ability to avoid the use of amine bases used in other silanol-chlorosilane type condensations, which are necessary to wash away HCl produced during the reaction to minimize decomposition between the reactants and / or unwanted reactions. Such other conditions have been observed to result in incomplete conversion of the organosilanol compound to the desired condensation product, for example, due to incomplete reactions, self-condensation of the organosilanol compound, etc. Certain components and conditions of the method described herein can be used to overcome such limitations and to enable a higher conversion rate of organosilanol compound (A) to the polyfunctional organosilicon compound, and / or an overall yield of the polyfunctional organosilicon compound, compared to the use of other methods for preparing the polyfunctional organosilicon compound from components (A) and (B). For example, in certain embodiments, the method provides an overall conversion rate of organosilanol compound (A) of at least 90%, or at least 95%, or at least 96%, or at least 98%. In these or other embodiments, the method provides an overall yield of at least 90%, or at least 95%, or at least 96%, or at least 98% of the polyfunctional organosilicon compound.

[0075] Typically, components (A), (B), (C), and optionally (D) are reacted in a vessel or reactor to prepare a polyfunctional organosilicon compound. If the reaction is carried out at high or low temperatures as described below, the vessel or reactor may be heated or cooled in any preferred manner, for example, via a jacket, mantle, exchanger, bath, coil, etc. Similarly, the vessel or reactor may be equipped with a gas inlet, condenser, bubbler, circulator, agitator, and / or other such equipment that can be used to control one or more conditions of the reaction used when carrying out this method, as will be readily understood from the description and examples herein.

[0076] Components (A), (B), (C), and optionally (D) may be supplied together or separately in a container, or may be distributed in a container in any combination and in any order of addition. In general, references to “reaction mixture” herein generally refer to a mixture comprising components (A), (B), (C), and optionally (D), if used, such as, for example, by combining these components.

[0077] In one particular embodiment, the method includes preparing a reaction mixture by adding component (A), component (C), and optionally component (D) to a container containing component (B). In another embodiment, the method includes preparing a reaction mixture by adding component (B) and component (C) (for example, simultaneously or sequentially) to a container containing component (A) and optionally component (D). In both such embodiments, the reaction mixture promotes in-situ formation of an acetoxyhydridosilane intermediate in the presence of component (A). In another embodiment, the method includes combining component (B) and component (C) to form a reactive premixture, and subsequently combining component (A) with the reactive premixture to prepare a polyfunctional organosilicon compound. In such embodiments, the reactive premixture may include an acetoxyhydridosilane intermediate formed in situ from, for example, a hydridosilane compound (B) and an acetate (C). In these embodiments, component (A) may be added slowly and / or in portions to the reactive premixture to stabilize the reaction conditions, for example, by increasing the conversation rate of the reaction, minimizing unwanted side reactions, and controlling exothermic reactions.

[0078] This method may further include stirring the reaction mixture. Stirring, for example, when combined in the reaction mixture, can increase the mixing and contact of the reactants with each other. Such contact can also be achieved independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), using other conditions. Other conditions can be adjusted to increase the contact of specific components of the reaction (e.g., component (B) and component (C), component (A) and the acetoxyhydridosilane intermediate, etc.), and consequently the reaction between component (A) and component (B), in order to prepare a polyfunctional organosilicon compound. Other conditions may also be effective in increasing the reaction yield or in minimizing the amount of specific reaction byproducts included in the reaction product along with the polyfunctional organosilicon compound.

[0079] Regardless of the order, the components may react in the presence of a carrier vehicle (e.g., a solvent, diluent, fluid, or combination thereof) so that the reaction takes place in a solution, emulsion, suspension, slurry, two-phase mixture, or a combination thereof. The specific solvent, carrier, and / or diluent used, and the respective amounts employed, can be independently selected by those skilled in the art, for example, based on a specific organosilanol compound (A), hydridosilane compound (B), acetate (C), and / or reaction inhibitor (D) (if used), the specific polyfunctional organosilicon compound to be prepared, etc.

[0080] Generally, the reaction may be carried out under heterogeneous conditions (e.g., one or more components suspended in a carrier vehicle but not dissolved) or heterogeneous conditions (e.g., in solution). For example, in some embodiments, the acetate (C) is not soluble in the carrier vehicle so that the reaction proceeds heterogeneously. Generally, one or more of the components or a combination thereof (e.g., a reactive premixture) may be employed in the form of a homogeneous mixture / solution (i.e., the components are dissolved and / or supplied in the carrier vehicle before a reaction reaction with it is formed). For example, a portion of the carrier vehicle or solvent may be added to the organosilanol compound (A), hydridosilane compound (B), acetate (C), and / or any other components of the reaction, or, in other combinations, the polyfunctional organosilicon compounds may be prepared individually, together with a mixture of one or more components, or together with the whole reaction mixture.

[0081] The carrier vehicle is not particularly limited and typically includes, or is, a solvent, an oil (e.g., organic oil and / or silicone oil), a fluid, or any one or more of the above, or a combination thereof.

[0082] In some embodiments, the carrier vehicle contains or is an organic solvent. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, methylene chloride, and chloroform; processed hydrocarbon mixtures such as white spirits, mineral spirits, naphtha, and hydrogenated isoparaffinic hydrocarbons; dimethyl sulfoxide; dimethylformamide; acetonitrile; tetrahydrofuran, n-methylpyrrolidone, and others, as well as derivatives, modifiers, and combinations thereof. As can be understood from the above examples, organic solvents are typically aprotic and can be aromatic or non-aromatic, polar or nonpolar, etc. In certain embodiments, the organic solvent is a nonpolar aprotic solvent. In some such embodiments, the organic solvent is aromatic.

[0083] In certain embodiments, the carrier vehicle contains, or is, an organic fluid, typically containing organic oils including volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. General examples of such organic fluids include C6-C6. 16 Alkane, C8~C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8~C 16 Examples of suitable organic fluids include volatile hydrocarbon oils such as branched esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), as well as their derivatives, modifiers, and combinations. Additional examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alkyl halides, aromatic halides, and combinations thereof. Examples of hydrocarbons include isododecane, isohexadecane, and Isopar L(C) 11 ~C 13 ), Isopar H(C 11 ~C 12 Examples include hydrogenated polydecene.

[0084] In certain examples, the carrier vehicle includes or is toluene, xylene, heptane, hydrogenated isoparaffinic hydrocarbons (e.g., Isopar), or any combination thereof. In some such embodiments, the carrier vehicle is water-free or substantially water-free so that the reaction is carried out substantially anhydrous.

[0085] The reaction temperature is selected and controlled depending on the specific reactants chosen, the specific polyfunctional organosilicon compounds to be prepared, for example, with respect to the volatility and / or reactivity of any such components of the reaction. Generally, the reaction can be carried out at temperatures from -78°C to 100°C. However, a specific range (e.g., -10°C to 10°C, 20°C to 25°C, 20°C to 60°C, etc.) may be selected based on the specific components (A), (B), and (C) to be reacted.

[0086] In certain embodiments, the reaction is carried out at low temperatures. Low temperatures are typically below 25°C (ambient temperature), for example, -78°C to below ambient temperature, or -30°C to below ambient temperature, or -15°C to below ambient temperature, or -10°C to below ambient temperature, or -10°C to 20°C, or -5°C to 20°C, or -5°C to 15°C, or 0°C to 15°C. In some embodiments, the reaction is carried out at a temperature of about 0°C (for example, using ice and / or an ice bath, circulator, or cooling device set to 0°C). In alternative embodiments, the reaction is carried out at room temperature (i.e., 20–25°C).

[0087] It should be understood that the reaction temperature may differ from the range described above. For example, in certain embodiments, the reaction is carried out at high temperatures such as greater than 25°C to 100°C. In some such embodiments, high temperatures are greater than 25°C to 90°C, or 30°C to 90°C, or 30°C to 80°C, or 30°C to 60°C. Similarly, it should be understood that reaction parameters may be modified during the reaction of components (A) and (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., room temperature and / or atmospheric pressure) and / or non-ambient parameters (e.g., low or high temperature and / or reduced or high pressure). Any parameter may also be dynamically modified, in real time, i.e., changed during the method, or statically (e.g., during or for any part of the duration of the reaction). As just one example, in a particular embodiment, the method includes preparing a reactive premixture at a first temperature and reacting component (A) with the reactive premixture at a second temperature (for example, by combining the same components as described above). In such embodiments, the first temperature may be lower or higher than the second temperature, for example, to control exothermic reactions.

[0088] (The time required for the reaction of components to prepare polyfunctional organosilicon compounds varies depending on the scale, reaction parameters and conditions, and the selection of specific components. In certain embodiments, the reaction time is from more than 0 hours to 48 hours, for example, from 1 minute to 48 hours. For relatively large-scale (e.g., more than 1 kg, or 5 kg, or 10 kg, or 50 kg, or 100 kg), the reaction may take place over a period of time such as 1 hour to 48 hours, or 2 hours to 36 hours, or 4 hours to 24 hours, or 6 hours, 12 hours, 18 hours, 24 hours, 36 hours, or 48 hours. On a small scale (grams, or less than 10, 5, or 1 kg), the reaction may take place over a period of 1 minute to 4 hours, for example, 5 minutes to 1 hour, 30 to 35 minutes, or 10, 15, 20, 25, or 30 minutes. Alternatively, on the same relatively small scale, the reaction may take place over a period of 30 minutes to 3 hours, such as 1 to 3 hours, or 2 to 3 hours. The specific reaction time will be readily determined by those skilled in the art by monitoring the conversion of the organosilanol compound (A), the formation of the polyfunctional organosilicon compound, etc. (for example, via chromatography and / or spectroscopy).

[0089] Generally, the reaction of components (A), (B), and (C) prepares a reaction product containing a polyfunctional organosilicon compound. In particular, during the reaction, the reaction mixture containing components (A), (B), and (C) contains an increasing amount of the polyfunctional organosilicon compound and a decreasing amount of components (A) and (B). Once the reaction is complete (e.g., one of components (A) or (B) is consumed, no additional polyfunctional organosilicon compound is prepared, etc.), the reaction mixture may be referred to as a reaction product containing a polyfunctional organosilicon compound. Thus, the reaction product typically contains any remaining amounts of components (A), (B), (C), and (D) (if present), as well as their decomposition and / or reaction products (e.g., materials not previously removed by distillation, stripping, etc.). If the reaction is carried out in any carrier vehicle or solvent, the reaction product may also contain such carrier vehicle or solvent.

[0090] In certain embodiments, the reaction product does not contain, or substantially does not contain, any by-products formed from the homocondensation of the organic silanol compound (A). In these or other embodiments, the reaction product contains less than 10%, less than 8%, less than 5%, or less than 3% of the organic silanol compound (A) based on the total amount of organic silanol compound (A) used (e.g., by weight or molar amount).

[0091] In certain embodiments, the method further includes isolating and / or purifying a polyfunctional organosilicon compound from the reaction product. As used herein, isolating a polyfunctional organosilicon compound is typically defined as increasing the relative concentration of the polyfunctional organosilicon compound compared to other compounds combined with it (e.g., in the reaction product or its purified product). Thus, as understood in the art, isolation / purification may include removing other compounds from such combinations (i.e., reducing the amount of impurities combined with the polyfunctional organosilicon compound, for example, in the reaction product), and / or removing the polyfunctional organosilicon compound itself from the combination. Any suitable techniques and / or protocols for isolation may be utilized. Examples of suitable isolation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, and chromatography. As will be understood by those skilled in the art, any of these techniques can be used in combination (i.e., sequentially) with any other technique to isolate a polyfunctional organosilicon compound. It should be understood that isolation may include the purification of the polyfunctional organosilicon compound, and therefore may be referred to as the purification of the polyfunctional organosilicon compound. However, the purification of the polyfunctional organosilicon compound may include alternative and / or additional techniques to those used for the isolation of the polyfunctional organosilicon compound. Regardless of the specific technique selected, the isolation and / or purification of the polyfunctional organosilicon compound may be performed sequentially with the reaction itself (i.e., in a line) and therefore automated. In other examples, purification may be a standalone procedure to which the reaction product containing the polyfunctional organosilicon compound is supplied.

[0092] In certain embodiments, isolating a polyfunctional organosilicon compound involves washing and / or extracting the reaction mixture by adding aqueous solutions (e.g., water, brine, etc.) and optionally non-aqueous solvents to the reaction mixture and separating the phases during partitioning. For example, in some embodiments, the method involves sequentially washing the reaction mixture with different aqueous solutions (e.g., water, aqueous sodium carbonate solution, brine, etc.) to remove aqueous components from the reaction mixture. In such embodiments, isolating a polyfunctional organosilicon compound typically also involves distilling and / or stripping volatile substances from the reaction product to remove, for example, non-aqueous solvents or other volatile substances from the reaction product. In both or either case (e.g., after removing aqueous components by washing / extraction and / or after removing volatile substances by stripping / distillation), the reaction product (i.e., separated here from other components of different solubility and / or volatility) can be referred to as the isolated polyfunctional organosilicon compound.

[0093] It is understood that other techniques and / or procedures may also be utilized. For example, in some embodiments, isolating a polyfunctional organosilicon compound involves filtering the reaction product (e.g., removing solids, salts, and other precipitates or suspensions from the reaction product). In such embodiments, as will be understood by those skilled in the art, solvents and / or diluents (e.g., organic solvents such as toluene and diethyl ether) can be used to solubilize and / or precipitate various components of the reaction product to facilitate the isolation of the polyfunctional organosilicon compound. In these or other embodiments, isolating a polyfunctional organosilicon compound may involve distilling and / or stripping volatile substances from the reaction product. For example, in certain embodiments, such as when a carrier vehicle is used, volatile substances are distilled and / or stripped from the reaction mixture containing the polyfunctional organosilicon. In both or either case, (e.g., after removal of solids by filtration and / or stripping / distillation of volatile substances), the reaction product (separated from solids and / or volatile substances) may be referred to as the isolated polyfunctional organosilicon compound.

[0094] In certain embodiments, the method further includes purifying the polyfunctional organosilicon compound. Any preferred technique for purification may be utilized. In certain embodiments, purifying the polyfunctional organosilicon compound includes removing the polyfunctional organosilicon compound (e.g., distillate) or stripping other compounds / components from it (i.e., leaving the polyfunctional organosilicon compound in the pot as a high-boiling component of the reaction mixture or the purified reaction mixture). As will be understood by those skilled in the art, distillation of the reaction product or the purified reaction product to purify and / or isolate the polyfunctional organosilicon compound is typically carried out under high temperature and reduced pressure. The high temperature and reduced pressure are selected independently, for example, based on the specific components of the reaction, the specific polyfunctional organosilicon compound to be prepared, and other isolation / purification techniques used, as will be readily determined by those skilled in the art. In some embodiments, the purification of the polyfunctional organosilicon compound can be defined as purifying the isolated polyfunctional organosilicon compound (e.g., when the purification is carried out after the isolation of the polyfunctional organosilicon compound).

[0095] As described above, this method prepares polyfunctional organosilicon compounds. More specifically, as can be understood by considering the structures of components (A) and (B) and the parameters of their reaction, this method prepares polyfunctional organosilicon compounds as addition products of an organosilicanol compound (A) and a hydridosilane compound (B), for example, by condensation-mediated substitution of an organosilicanol compound (A) with respect to the hydrolyzable group (Z) of a hydridosilane compound (B).

[0096] Typically, the polyfunctional organosilicon compounds prepared according to this method have the following general formula: [ka] (In the formula, each Y, R, R 5, subscript a, and subscript c are independently selected and have (as defined above). More specifically, each functional moiety Y is an independently selected alkoxysilyl or acryloxy moiety, each R is an independently selected hydrocarbyl group, and each R 5 is an independently selected hydrocarbyl group, each subscript a is independently 0, 1, or 2 in each moiety represented by subscript c, and subscript c is 2 or 3.

[0097] As will be understood by those skilled in the art in view of the description herein, the organosilanol compound (A) utilized in the present method forms a part of a polyfunctional organosilicon compound corresponding to the moiety specified by subscript c in the above general formula, and the hydridosilane compound (B) utilized in the present method, as described herein, has a partial formula -Si(H)(R 5 ) 3-c forms a part of a polyfunctional organosilicon compound corresponding to the moiety represented. Thus, if a formula, structure, moiety, group, or other such motif is shared between a polyfunctional organosilicon compound and the organosilanol compound (A) and / or the hydridosilane compound (B) utilized in the present method, the above description regarding such a shared motif may equally apply to the polyfunctional organosilicon compound (e.g., with respect to each Y, R, R 5 , subscript a, subscript c, etc.).

[0098] For example, a polyfunctional organosilicon compound comprises two or three functional moieties Y, each independently selected from an alkoxysilyl moiety and an acrylooxy moiety (i.e., each functional moiety Y includes at least one independently selected alkoxysilyl or acrylooxy substituent, as described above) (i.e., the subscript c is 2 or 3, as shown below). Thus, each functional moiety Y may be the same as or different from any other functional moiety Y in the polyfunctional organosilicon compound. In a particular embodiment, each functional moiety Y is the same. In another embodiment, at least one functional moiety Y is different from at least one other functional moiety Y of the polyfunctional organosilicon compound. In a particular embodiment, each functional moiety Y of the polyfunctional organosilicon compound is different from one another. In any case, since polyfunctional organosilicon compounds contain two or three functional moieties Y, any singular reference to a polyfunctional organosilicon compound, either "functional moiety Y" or simply "Y," in this specification should be understood as referring collectively to each of the functional moieties Y of the polyfunctional organosilicon compound (i.e., each of the two or three functional moieties Y shown in the general formula above).

[0099] The alkoxysilyl substituent or acrylooxy substituent of the functional moiety Y may be directly (e.g., via covalent bonds) or indirectly (e.g., via divalent linking groups) bonded to the silicon atom represented by the general formula of the polyfunctional organosilicon compound (i.e., the siloxane backbone of the polyfunctional organosilicon compound) as shown above. In certain embodiments, the alkoxysilyl substituent or acrylooxy substituent of the functional moiety Y is directly bonded to the siloxane backbone of the polyfunctional organosilicon compound, thereby Y itself representing the alkoxysilyl group or acrylooxy group as described above. For example, in some embodiments, the polyfunctional organosilicon compound has the following general formula: [ka] (In the formula, each R, R 1 , R 5 Each functional part Y has formula -DR such that D, subscript a, and subscript c are independently selected and defined above.1 has. More specifically, each R 1 independently selected contains an alkoxysilyl group or an acryloxy group, and each D is a divalent linking group independently selected.

[0100] For example, in some such embodiments, each linking group D has a hydrocarbon moiety having the formula -(CH2) m -(where the subscript m is 1 to 16, or 1 to 6). In these or other embodiments, each linking group D contains a substituted hydrocarbon. For example, in some embodiments, at least one linking group D is a hydrocarbon having a backbone containing an ether moiety. Each linking group D may be the same as or different from any other linking group D in the polyfunctional organosilicon compound (e.g., each functional moiety Y may contain the same or different D from any other functional moiety Y). In certain embodiments, each linking group D is the same. In other embodiments, at least one linking group D is different from at least one other D of the polyfunctional organosilicon compound. In any case, the polyfunctional organosilicon compound contains two or three functional moieties Y, each of which may have the formula R 1 -D-, and the reference herein to the singular linking group D may apply to only one linking group D in the polyfunctional organosilicon compound (i.e., in each of the two or three functional moieties Y) or to each linking group D.

[0101] As introduced above, each R 1 independently contains an alkoxysilyl group or an acryloxy group. These groups are not particularly limited and are exemplified by the general and specific examples herein. Each R 1 may be the same as or different from any other R 1 in the polyfunctional organosilicon compound (e.g., each functional moiety Y may contain the same or different R 1 from any other functional moiety Y). In certain embodiments, each R 1 is the same. In other embodiments, at least one R 1 is different from at least one other R 1 of the polyfunctional organosilicon compound. 1This is different. In certain embodiments, the polyfunctional organosilicon compound has at least two or three different R 1 It includes substituents. In any case, the polyfunctional organosilicon compound contains two or three functional moieties Y, each of which is a compound of formula R 1 It may have -D-, and in this specification, the singular R 1 The reference to is to only one R in a polyfunctional organosilicon compound (i.e., in each of the two or three functional moieties Y). 1 to or each R 1 It can be applied to this.

[0102] In a particular embodiment, R 1 The formula is as follows: [ka] (In the formula, each R 2 , R 3 , and subscript b are independently selected alkoxysilyl groups having (as defined above). More specifically, subscript b is 1, 2, or 3, and R 2 This is a hydrocarbyl group independently selected in each part indicated by the subscript b, and each R 3 R is an independently selected hydrocarbyl group. In these embodiments, the alkoxysilyl group R 1 It can be further defined as a mono, di, or trialkoxysilyl group, i.e., when the subscript b is 1, 2, or 3, respectively. Typically, an alkoxysilyl group R 1 However, the above subformula R 2 O-(in the formula, each R 2 is an alkoxysilyl group R 1 Any other R inside 2 The subscript b is 2 or 3, so that it includes at least two alkoxy groups represented by (which may be the same as or different from). In certain embodiments, the alkoxysilyl group R 1However, each R can be defined as a trialkoxysilyl, dialkoxyalkylsilyl, or alkoxyldialkylsilyl group, i.e., subscript b is 3, 2, or 1, respectively. 2 and R 3 R is independently selected from alkyl groups such as methyl and ethyl groups. For example, in a particular embodiment, R 1 The subscript b is 3, and each R is a trimethoxysilyl group (for example, (CH3O)3Si-), 2 is methyl. Similarly, in other embodiments, R 1 The subscript b is 3, and each R is a triethoxysilyl group (for example, (CH3CH2O)3Si-), and 2 is ethyl. In some embodiments, R 1 The subscript b is 2, and each R is a trimethoxysilyl group (for example, (CH3CH2O)3Si-). 2 is methyl, and R 2 It is methyl.

[0103] In a particular embodiment, R 1 The formula is as follows: [ka] (In the formula, R 4 R is an independently selected acryloyl group having the above definition. More specifically, 4 is H, or an independently selected hydrocarbyl group (e.g., a substituted or unsubstituted hydrocarbyl group, e.g., having 1 to 4 carbon atoms). In certain embodiments, an acrylooxy group R 1 R can be defined as an acrylate group, 4 is H. In other embodiments, the acrylooxy group R 1 R can be defined as an alkyl acrylate group, 4 is an alkyl group (e.g., methyl, ethyl, propyl, butyl, etc.). In certain embodiments, the acrylic oxy group R 1 R can be defined as a methacrylate group, 4It is methyl.

[0104] The subscript c of a polyfunctional organosilicon compound is either 2 or 3. Therefore, in certain embodiments, the subscript c is 2, and the polyfunctional organosilicon compound has the following general formula: [ka] (In the formula, each R, R 5 , Y, and subscript b are independently selected and have the following definitions. In other embodiments, subscript c is 3, and the polyfunctional organosilicon compound has the following general formula: [ka] (wherein each R, Y, and subscript a is independently selected and as defined herein)

[0105] Each subscript a of a polyfunctional organosilicon compound is independently 0, 1, or 2 in each part designated by subscript c. Therefore, those skilled in the art will readily understand that each part indicated by subscript c may independently be of the subformula Y-Si(R)2O- (i.e., monosiloxane, where b is 0), Y-Si(R)2O-Si(R)2O- (i.e., disiloxane, where b is 1), or Y-Si(R)2O-Si(R)2O-Si(R)2O- (i.e., trisiloxane, where b is 2). In any such case, each Y and R is independently selected and as defined herein.

[0106] For example, in a particular embodiment, in each part designated by the subscript c, each subscript a is 0. In some such embodiments, the subscript c is 2, and the polyfunctional organosilicon compound is given by the following general formula: [ka] (In the formula, each R, R 5, and Y are independently selected and have the definitions set forth herein. In other such embodiments, the subscript c is 3, and the polyfunctional organosilicon compound has the following general formula: [ka] (wherein each R and Y is independently selected and as defined herein)

[0107] In certain embodiments, in each part designated by the subscript c, each subscript a is 1. In some such embodiments, the subscript c is 2, and the polyfunctional organosilicon compound is given by the following general formula: [ka] (In the formula, each R, R 5 , and Y are independently selected and have the definitions set forth herein. In other such embodiments, the subscript c is 3, and the polyfunctional organosilicon compound has the following general formula: [ka] (wherein each R and Y is independently selected and as defined herein)

[0108] In certain embodiments, in each part designated by the subscript c, each subscript a is 2. In some such embodiments, the subscript c is 2, and the polyfunctional organosilicon compound is given by the following general formula: [ka] (wherein each R and Y is independently selected and as defined herein) has the following: In other such embodiments, the subscript c is 3, and the polyfunctional organosilicon compound is represented by the following general formula: [ka] (wherein each of the formulas and Y are independently selected and are as defined herein)

[0109] As stated above, the subscripts 'a' in a polyfunctional organosilicon compound do not need to be the same; instead, they may be different from other subscripts 'a'. For example, if the subscript c is 2, and the polyfunctional organosilicon compound contains one part indicated by subscript c (where subscript a is 0) and another part indicated by subscript c (where subscript a is 1), then the resulting polyfunctional organosilicon compound is represented by the following formula: [ka] (In the formula, each R, R 5 , and Y are independently selected and have the definitions specified herein.

[0110] The polyfunctional organosilicon compounds prepared according to this method can be used in a variety of end uses, for example, as separate components in a composition (e.g., a curable composition) or as components in a reaction for preparing functionalized compounds. For example, since the polyfunctional organosilicon compounds contain at least one silicon-bonded hydrogen atom per molecule (i.e., from hydridosilane compound (B)), they can be used in hydrosilylation reactions. Therefore, the polyfunctional organosilicon compounds can be used, for example, to prepare functionalized siloxane compounds via reaction with a polysiloxane containing at least one silicon-bonded ethylenically unsaturated group in the presence of a hydrosilylation catalyst.

[0111] Similarly, since polyfunctional organosilicon compounds also contain alkoxysilyl and / or acrylicoxy functional moieties, polyfunctional organosilicon compounds and functionalized siloxane compounds prepared using them can be used as components in curable compositions. For example, if the polyfunctional organosilicon compound is prepared from an acrylicoxy functional organosilicon compound (A), the polyfunctional organosilicon compound and functionalized siloxane compounds prepared using it can be used as components in a hydrosilylated curable composition. Similarly, if the polyfunctional organosilicon compound is prepared from an alkoxysilyl functional organosilicon compound (A), the polyfunctional organosilicon compound and functionalized siloxane compounds prepared using it can be used as components in a condensation curable composition.

[0112] When combined with one or more additives, condensation and / or hydrosilylation curable compositions containing polyfunctional organosilicon compounds and / or functionalized siloxane compounds can be used in or as adhesive compositions. Examples of suitable additives for preparing such adhesive compositions include fillers, treatment agents (e.g., filler treatment agents), crosslinking agents, adhesion promoters, surface modifiers, drying agents, fillers, biocides, flame retardants, plasticizers, end-sealing agents, binders, anti-aging agents, water-releasing agents, pigments, rheology modifiers, carriers, tackifiers, corrosion inhibitors, catalyst inhibitors, viscosity modifiers, UV absorbers, antioxidants, light stabilizers, and combinations thereof.

[0113] The following examples are intended to illustrate the present invention and should not be considered to limit its scope. The following brief summary provides information on certain abbreviations, notations, and components used in the examples. All reaction products were NMR ( 1 H, 13 C, and 29 Identified by Si) and GC-FID.

[0114] Organic silanol compound (A)

[0115] "AMA silanol" is an organic silanol compound having the following formula: [ka]

[0116] "ETM silanol" is an organic silanol compound having the following formula: [ka] Polyfunctional organosilicon compounds

[0117] The "bifunctional AMA Si-H converter" is a polyfunctional organosilicon compound having the following formula: [ka] The following are prepared using Example 1 and Comparative Example 1.

[0118] The "trifunctional AMA Si-H converter" is a polyfunctional organosilicon compound having the following formula: [ka] It is prepared in the following Example 2.

[0119] The "bifunctional ETM Si-H converter" is a polyfunctional organosilicon compound having the following formula: [ka] It is prepared in the following Example 3.

[0120] Example 1: Preparation of a bifunctional AMA Si-H converter

[0121] A dry jacketed reactor (300 mL) equipped with a mechanical stirrer is filled with sodium acetate (anhydrous; 202 mmol; 1.2 equivalents) and toluene (anhydrous; 54 mL) to obtain a heterogeneous mixture. This mixture is cooled to 15°C under a nitrogen atmosphere while stirring (250 rpm) and maintained therein. Dichloromethylsilane (101 mmol; 0.6 equivalents) is gradually added to the mixture in the reactor over 5 minutes to generate an exothermic reaction at 20°C to obtain a reactive premixture. This is stirred for 30 minutes. Next, AMA silanol (167 mmol; 1 equivalent; 3.0 M in toluene) is gradually added to the reactive premixture over 30 minutes (rate: 1.5 mL / min), while maintaining the reaction temperature below 20°C. The resulting reaction mixture is stirred at 15°C for 30 minutes, then filled with water (33 mL), and stirred for another 10 minutes. The resulting mixture was washed with water (33 mL), aqueous sodium carbonate solution (3 M; 33 mL), and brine (33 mL), and the organic matter was concentrated (by vacuum distillation) to obtain the product as a clear viscous liquid (bifunctional AMA Si-H converter; 49.2 g; 99% yield; 2% residual silanol (GCMS)).

[0122] Example 2: Preparation of a trifunctional AMA Si-H converter

[0123] A dry jacketed reactor (300 mL) equipped with a mechanical stirrer is filled with sodium acetate (anhydrous; 193 mmol; 1.1 equivalents) and toluene (anhydrous; 58 mL) to obtain a heterogeneous mixture. This mixture is cooled to 15°C under a nitrogen atmosphere while stirring (250 rpm) and maintained there. Trichlorosilane(61.4 mmol; 0.35 equivalents) is gradually added to the mixture in the reactor over 15 minutes to generate an exothermic reaction at 8°C and obtain a reactive premixture. This is stirred for 90 minutes. Next, AMA silanol (174 mmol; 1 equivalent; 3.0 M in toluene) is gradually added to the reactive premixture over 30 minutes (rate: 1.5 mL / min), while maintaining the reaction temperature below 22°C. The resulting reaction mixture is stirred at 15°C for 150 minutes, then water (33 mL) is added and stirred for 10 minutes. The resulting mixture is washed with water (33 mL), aqueous sodium carbonate solution (3 M; 33 mL), and brine (33 mL), and the organic matter is concentrated (by vacuum distillation) to obtain the product as a clear viscous liquid (trifunctional AMA Si-H converter; 47.5 g; 96% yield).

[0124] Example 3: Preparation of a bifunctional ETM Si-H converter

[0125] A dry reactor equipped with a stirrer and nitrogen sweep is filled with sodium acetate (anhydrous, oven-dried; 2.6 g; 31.6 mmol; 1.26 equivalents) and toluene (anhydrous; 50 mL) under a nitrogen atmosphere to obtain a heterogeneous mixture. This is cooled to 0°C in an ice bath and maintained therein. Next, dichloromethylsilane (1.2 mL; 11.5 mmol; 0.46 equivalents) is added to the mixture in the reactor to obtain a reactive premixture. Then, ETM silanol (7.5 g; 25 mmol; 1 equivalent) is added dropwise to the reactive premixture over 15 minutes to obtain a reaction mixture. This is stirred for 30 minutes, then filtered and washed with water (50 mL), NaOH (1 M); 50 mL, and brine (50 mL). Subsequently, the organic matter was dried with MgSO4, filtered, concentrated (using a rotary evaporator), and dried under high vacuum to obtain the product (bifunctional ETM Si-H converter; 4.72g; 64% yield).

[0126] Comparative Example 1: Preparation of a bifunctional AMA Si-H converter

[0127] A two-necked flask (100 mL) equipped with a nitrogen outlet, thermocouple, dropping funnel, and stirring rod is filled with dichloromethylsilane (5 mmol; 0.5 equivalents) and diethyl ether (20 mL) to obtain a solution. This is cooled to 0°C in an ice bath and maintained there. AMA-silanol (2.76 g; 10 mmol; 1 equivalent), pyridine (0.8 mL; 10 mmol; 1 equivalent), and diethyl ether (5 mL) are filled into the dropping funnel, and the resulting mixture is added dropwise to the stirred solution in the flask to obtain a reaction mixture. This immediately forms a white precipitate and generates heat at 6°C. The ice bath is removed, and the reaction mixture is stirred while warming it to room temperature. The reaction mixture is then filtered (using a plastic frit funnel) to remove the precipitate, and the filtrate is transferred to a separation funnel. Next, the organic matter is washed with aqueous HCl solution (1M; 10 mL), saturated NaHCO3 (10 mL), and brine (10 mL), dried over MgSO4, filtered, and concentrated (rotary evaporator) to obtain a clear liquid. This is then dried under high vacuum to obtain the product (bifunctional AMA Si-H converter; 2.4 g; 80% yield; 8% residual silanol (GCMS)).

[0128] It should be understood that the attached claims are intended to express “modes for carrying out the invention” and are not limited to the specific compounds, compositions, or methods described herein, and may vary between specific embodiments within the scope of the attached claims. With respect to any Markush group on which this specification is used to describe specific features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each member of each Markush group, which is independent of all other Markush members. Each element of a Markush group may be relied upon individually or in combination to provide a suitable basis for a particular embodiment within the scope of the attached claims.

Claims

1. A method for preparing a polyfunctional organosilicon compound, wherein the method is A method comprising reacting (A) an organosilanol compound containing a functional moiety selected from an alkoxysilyl moiety and an acrylicoxy moiety, with (B) a hydridosilane compound having at least two silicon-bonded hydrolyzable groups (Z), in the presence of (C) an acetate, thereby preparing the polyfunctional organosilicon compound. A method wherein each of the hydrolyzable groups (Z) is a halogen.

2. The aforementioned organic silanol compound (A) has the following general formula: 【Chemistry 1】 The method according to claim 1, wherein Y is a functional moiety selected from an alkoxysilyl moiety and an acrylicoxy moiety, each R is an independently selected hydrocarbyl group, and the subscript a is 0, 1, or 2.

3. The aforementioned functional portion Y is given by formula R １ -D- (wherein, R １ D contains an alkoxysilyl group or an acrylooxy group, and D is (i) formula - (CH ２ ) ｍ The method according to claim 2, wherein the hydrocarbon group is (wherein the formula the subscript m is 1 to 6), (ii) an ether moiety, or (iii) a divalent linking group comprising both (i) and (ii).

4. R of the aforementioned functional portion Y １ However, the following formula: 【Chemistry 2】 (In the formula, the subscript b is 1, 2, or 3, and each R ２ R is an independently selected hydrocarbyl group, and each R ３ The method according to claim 3, wherein is an alkoxysilyl group having an independently selected hydrocarbyl group.

5. R of the aforementioned functional portion Y １ However, the following formula: 【Transformation 3】 (wherein each R ４ is independently selected hydrocarbyl or H) is an acryloxy group having the method according to claim 3.

6. The hydridosilane compound (B) has the following general formula: 【Chemistry 4】 (In the formula, each Z is a halogen, and each R ５ The method according to any one of claims 1 to 5, wherein is an independently selected hydrocarbyl group, and the subscript c is 2 or 3.

7. The acetate (C) is of the general formula [R ６ C(O)O] － [M] ＋ (In the formula, R ６ The method according to any one of claims 1 to 6, comprising a complex having (where is a substituted or unsubstituted methyl group, and M is an alkali metal).

8. The method according to any one of claims 1 to 7, comprising reacting the organic silanol compound (A) and the hydridosilane compound (B) in the presence of the acetate (C) to form a reactive premixture by combining the hydridosilane compound (B) and the acetate (C), and subsequently combining the reactive premixture with the organic silanol compound (A) to prepare the polyfunctional organosilicon compound.

9. The method according to claim 8, wherein the reactive premixture comprises an acetoxyhydridosilane intermediate formed in situ from the hydridosilane compound (B) and the acetate (C), and the polyfunctional organosilicon compound is obtained by the reaction of the organosilanol compound (A) with the acetoxyhydridosilane intermediate.

10. The method according to any one of claims 1 to 9, wherein a reaction product containing the polyfunctional organosilicon compound is obtained by reacting the organosilanol compound (A) and the hydridosilane compound (B) in the presence of the acetate (C), wherein (i) the reaction product substantially does not contain by-products formed from the homocondensation of the organosilanol compound (A); (ii) the reaction product contains a residual amount of less than 5% of the organosilanol compound (A) based on the total amount of the organosilanol compound (A) used; (iii) the method further comprises isolating the polyfunctional organosilicon compound from the reaction product; or (iv) any combination of (i) to (iii).

11. A method for preparing a polyfunctional organosilicon compound, wherein the method is A method comprising reacting (A) an organosilanol compound containing a functional moiety selected from an alkoxysilyl moiety and an acrylicoxy moiety, (B) a hydridosilane compound having at least two silicon-bonded hydrolyzable groups, each of which is a halogen, in the presence of (C) an acetate, thereby preparing the polyfunctional organosilicon compound. The aforementioned polyfunctional organosilicon compound has the following general formula: 【Transformation 5】 (In the formula, each R is an independently selected hydrocarbyl group, and each R １ Each R comprises an independently selected alkoxysilyl group or an acrylicoxy group, ５ A method comprising (where is an independently selected hydrocarbyl group, each D is a divalent linking group, each subscript a is independently 0, 1, or 2, and subscript c is 2 or 3).

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