Liquid silicone resin

Abstract

A liquid silicone resin composition includes (A) a polysiloxane, (B) a polyether alcohol compound, and optionally (C) an amino silicone compound. The polysiloxane (A) includes an MQ resin that is dispersed in and optionally functionalized with the polyether alcohol compound (B), and which can also optionally have an amino functionality. The liquid silicone resin composition includes an adjustable viscosity that can range from 100 cps to 800,000 cps at 25°C. A method of making a liquid silicone resin includes combining together a solid silicone resin and the polyether alcohol compound (B) to obtain a mixture including the polysiloxane (A) and the polyether alcohol compound (B), and liquefying the mixture to thereby make the liquid silicone resin composition. The method can optionally include the amino silicone compound (C).

Description

[0001] Cross-references to related applications

[0002] This application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 107,643, filed October 30, 2020, the contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to organosilicon compositions, and more specifically to a liquid organosilicon resin composition and a method for preparing the same.

[0004] Related technical descriptions

[0005] Organosilicones are polymeric materials used in many commercial applications, primarily due to their significant advantages over their carbon-based analogs. More specifically, organosilicones, known as polymeric siloxanes or polysiloxanes, comprise an inorganic silicon-oxygen backbone (…-Si-O-Si-O-Si-O-…) with organic side groups attached to silicon atoms. These organic side groups can be used to link two or more of these backbones together. By varying the -Si-O- chain length, side groups, and crosslinking, organosilicones with diverse properties and compositions can be synthesized, with the consistency of the organosilicon network ranging from liquid to gel to rubber to hard plastics. Organosilicon materials and siloxane materials are used in a wide range of end-use applications and environments, including as components in a broad variety of industrial, home care, and personal care formulations.

[0006] Organosilicon materials and siloxane materials are known in the art and are used in a wide variety of end-use applications and environments. The most common organosilicon materials are based on linear organopolysiloxanes, such as polydimethylsiloxane (PDMS), a type of silicone oil. These organopolysiloxanes are used in many industrial, home care, and personal care formulations. The second largest group of organosilicon materials are based on organosilicon resins formed from branched and cage-like oligomeric siloxanes. Unfortunately, the use of siloxane materials remains limited in certain applications where the specific inherent properties of organopolysiloxanes (e.g., low loss and stable optical transmission, thermal and oxidative stability, etc.) might benefit, due to the weak mechanical properties of conventional organosilicon networks suitable for functionalization and / or further reactions. This may manifest in materials with poor or unsuitable characteristics, such as low tensile strength, low tear strength, etc. Furthermore, since conventional organosilicon networks and carbon-based polymers are generally incompatible and / or have antagonistic properties relative to each other, further research is needed to determine useful methods for efficiently and effectively functionalizing organosilicones (such as organosilicon resins).

[0007] For example, many conventional silicone materials (e.g., siloxanes, silicone resins) are hydrophobic and therefore difficult to mix with polar organic materials under a wide range of conditions. Consequently, these silicone materials are typically used in solid form or, where a solution / dispersion is required, with nonpolar organic (e.g., hydrocarbon) solvents such as benzene, toluene, ethylbenzene, and xylene (i.e., BTEX solvents). Unfortunately, such conditions are often incompatible with certain polar organic materials and the process conditions necessary for their use. Furthermore, the properties of BTEX solvents, which present numerous environmental and health-related issues, require further investigation to ensure the safe and efficient use of silicone materials in non-traditional applications. Summary of the Invention

[0008] A liquid silicone resin composition (“Composition”) is disclosed. The composition comprises (A) a polysiloxane having the following general formula:

[0009] (R 1 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R'R 2 SiO 2 / 2 ) b’ (R 2 SiO 3 / 2 ) c (R'SiO 3 / 2 ) c’ (SiO 4 / 2 ) d Let R be a series of subscripts a, b, b', c, c', and d, each representing a mole fraction such that a + b + b' + c + c' + d = 1, provided that 0 < a < 1, 0 ≤ b < 0.2, 0 ≤ b' ≤ 0.1, 0 < c < 0.2, 0 ≤ c' ≤ 0.1, 0 < d < 1, and 0 ≤ b' + c' ≤ 0.1. The ratio of subscript a to subscript d is between 0.5 and 1.5 (a:d). 1 Independently selected from hydrocarbon groups having 1 to 30 carbon atoms, -OH, and H; each R 2 Independently selected from R 1 and -OX, wherein each X is independently H, a hydrocarbon group R having 1 to 30 carbon atoms, or having the general formula -YR. 3 (-[Y] j -Z) i The polyether portion, wherein R 3 For substituted or unsubstituted hydrocarbon segments, each Y is an independently chosen general formula (C n H 2n O) mThe composition comprises oxidized olefin segments, wherein subscript m is from 1 to 50 and subscript n is independently selected from 2 to 4 in each segment represented by subscript m, each Z is independently H or a resin organosilicon segment, subscript i is from 0 to 8, and subscript j is independently 0 or 1 in each segment represented by subscript i; and each R' includes independently selected amino groups. The composition also comprises (B) having the general formula HO-YR 3 (-[Y] j -Z) i Polyether alcohol compounds, wherein each Y, R 3 Z, subscript j, and subscript i are defined as above.

[0010] A method for preparing a liquid silicone resin composition is also disclosed. The method includes (I) combining a solid silicone resin and a polyether alcohol compound (B) to obtain a mixture comprising a polysiloxane (A) and a polyether alcohol compound (B). The solid silicone resin has the following general formula:

[0011] (R 1 3SiO 1 / 2 ) a (R 4 2SiO 2 / 2 ) b (R 4 SiO 3 / 2 ) c (SiO 4 / 2 ) d ,

[0012] Each R 4 Independently selected from R 1 And -OR, the condition is R 4 In at least one T-methoxy unit denoted by the subscript c, the group is selected from -OH and -OR, and each R 1 R and subscripts a, b, c and d are as defined above. The method further includes (II) liquefying the mixture comprising polysiloxane (A) and polyether alcohol compound (B) to prepare a liquid silicone resin composition. The method may optionally utilize (C) an aminosilicone compound. Detailed Implementation

[0013] This document provides a liquid silicone resin composition (“composition”) and a method for its preparation. As will be understood from the description herein, the composition provides a functional MQ resin in liquid form optionally end-capped with one or more polyether-containing moieties, without the need for solvents or other carrier media. “Liquid” means that the composition is flowable and has a viscosity measurable at 25°C. The specific materials and conditions used provide the composition with a highly tunable liquid viscosity, thus providing the composition with numerous uses in a variety of compositions and methods, including the preparation of curable compositions (e.g., those based on one or more silicones) and their various components. Furthermore, due to its unique structural characteristics, the liquid composition is suitable for dispersion in water, polyols, or other polar liquid formulations (e.g., those containing anionic and / or nonionic surfactants).

[0014] The composition typically includes (A) a polysiloxane, (B) a polyether alcohol compound and optionally (C) an aminosilane compound, as described in sequence below, as well as other compounds that may be present in the composition, which herein may be collectively referred to as “components” of the composition (i.e., “component (A)”, “component (B)”, etc., respectively), or similarly as “compounds” and / or “reagents” (A) and / or (B), etc.

[0015] As will be understood by those skilled in the art, siloxanes can be characterized by the [M], [D], [T], and / or [Q] units / siloxy groups therein. More specifically, these [M], [D], [T], and [Q] siloxy groups each represent a structural unit of a separate functional group present in polysiloxanes such as organosiloxanes and organopolysiloxanes. In particular, [M] represents the general formula R”3SiO 1 / 2 The single functional unit; [D] represents the general formula R”2SiO 2 / 2 The bifunctional unit; [T] represents the general formula R”SiO 3 / 2 The three functional units; and [Q] represents the general formula SiO 4 / 2 The four functional units are shown in the following general structural part:

[0016]

[0017] In these general structural portions, each R” is independently a monovalent or polyvalent substituent. As understood in the art, there are no particular limitations on the specific substituents applicable to each R”, and they can be monoatomic or polyatomic, organic or inorganic, straight or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, and combinations thereof. Typically, each R” is independently selected from hydrocarbon groups, alkoxy and / or aryloxy groups, and silanoxy groups, such as those represented by any one or a combination of the above [M], [D], [T] and / or [Q] units.

[0018] As described above, the composition comprises a polysiloxane (A). As will be appreciated from the description herein, the polysiloxane (A) may be classified or otherwise referred to as an MQ resin, wherein, as described above, M represents a monofunctional siloxy group (i.e., R”3SiO) 1 / 2 (where R" represents a silicon-bonded substituent) and Q represents a tetrafunctional silyloxy unit (i.e., SiO2). 4 / 2 Such MQ resins are known in the art as macromolecular polymers consisting primarily of M and Q units and optionally a limited number of D and / or T units (e.g., ≤20 mol% in total), and are typically present in solid form (e.g., powder or flakes) unless placed in a solvent. These MQ resins are generally simply represented by the general formula [M]x[Q], where the subscript x refers to the molar ratio of M siloxy units to Q siloxy units when the molar number of Q siloxy units is normalized to 1. In such cases, the larger the value of x, the lower the crosslinking density of the MQ resin. Conversely, as the value of x decreases, the number of M siloxy units decreases, and therefore more Q siloxy units are networked without being capped by M siloxy units. However, it should be appreciated that the normalized content of Q siloxy units does not imply or limit the MQ resin to only one Q unit. Rather, MQ resins typically comprise multiple Q siloxy units clustered or bonded together, as will be understood from the following description.

[0019] Typically, polysiloxane (A) has the following general formula:

[0020] (R 1 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R'R 2 SiO 2 / 2 ) b '(R 2 SiO 3 / 2 ) c (R'SiO 3 / 2 ) c’ (SiO 4 / 2 ) d ,

[0021] Where subscripts a, b, b', c, c', and d are mole fractions such that a + b + b' + c + c' + d = 1, provided that 0 < a < 1, 0 ≤ b < 0.2, 0 ≤ b' ≤ 0.1, 0 < c < 0.2, 0 ≤ c' ≤ 0.1, 0 < d < 1, 0 ≤ b' + c' ≤ 0.1, and the ratio of subscript a to subscript d is 0.5 to 1.5 (a:d); each R 1 Independently selected from hydrocarbon groups having 1 to 30 carbon atoms, -OH, and H; each R 2 Independently selected from R 1 and -OX, wherein each X is independently H, a hydrocarbon group R having 1 to 30 carbon atoms, or a polyether moiety as described below; and each R' includes an independently selected amino group.

[0022] Referring to the general formula of polysiloxane (A) above, it is applicable to R 1The hydrocarbon group includes a monovalent hydrocarbon moiety, as well as its derivatives and modifications, which can be independently substituted or unsubstituted, straight-chain, branched, cyclic, or combinations thereof, and saturated or unsaturated. Regarding such hydrocarbon groups, the term "unsubstituted" describes a hydrocarbon moiety consisting of carbon and hydrogen atoms, i.e., without heteroatom substituents. The term "substituted" describes a hydrocarbon moiety in which at least one hydrogen atom is replaced by an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a side-substituent or a terminal substituent), a carbon atom within the chain / main chain of the hydrocarbon is replaced by an atom other than carbon (e.g., a heteroatom, such as oxygen, sulfur, nitrogen, etc.) (i.e., as part of the chain / main chain), or both conditions are met. Therefore, a suitable hydrocarbon group may comprise or be a hydrocarbon moiety having one or more substituents (i.e., attached to and / or integrated with the carbon chain / main chain) in and / or on its carbon chain / main chain, such that the hydrocarbon moiety may comprise or be an ether, ester, etc. Straight-chain and branched hydrocarbon groups may be independently saturated or unsaturated, and when unsaturated, may be conjugated or non-conjugated. Cyclic hydrocarbon groups may be independently monocyclic or polycyclic, and encompass cycloalkyl groups, aryl groups, and heterocycles, which may be aromatic, saturated, and non-aromatic and / or non-conjugated, etc. Examples of combinations of straight-chain and cyclic hydrocarbon groups include alkylaryl groups, aralkyl groups, etc. General examples suitable for use as a hydrocarbon moiety in or as a hydrocarbon group include alkyl groups, aryl groups, alkenyl groups, alkynyl groups, haloalkyl groups, etc., and their derivatives, modifications, and combinations thereof. Examples of 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, etc. (i.e., other straight-chain or branched saturated hydrocarbon groups, such as those having more than 6 carbon atoms). Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethylphenyl, etc., and their derivatives and modifications, which may overlap with alkylaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethylphenyl, etc.). Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl, etc., and their derivatives and modifications. General examples of haloalkyl groups include haloderivatized derivatives of the hydrocarbon moiety described above, such as haloalkyl groups (e.g., any of the alkyl groups described above, wherein one or more hydrogen atoms are replaced by halogen atoms (such as F or Cl), aryl groups (e.g., any of the aryl groups described above, wherein one or more hydrogen atoms are replaced by halogen atoms (such as F or Cl), and combinations thereof.Examples of halogenated alkyl groups 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, 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, etc., as well as their derivatives and modifications. Examples of halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl groups, etc., as well as their derivatives and modifications.

[0023] In some implementations, at least one R 1 It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. For example, in some such embodiments, at least one R 1 Alkyl groups are independently selected substituted or unsubstituted groups, such as alkyl groups having 1 to 24, alternatively 1 to 18, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, or alternatively 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl groups, ethyl groups, propyl groups (e.g., n-propyl and isopropyl groups), butyl groups (e.g., n-butyl, sec-butyl, isobutyl, and tert-butyl groups), pentyl groups, hexyl groups, heptyl groups, etc., and their derivatives and / or modifications. Examples of derivatives and / or modifications of such alkyl groups include their substituted forms. For example, R 1 It may include, or alternatively may include, a hydroxyethyl group, which will be understood as a derivative and / or modified form of the aforementioned ethyl group. Similarly, R 1 It may include, or alternatively may be independently selected, substituted or unsubstituted alkenyl groups having 2 to 6 carbon atoms, such as 2 to 5, alternatively 2 to 4, or alternatively 2 to 3 carbon atoms. In some embodiments, the polysiloxane (A) comprises at least two R groups containing alkenyl functional groups. 1 Groups (i.e., at least two R groups) 1 Selected from substituted or unsubstituted alkenyl groups). In these or other embodiments, each R 1 Independently selected from H, -OH, C1-C6 alkyl groups, aryl groups, alkenyl groups, phenyl groups, vinyl groups, and combinations thereof. In some embodiments, all R... 1 At least 50 mol% of the group, alternatively at least 60 mol%, alternatively at least 70 mol%, alternatively at least 80 mol%, alternatively at least 90 mol% is a hydrocarbon group.

[0024] Continuing with reference to the general formula for polysiloxane (A) above, each R2 Independently selected from R 1 and -OX, where each X is independently H (i.e., such that R 2 (i.e., a hydroxyl group), a hydrocarbon group R having 1 to 30 carbon atoms (i.e., R such that R...) 2 The alkyl group (of formula -OR) or polyether moiety is used. When X is an alkyl group, the alkyl group R can be selected from any alkyl group having 1 to 30 carbon atoms as described above. Therefore, examples of alkyl groups suitable for X include alkoxy and aryloxy groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, benzyloxy, etc., and their derivatives and modifications. Examples of aryloxy groups include phenoxy, toluoxy, pentafluorophenoxy, etc., and their derivatives and modifications. In some embodiments, each R 2 Independently selected from R 1 and -OR, where each R 1 The R is independently selected from H, -OH, and alkyl and aryl groups containing 1 to 30 carbon atoms, and each R is independently selected from alkyl and aryl groups containing 1 to 30 carbon atoms. In these or other embodiments, each R 2 The R is independently selected from -OH and -OR, wherein each R is independently selected from alkyl and aryl groups containing 1 to 30 carbon atoms.

[0025] As described above, in some implementations, at least one R 2 It has the formula -OX, where X is the polyether moiety. In these embodiments, the polyether moiety is not particularly limited and generally contains the general formula (C n m 2n O) m The olefin oxide segment, wherein the subscript m is 1 to 50 and the subscript n is independently 2, 3, or 4 in each portion represented by the subscript m. In some embodiments, the subscript m is 1 to 45, such as 1 to 40, alternatively 1 to 30, alternatively 1 to 25, alternatively 1 to 20, alternatively 1 to 15. In a specific embodiment, the subscript m is at least 2, such that the polyoxyethylene portion may contain one or more olefin oxide units selected from: ethylene oxide units (e.g., -(C2H4O)-, i.e., where the subscript n is 2), propylene oxide units (e.g., -(C3H6O)-, i.e., where the subscript n is 3), and butene oxide units (e.g., -(C4H8O)-, i.e., where the subscript n is 4). When the olefin oxide segment contains more than one type of olefin oxide unit (i.e., a polyoxyethylene), the olefin oxide units may be arranged in any manner, such as in block form (e.g., ordered blocks and / or random blocks), random form, or combinations thereof. In specific embodiments, the olefin oxide segment comprises both ethylene oxide and propylene oxide units. In some such embodiments, the olefin oxide segment is an ethylene oxide-propylene oxide block copolymer.

[0026] The polyether moiety may contain more than one oxidized olefin segment. For example, in some embodiments, X comprises a segment having the general formula -YR. 3 (-[Y] j -Z) i The polyether portion, wherein R 3 For substituted or unsubstituted hydrocarbon segments, each Y is an independently chosen general formula (C) as described above. n H 2n O) m The oxidized olefin segment, Z is the end group, subscript i is 0 to 8, and in each part represented by subscript i, subscript j is independently 0 or 1. In these embodiments, R 3 It is a hydrocarbon linking group with at least a divalent charge. More specifically, as used in this context, the hydrocarbon segment R... 3 The valence refers to the formula (-[Y]) bonded to it, excluding the olefinic segment Y. j The number of substituents (-Z). Therefore, in this context, the hydrocarbon segment R 3 The valence can be described by the subscript i+1.

[0027] Typically, each hydrocarbon segment R 3 Independently comprising one or more substituted or unsubstituted hydrocarbon groups, i.e., optionally modified or substituted hydrocarbon groups, such as those modified or substituted by side-attached alkoxy, carbonyl, siloxy, silyl, amino, amide, acetoxy, or aminooxy groups and / or internal O, N, or S atoms (i.e., in the main chain). For example, in some embodiments, the polysiloxane (A) comprises at least one X corresponding to the general formula of the polyether moiety above, wherein the hydrocarbon segment R 3 It comprises, or alternatively, a straight-chain or branched hydrocarbon group having 3 to 30 carbon atoms, optionally comprising one or more aromatic groups, ether groups, amine groups, or combinations thereof. In some such embodiments, the hydrocarbon segment R 3 It is a C1-C20 hydrocarbon group. In these or other embodiments, each hydrocarbon segment R 3 Independently comprising an aromatic group, an ether group, an amine group, or a combination thereof. As will be appreciated from the description herein, the above-mentioned hydrocarbon segment R 3 The ether and amine groups can be internal (e.g., containing O or N atoms in the main chain of a straight or branched hydrocarbon group) or side-attached (e.g., containing alkoxy or amine groups bonded to the main chain of a straight or branched hydrocarbon group).

[0028] Each hydrocarbon segment R 3 It can exist independently as a straight chain or a branched chain. More specifically, as will be recognized from the description herein, R 3 It typically includes at most i branches (i.e., 0 to 8 branches), where for a given R...3 For each branch leading to the terminal group Z, the subscript j is 1. In some embodiments, each hydrocarbon segment R 3 It contains branched hydrocarbon groups having 3 to 16 carbon atoms. In some embodiments, each oxidized olefin segment Y independently has the formula (C2H4O). x (C3H6O) y (C4H8O) z , where the subscript x is from 1 to 50, the subscript y is from 0 to 50, and the subscript z is from 0 to 50, and the unit represented by the subscripts x, y and z can be random or block in the oxidized olefin segment.

[0029] In some embodiments, the polysiloxane (A) comprises at least one X corresponding to the general formula of the polyether moiety above, wherein the subscript i is 0 and each hydrocarbon segment R 3 It independently comprises a straight-chain or branched hydrocarbon group having 3 to 30 carbon atoms. In these or other embodiments, the polysiloxane (A) comprises at least one X, where the subscript i is 1, and the hydrocarbon segment R 3 It comprises at least one group selected from: straight-chain or branched hydrocarbon groups having 3 to 30 carbon atoms, phenols, tetrahydrofurans, and alkylamines, each optionally substituted with one or more alkoxy groups. In these or other embodiments, the polysiloxane (A) comprises at least one X, wherein the subscript i is at least 2, and the hydrocarbon segment R 3 It contains at least one group selected from the following: straight-chain or branched hydrocarbon groups having 3 to 30 carbon atoms, alkylamines, polyamines, polyamides, polyaziridines, polyphenols, and polyesters.

[0030] Typically, each end group Z is independently selected from H (i.e., making the polyether portion terminally hydroxyl-functional) or the silicone portion of the resin (i.e., condensation from the terminal hydroxyl functional group with the condensable silicon-bonded portion of the polysiloxane (A)). For example, when the subscript i is at least 1, the end group Z may represent a crosslinking with another silanol group of the polysiloxane (A). Similarly, when i > 1, the polysiloxane (A) may contain more than one crosslink. Those skilled in the art will recognize that the presence and density of such crosslinking in the polysiloxane (A) in the composition depends on many factors, such as the hydroxyl (e.g., silanol) functionality of the selected silicone resin, the functionality of the selected polyether alcohol compound (B), the ratio of the silicone resin to the polyether alcohol compound (B) used to prepare the composition, the degree of conversion, etc., as described below with respect to the methods. Likewise, the presence of such crosslinking can be determined by methods known in the art, such as by rheological measurements of the gel point, which is due to the increase in average molecular weight in response to crosslinking (i.e., where the gel point indicates the divergence of weight-average molecular weight towards infinity). For example, a rheometer (e.g., a rheomechanical spectrometer using a parallel-plate geometry) can be used to perform frequency-scanning experiments to determine the dynamic storage modulus, equilibrium modulus, and modulus changes during composition preparation. Given the methods described herein, a better understanding of the full range of end-group Z and the potential for crosslinking polysiloxanes (A) will be achieved.

[0031] Each R′ independently contains an amino group. In some embodiments, each R' is an amino group. The amino group of R' may have the formula -N(H). f R 2-f Each R is independently selected and defined above, i.e., each R is an independently selected hydrocarbon group, and the subscript f is independently 0, 1, or 2. In other embodiments, each R' independently comprises a hydrocarbon group substituted with an amino group. Suitable hydrocarbon groups are as described above. In a specific embodiment, each R' independently comprises an aliphatic hydrocarbon group substituted with an amino group. The aliphatic hydrocarbon group may be linear or cyclic and is typically saturated. In a specific embodiment, each R' comprises an alkylamino group. For example, each R' may have the formula -(CH2). g N(H) f R 2-f Each subscript g is independently 1 to 30, alternatively 1 to 25, alternatively 1 to 20, alternatively 1 to 15, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 2 to 4, and R' and subscript f are as defined above. In a specific implementation, subscript g is 3 and subscript f is 2, such that each R' has the formula -(CH2)3N(H)2.

[0032] Continuing with reference to the general formula for polysiloxane (A) above, subscripts a, b, b', c, c', and d each represent a mole fraction, such that a + b + b' + c + c' + d = 1. As those skilled in the art will recognize, subscripts a, b, c, d, and e correspond to M, D, T, and Q siloxy units, respectively. Subscripts b and b' in the above formula both represent D siloxy units, and subscripts c and c' in the above formula both represent T siloxy units, but with different silicon-bonded substituents (R). 2 Relative to R'). Typically, the fraction of each siloxy unit is selected such that 0 < a < 1, 0 ≤ b < 0.2, 0 ≤ b' ≤ 0.1, 0 < c < 0.2, 0 ≤ c' ≤ 0.1, 0 < d < 1 and 0 ≤ b' + c' ≤ 0.1, that is, wherein the polysiloxane (A) optionally excludes D siloxy units (including those indicated by subscripts b and / or b'), optionally excludes T siloxy units indicated by subscript c', but includes at least one of each of M, T, and Q siloxy units (as indicated by subscripts a, c, and d). However, it will be appreciated that in such embodiments, the polysiloxane (A) will generally be configured such that in at least one, alternatively most, alternatively substantially all of the T siloxy units indicated by subscript c and present therein, R 2 The value is -OX. Similarly, although optionally excluding D-siloxy units, the polysiloxane (A) may contain a limited proportion of D-siloxy units. However, typically, the subscripts b and c together are less than 0.2 (i.e., b + c ≤ 0.2). In some embodiments, the subscript a is selected from 0.3 to 0.6. In these or other such embodiments, the subscript d is selected from 0.4 to 0.7. In a specific embodiment, the subscript c' is 0. In other embodiments, the subscript c' is greater than 0 to 0.1, alternatively greater than 0 to 0.05, alternatively greater than 0 to 0.04, alternatively 0.01 to 0.04. In other specific embodiments, the subscript b' is 0. In yet another embodiment, the subscript b' is greater than 0 to 0.1, alternatively greater than 0 to 0.05, alternatively greater than 0 to 0.04, alternatively 0.01 to 0.04. In yet another embodiment, b' and c' are each 0. In other implementations, (b'+c') is greater than 0 to 0.1, or alternatively greater than 0 to 0.05, or alternatively greater than 0 to 0.04, or alternatively 0.01 to 0.04.

[0033] It will be appreciated that the subscripts a and d generally refer to the MQ resin portion of the polysiloxane (A), such that the ratio of subscript a to subscript d can be used to characterize the polysiloxane (A). For example, in some embodiments, the ratio of M siloxy units represented by subscript a to Q siloxy units represented by subscript d is 0.5 to 1.5 (a:d). In these or other embodiments, the ratio of M siloxy units represented by subscript a to Q siloxy units represented by subscript d is 0.7 to 1.2 (a:d).

[0034] As will be recognized according to the methods further described below, the characteristics and properties of the polysiloxane (A) will be selected and controlled by the specific components used to prepare the liquid silicone resin composition as a whole.

[0035] As described above, the composition also comprises a polyether alcohol compound (B). Typically, the polyether alcohol compound (B) has the general formula HO-YR. 3 (-[Y] j -H) i Each Y, R 3 The subscripts i and j are as defined above. More specifically, R 3 Y is a substituted or unsubstituted hydrocarbon segment, each Y being an independently selected oxidized olefin segment, with subscripts i ranging from 0 to 8, and in each segment represented by subscript i, subscript j independently being 0 or 1. Further descriptions and examples of polyether alcohol compounds (B) are provided below. However, as will be further appreciated in detail according to the methods described herein, the general formula of polyether alcohol compounds (B) consists of Y and R... 3 The groups represented are the same as those represented above in the polyether portion of polysiloxane (A) (i.e., in terms of scope). Therefore, for each Y and R 3 The description of the parts indicated by the subscripts .j and i also applies to the conservative part of the formula for the polyether portion of both polysiloxane (A) and polyether alcohol compound (B).

[0036] Generally, the polyether alcohol compound (B) comprises (b-1) a compound containing at least one alkoxylable group (e.g., a functional group containing an unstable hydrogen atom bonded to a nucleophilic O, N, or S atom, such as a -OH, -NH, or SH group) (i.e., the alkoxylable compound (b-1)) and (b-2) an alkoxylating agent (e.g., an alkylene oxide, a polyoxyalkylene compound, etc.), as will be understood by those skilled in the art. The alkoxylation reaction is not limited and will be selected based on the specific alkoxylable compound (b-1) and alkoxylating agent (b-2) used.

[0037] Typically, the alkoxylated compound (b-1) is an organic alcohol, i.e., an organic compound comprising a carbon backbone and at least one hydroxyl (i.e., -OH) group. In such embodiments, the alkoxylated compound (b-1) may be more specifically referred to as an alcohol compound (b-1). As will be understood from the examples and descriptions below, the alcohol compound (b-1) can be a monool (i.e., containing only one hydroxyl functional group) or a polyol (i.e., containing at least two hydroxyl groups), such as diols, triols, etc. The carbon backbone of the alcohol compound (b-1) can be substituted or unsubstituted, for example, substituted by any of the functional groups described herein. When substituted, the carbon backbone of the alcohol compound (b-1) may contain side-chain substitutions (i.e., substitutions for hydrogen atoms attached to the carbon backbone) or substitutions of carbon atoms within the backbone itself (e.g., through other heteroatoms, such as O, S, N, etc.). Therefore, it should be recognized that although characterized as or otherwise referred to as an organic alcohol, the alcohol compound (b-1) may be alternatively or further defined according to other functional groups (when present) (e.g., as an amino alcohol, etc.). In addition, the carbon backbone may be straight or branched, and thus may contain straight, branched and / or cyclic hydrocarbon segments.

[0038] As will be understood from the description herein, alcohol compounds (b-1) generally correspond to the general formula HO-R. 3 (-OH) i , where R 3 The subscript i is as defined above. More specifically, R 3 The hydrocarbon segment is represented by the subscript i, which ranges from 0 to 8. In such embodiments, it should be recognized that the hydrocarbon segment R... 3 The carbon backbone of the alcohol compound (b-1), as indicated by the subscript i, may contain 0 to 8 hydroxyl groups in addition to the required hydroxyl groups.

[0039] In some embodiments, the subscript i is 0, such that the alcohol compound (b-1) has the general formula HO-R. 3 Alcohols. In some such embodiments, R 3 It includes, or alternatively, a straight-chain or branched hydrocarbon group having 3 to 30 carbon atoms. For example, in some embodiments, R 3 It is a branched hydrocarbon group having 3 to 30 carbon atoms. In some such embodiments, the alcohol compound (b-1) has the following formula:

[0040]

[0041] Where R 5 R 6 and R 7 Independently selected from C1-C13 alkyl groups. For example, in some such embodiments, R 5 and R 6Each is independently selected from C1-4 alkyl groups, and R 7 It is an H or C1-C13 alkyl group. In some of these embodiments, R 3 It contains a total of 7 to 16 carbon atoms, such as 9 to 12 carbon atoms. In some embodiments, R 3 It contains a branching degree of at least 3. In this context, the term "branching degree" as used herein refers to the total number of methyl (-CH3) groups minus 1. For example, R containing an alkyl group with four methyl substituents. 3 It contains a branching degree of 3. In some implementations, R 5 An alkyl group comprising 3 to 12 carbon atoms, such as a C3-C8 alkyl group, or alternatively a C4-C6 alkyl group. In such embodiments, R 5 It contains at least two methyl groups. In these or other embodiments, R 6 An alkyl group comprising 3 to 12 carbon atoms, such as a C4-C10 alkyl group, and alternatively a C6-C8 alkyl group. In some embodiments, R 7 It contains at least two methyl groups. For example, in some embodiments, R 7 It is a C1-C3 alkyl group. In other embodiments, R 7 For H. In some implementations, R 5 The resultant is CH3(CH2)2CH(CH3)(CH2)2CH(CH3), and R 6 For H, and R 7 The form is CH3. In a specific embodiment, the alcohol compound (b-1) is (3-methyl-6-ethyl)-2-nonanol.

[0042] In some embodiments, the subscript i is 1, such that the alcohol compound (b-1) has the general formula HO-R. 3 -OH diols, wherein the hydrocarbon segment is a divalent linker. In some embodiments, for example, R 3 It includes, alternatively, an alkyl group (i.e., making the alcohol compound (b-1) a diol) or a substituted alkyl group (e.g., a diethylamino group, making the alcohol compound (b-1) a diethanolamine), an aryl group (e.g., phenyl, benzyl, tolyl, etc.), a tetrahydrofuran group, or other bifunctional materials, such as those derived from the ring-opening of epoxy adducts or alkoxydiols.

[0043] In certain embodiments, the subscript i ≥ 2, such that the alcohol compound (b-1) can be further defined as a polyol, such as a triol, a tetraol, etc. In such embodiments, the alcohol compound (b-1) is exemplified as glycerol, pentaerythritol, sugar alcohols (e.g., sorbitol, xylitol, mannitol, etc.), etc. In some such embodiments, R... 3Includes, and alternatively selected from, alkylamines, polyamines, polyamides, polyaziridines, polyphenols, and polyesters. In some embodiments, for example, R 3 This includes, and alternatively, phenolic resins, epoxy adducts of glycidyl ethers and polyols, and epoxy adducts of glycidyl ethers and diamines or polyamines (e.g., secondary diamines). In any of these embodiments, the subscript i may be 2 to 8, such that the alcohol compound (b-1) comprises 2 to 8 hydroxyl groups, such as 3 to 8, alternatively 3 to 6, or alternatively 3 to 5 hydroxyl groups.

[0044] It should be recognized that other polyols and alcohols can also be used as alcohol compounds (b-1) to prepare polyether alcohol compounds (B). For example, in some embodiments, alcohol compound (b-1) is selected from polyether polyols, polyester polyols, polycarbonate polyols, acrylic polyols, polyols derived from isocyanate prepolymers (e.g., those with a functionality of 2 to 8, etc.).

[0045] The alkoxylating agent (b-2) is not limited and may be or include any alkoxylating compound suitable for replacing the alkoxylable compound (b-1) to obtain the polyether alcohol compound (B) as described herein. Typically, the alkoxylating agent (b-2) is selected from alkylene oxides, polyoxyethylene compounds, and combinations thereof. For example, in some embodiments, the alkoxylating agent (b-2) is selected from ethylene oxide, propylene oxide, butane oxide, and combinations thereof. In other embodiments, the alkoxylating agent (b-2) is selected from polyethylene oxide, polypropylene oxide, polybutylene oxide, and combinations thereof (e.g., in random or block polymer form). Those skilled in the art will recognize that, as used herein, the term "alkoxylation," for example, relating to precursors (b-1) and (b-2) of the polyether alcohol compound (B), can be considered functional and / or descriptive and also includes ether / etherified products.

[0046] Those skilled in the art will recognize that the number of hydroxyl groups present on the alkoxylated compound (b-1) will affect the overall structure of the polyether alcohol compound (B) itself. In particular, the polyether alcohol compound (B) may contain up to i=1 polyoxyalkylene groups, i.e., the alkoxylated groups of the alcohol compound (b-1) are alkoxylated with an alkoxylating agent (b-2).

[0047] Regarding the polyether alcohol compound (B) itself, for example, corresponding to the general formula HO-YR 3 (-[Y] j -H) i Each oxidized olefin segment Y can independently have the formula (C2H4O). x (C3H6O) y (C4H8O) zThe subscripts x, y, and z are 1 to 50, y, and z, respectively, and the units represented by the subscripts x, y, and z in each olefinic segment can be independently random or block in form. In some embodiments, in each olefinic segment Y, the subscripts x, y, and z are 1 to 20, y, and z are 0 to 20. In some such embodiments, x + y + z = 1 to 50, such as 1 to 20, alternatively 10 to 20. In a specific embodiment, the subscripts x, y, and z are both 0, such that the polyether alcohol compound (B) can be further defined as polyoxyethylene alcohol.

[0048] In some embodiments, the polyether alcohol compound (B) is a nonionic surfactant. For example, in some such embodiments, the polyether alcohol compound (B) may be selected from linear ethoxylates, branched ethoxylates (e.g., polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether), amine ethoxylates (e.g., tertiary amine ethoxylates, aliphatic amine ethoxylates and / or propoxylates), ethoxylated diols, propoxylated diols and / or butoxylated diols, etc.

[0049] As will be apparent from the above description, in some embodiments, the polyether alcohol compound (B) may have the general formula HO-(C2H4O). x (C3H6O) y (C4H8O) z -CR 5 R 6 R 7 , where R 5 R 6 R 7 The subscripts x, y, and z are as defined above. In some such implementations, for example, the subscript x is 1 to 40, and the subscripts y and z are chosen such that y + z = 1 - 6, R 5 and R 6 For independently selected C1-C4 alkyl groups, and R 7 It is H or C1-C13 alkyl. In some such embodiments, it is composed of the derivative formula -CR 5 R 6 R 7 The represented portion contains a total of 7 to 16 carbon atoms and a branching degree of at least 3.

[0050] In some embodiments, the polyether alcohol compound (B) has the following formula:

[0051]

[0052] Where R 8 H or isopropyl; R 9It is CH3 or CH2CH3; the subscript y' is 1 to 5, such as 1 to 4, alternatively 2 to 4; and the subscript x is 2 to 30, such as 2 to 20, alternatively 2 to 10, alternatively 2 to 9, alternatively 5 to 9. In some of these embodiments, R 8 For H and R 9 The form is CH3, which gives the polyether alcohol compound (B) the formula:

[0053]

[0054] The subscripts y' and x are as defined above. In other implementations, R 8 The isopropyl group gives polyether alcohol compound (B) the formula:

[0055]

[0056] The subscripts y' and x are defined as above.

[0057] Typically, the polyether alcohol compound (B) can be prepared with a narrow molecular weight distribution or otherwise obtained, as expressed by the polydispersity index (PDI) (i.e., weight-average molecular weight / number-average molecular weight (Mw / Mn), determined, for example, by gel permeation chromatography). For example, in some embodiments, the polyether alcohol compound (B) contains a PDI of 1.15 or less, alternatively 1.1 or less. In some embodiments, the molecular weight (Mw) of the polyether alcohol compound (B) is less than 5000, for example, Mw is 10 to less than 5000, alternatively 10 to 4500, alternatively 50 to 4000, alternatively 100 to 3000, alternatively 100 to 2000.

[0058] In these or other embodiments, the polyether alcohol compound (B) comprises a low level of residual unreacted alkoxylated compound (b-1), such as alcohol compound (b-1) (i.e., unalkoxylated alcohol). For example, in some embodiments, the polyether alcohol compound (B) comprises less than 3% by weight, alternatively less than 2% by weight, alternatively less, alternatively 1% by weight or less, alternatively 0.5% by weight of residual / unreacted alcohol compound (b-1). In some embodiments, the composition comprises a mixture of more than one polyether alcohol compound (B), such as 2, 3, 4, 5 or more individually selected polyether alcohol compounds (B).

[0059] The amounts of components (A) and (B) in the composition may vary. In some embodiments, for example, the composition comprises 10% to 80% by weight of polysiloxane (A) based on the total weight of the composition. Similarly, in these or other embodiments, the composition comprises 10% to 95% by weight of polyether alcohol compound (B) based on the total weight of the composition. In specific embodiments, the composition comprises 10% to 80% by weight, alternatively 20% to 80% by weight, alternatively 20% to 70% by weight, or alternatively 30% to 70% by weight of polysiloxane (A) based on the total weight of the composition. In these embodiments, the balance of the composition may consist only of polyether alcohol compound (B), or alternatively, may consist of a combination of polyether alcohol compound (B) with one or more additional components of the composition. For example, the composition may contain a catalyst, or a solvent or carrier medium, as will be better understood according to the methods described below. However, in some embodiments, the composition does not, or alternatively substantially does not contain a catalyst. In these or other embodiments, the composition does not, or alternatively substantially does not contain cyclic siloxanes. In these or other embodiments, the composition contains less than 1% by weight of solvent based on the total weight of the composition. In other embodiments, the composition is free from, or alternatively substantially free from, solvents or carrier media (i.e., other than component (B) itself).

[0060] In some embodiments, the composition further comprises (C) an aminosilicone compound. Typically, the aminosilicone compound (C) is used to impart a D-siloxy unit (if present) indicated by subscript b and / or a T-siloxy unit (if present) indicated by subscript c' to the polysiloxane (A), as described below with reference to the method of preparing the composition. The use of the aminosilicone compound (C) is optional in the preparation of the polysiloxane (A) and / or the composition. When used, some residual amount of the aminosilicone compound (C) may be present in the composition; that is, the aminosilicone compound (C) may not be completely consumed during the preparation of the polysiloxane (A) and / or the composition.

[0061] Aminosilicone compounds (C) include silicon-bonded substituents containing an amino group, which, if present, can be substituents represented by R' in polysiloxanes (A). Typically, aminosilicone compounds (C) also include silicon-bonded hydroxyl groups and / or hydrolyzable groups, such as alkoxy groups.

[0062] In a specific embodiment, the aminosilane compound (C) comprises, and alternatively is, an aminosilane, such as R'R 10 h Si(OR 10 ) 3-h The aminosilane, where the subscript h is 0 or 1, R' is defined above, and each R 10The alkyl group is selected independently and has 1 to 18, alternatively 1 to 16, alternatively 1 to 14, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, or alternatively 1 to 4 carbon atoms. In one embodiment, the subscript h is 0 and the aminosilicone compound (C) has the formula R'Si(OR) 10 3. A specific example of such an aminosilane is 3-propylaminotriethoxysilane. In another embodiment, the subscript h is 1 and the aminosilane compound (C) has the formula R'R 10 Si(OR 10 2. A specific example of such an aminosilane is 3-propylamino(diethoxy)methylsilane.

[0063] When using an aminosilicone compound (C) and it has the formula R'Si(OR) 10 At step 3, at least some of the aminosilicone compounds (C) used are typically hydrolyzed and condensed to produce, in polysiloxane (A), the product represented by the subscript c', i.e., having the formula R'SiO. 3 / 2 The T-siloxane-oxy unit. Typically, each alkoxy group of the aminosiloxane compound (C) is completely hydrolyzed and condensed to produce this T-siloxane-oxy unit in the polysiloxane (A). During the preparation of the polysiloxane (A), when used, the aminosiloxane compound (C) can generate a partially condensed product during the reaction of the polysiloxane (A). When using the aminosiloxane compound (C) and it has the formula R'Si(OR) 10 At 3, some condensation products have the formula (R'(OZ)). q SiO 3-q / 2 ), where the subscript q is independently 0, 1, or 2, and each Z is independently H or R. 10 .

[0064] When using an aminosilicone compound (C) and it has the formula R'R 10 Si(OR 10 At time 2, at least some of the aminosilicone compounds (C) used are typically hydrolyzed and condensed to produce, in polysiloxane (A), the product indicated by the subscript b', i.e., having the formula R'R. 2 SiO 2 / 2 The D-siloxy unit. Typically, each alkoxy group of the aminosiloxane (C) is completely hydrolyzed and condensed to produce this D-siloxy unit in the polysiloxane (A). During the preparation of the polysiloxane (A), when used, the aminosiloxane compound can generate a partially condensed product during the reaction of the polysiloxane (A). When using the aminosiloxane compound (C) and it has the formula R'R 10 Si(OR 10 At 2, some condensation products have the formula R'R 10 (OZ)rSiO2-r / 2 The subscript r is independently 0 or 1, and each Z is independently H or R. 10 .

[0065] Combinations of different aminosilicone compounds can be used together as aminosilicone compounds (C).

[0066] Based on the total weight of the composition, the aminosilicone compound (C) is typically present in the composition in an amount of 0% to 25% by weight, alternatively 0% to 20% by weight, or alternatively 0% to 15% by weight.

[0067] As described above, the composition contains an adjustable liquid viscosity. Specifically, the composition typically contains a viscosity of 100 cps to 800,000 cps at 25°C. For example, in some embodiments, the composition contains a viscosity of 185 cps to 700,000 cps, depending, for example, on the specific polyether alcohol compound (B) selected, the ratio of the polysiloxane (A) to the polyether alcohol compound (B) used, the presence or absence of the aminosilicone compound (C), etc. Furthermore, as will be recognized by the following method, the ratio of the -OX=polyether portion to the -OX=H portion (i.e., the end-capping ratio) within the polysiloxane (A) can also be independently selected and controlled to provide a composition in liquid form. Because the composition has an adjustable liquid viscosity, the viscosity can be selectively controlled based on the desired end-use application and its properties.

[0068] A method for preparing a liquid silicone resin composition is also provided. The method includes (I) combining a solid silicone resin, a polyether alcohol compound (B), and optionally an aminosilicone compound (C) to obtain a mixture comprising a polysiloxane (A), a polyether alcohol compound (B), and optionally an aminosilicone compound (C). The method further includes (II) liquefying the mixture comprising the polysiloxane (A) and the polyether alcohol compound (B) to prepare the liquid silicone resin composition. As described below, in some embodiments using the aminosilicone compound (C), the aminosilicone compound (C) is incorporated during and / or after the step of liquefying the mixture.

[0069] As will be appreciated from the description herein, the polyether alcohol compound (B) is capable of liquefying the solid silicone resin, optionally without reacting with it. Therefore, when optionally combined with the polyether alcohol compound (B) in the presence of a carrier medium, the solid silicone resin is generally solid, as described below. The term "solid" is used herein with respect to solid silicone resin to describe silicones such as those having a softening point and / or melting point above room temperature, such that the silicone resin is solid or substantially solid at room temperature.

[0070] The solid organosilicon resin has the following general formula:

[0071] (R1 3SiO 1 / 2 ) a (R 4 2SiO 2 / 2 ) b (R 4 SiO 3 / 2 ) c (SiO 4 / 2 ) d ,

[0072] Each R 4 Independently selected from R 1 And -OR, the condition is R 4 In at least one T-methoxy unit denoted by the subscript c, the group is selected from -OH and -OR, and each R 1 R and the subscripts a, b, c and d are as defined above.

[0073] Regarding the foregoing formula, as those skilled in the art will recognize from the description herein, the solid silicone resin used in this method forms the siloxane backbone of the polysiloxane (A). Therefore, the above description of the M, D, T, and Q silanoxy units of the polysiloxane (A), respectively denoted by subscripts a, b, c, and d, also applies to the solid silicone resin of this method. For example, in some embodiments, the solid silicone resin contains an MQ ratio of 0.5 to 1.5 (a:d), i.e., the ratio of M silanoxy units denoted by subscript a to Q silanoxy units denoted by subscript d. In these or other embodiments, the ratio of M silanoxy units denoted by subscript a to Q silanoxy units denoted by subscript d in the solid silicone resin is 0.7 to 1.2 (a:d). However, as is readily understood in the art, although the ranges of subscripts a, b, c, and d apply to both solid silicone resins and polysiloxanes (A), each of subscripts a, b, c, and d can be independently different between solid silicone resins and polysiloxanes (A). For example, when the method of preparing the composition involves liquefaction, certain siloxane bonds can be cleaved to produce SiOZ moieties, where Z is independently H or alkyl. For this purpose, based on mole fraction, polysiloxanes (A) may have, for example, fewer Q siloxane units than solid silicone resins. For example, a Q siloxane unit in a solid silicone resin can cause a T(OZ) siloxane unit (i.e., a T siloxane unit having three siloxane bonds and a SiOZ group) in polysiloxane (A) to cleave one siloxane bond. The SiOZ groups may be retained in the polysiloxane (A) or may be condensed with a polyether alcohol compound (B) and / or an aminosilicone compound (C) (if used) to generate functional groups (i.e., polyether groups and / or amino groups) in the polysiloxane (A). In some embodiments, the solid silicone resin has a SiOZ content of greater than 0% to 10% by weight, alternatively greater than 0% to 8% by weight, alternatively greater than 0% to 6% by weight, and alternatively 0.5% to 4% by weight of SiOZ groups.

[0074] Typically, solid silicone resins have a weight-average molecular weight of 2,000 to 30,000, such as 3,000 to 30,000, alternatively 4,000 to 30,000, alternatively 4,000 to 25,000, alternatively 5,000 to 25,000, alternatively 5,000 to 20,000, or alternatively 6,000 to 20,000. As those skilled in the art will understand, the weight-average molecular weight, in Daltons, can be readily determined using triple-detector gel permeation chromatography (e.g., using light scattering, refractive index, and viscosity detectors) against polystyrene standards.

[0075] It will be recognized that the polyether alcohol compound (B) used in this method (e.g., for end-capping and / or liquefying polysiloxane (A)) is the same component as described above regarding the polyether alcohol compound (B) of the composition. Therefore, the above description of the polyether alcohol compound (B) and its various components also applies to this method.

[0076] As described above, the method for preparing a liquid silicone resin composition involves combining a solid silicone resin and a polyether alcohol compound (B), along with any other optional components used (collectively, "method components"), to prepare a mixture thereof. As those skilled in the art will understand, a proactive step is generally not required other than combining the reactive components, although certain processes described below may be used. Furthermore, while one aspect of the method involves reacting the solid silicone resin with the polyether alcohol compound (B) (e.g., via a condensation reaction) to prepare a polysiloxane (A) and thereby obtain the composition, it should be recognized that, in another aspect, the method can be used to prepare the composition by simply liquefying the polysiloxane (A) in the presence of the polyether alcohol compound (B) without reacting / capping it.

[0077] Furthermore, as described above, the aminosilicone compound (C) may optionally be used in this method. When used, the aminosilicone compound (C) may be incorporated at any time during the method of preparing the composition. For example, in one embodiment, the aminosilicone compound (C) is combined with a solid organosilicon resin and a polyether alcohol compound (B) such that the aminosilicone compound (C) is present in the mixture. Alternatively or additionally, the aminosilicone compound (C) may be combined with the mixture after its formation. Furthermore, as described below, the aminosilicone compound (C) may be combined during and / or after the liquefaction of the mixture.

[0078] Regarding the method components, the solid silicone resin can be prepared or otherwise obtained, i.e., as the resin to be prepared. Methods for preparing MQ resins such as solid silicone resins are known in the art, wherein suitable precursors and starting materials are commercially available from various suppliers. When as part of the method, the preparation of the solid silicone resin is typically carried out prior to its combination with the polyether alcohol compound (B). The polyether alcohol compound (B) can also be prepared as part of the method or otherwise obtained for use therein. In a particular embodiment, the polyether alcohol compound (B) is prepared by reacting an alkoxylated compound (b-1) with an alkoxylating agent (b-2) (e.g., alkoxylation). When selecting the alkoxylating agent (b-2), for example when using an alkylene oxide, those skilled in the art will recognize that propylene oxide and / or butane oxide can be used to increase the flexibility of the product of the alkoxylation and / or condensation reaction of the method, and thereby change the viscosity by increasing the flowability of the polyether alcohol compound (B) and optionally the polysiloxane (A) prepared therefrom.

[0079] Typically, method components are combined in a vessel or reactor to prepare a composition. The method components may be fed into the vessel together or separately, or may be added in any order and in any combination, as illustrated below. The method may also include stirring the mixture, for example to enhance the mixing and contact of the method components during combination. This contact may be achieved independently using other conditions, with (e.g., simultaneously or sequentially) or without (i.e., independently of, alternatively to) stirring, and will generally be implemented to aid in the preparation of the polysiloxane (A) and / or liquefaction mixture in the mixture. Other conditions may be used in addition to or in lieu of those described herein, and these other conditions may be effective conditions for enhancing the results of condensation, liquefaction, etc., during the course of the method.

[0080] This method can utilize any amount of method components, and more specifically, may include combining solid silicone resin, polyether alcohol compound (B), and optionally aminosilicone compound (C) in different amounts or ratios, depending on the desired properties of the resulting composition and / or the characteristics of the starting materials used. For example, the amount of solid silicone resin and polyether alcohol compound (B) may be set to provide a specific end-capping ratio (i.e., the molar ratio of the silanol functional groups of the MQ resin to the hydroxyl functional groups of the polyether alcohol compound (B)) to the polysiloxane (A) prepared therefrom (e.g., an end-capping ratio of 0.25 to 1.0, such as 0.5 to 0.75, etc.). Thus, as those skilled in the art will understand, solid silicone resin and polyether alcohol compound (B) may be used in a molar ratio of 1:≥1 that is advantageous for either component. For example, solid silicone resin and polyether alcohol compound (B) can be used in molar ratios of 1:10 to 10:1, alternatively 1:5 to 5:1, alternatively 1:2 to 2:1, or alternatively 1:1.1 to 1.1:1. As shown, either component can also be used in excess (e.g., slight excess, moderate excess, or extreme excess).

[0081] Solid silicone resin, polyether alcohol compound (B), and optional aminosilicone compound (C) can be combined in any order, optionally under shear or mixing conditions. For example, in some embodiments, the mixture is prepared by combining the solid silicone resin and polyether alcohol compound (B), optionally with any other component used, such as aminosilicone compound (C). These components can be combined in any order, simultaneously, or in any combination thereof (e.g., in various multipart compositions that are ultimately combined with each other). Similarly, unless otherwise stated herein, the mixture can be prepared by batch, semi-batch, semi-continuous, or continuous processes. Typically, once combined, the components of the mixture are homogenized, for example, by mixing, which can be done using any of the various techniques known in the art using any equipment suitable for mixing. Examples of suitable mixing techniques typically include ultrasonication, dispersion mixing, planetary mixing, three-roll milling, etc. Examples of mixing equipment include stirred batch mixers, screw mixers, solution mixers, co-kneaders, twin-rotor mixers, Banbury mixers, mills, extruders, etc., for compositions with relatively high flowability (low dynamic viscosity). These can be batch or continuous mixing equipment and can be used alone or in combination with one or more mixers of the same or different types.

[0082] In some embodiments, a solid silicone resin, a polyether alcohol compound (B), and optionally an aminosilicone compound (C) are combined in the presence of a carrier medium. The carrier medium is not limited and is typically selected based on the specific solid silicone resin and / or polyether alcohol compound (B) used, the desired end use of the composition, etc. Generally, carrier media include, and alternatively, solvents, fluids, oils (e.g., organic oils and / or silicone oils), or combinations thereof.

[0083] In some embodiments, the carrier medium comprises a silicone fluid. The silicone fluid is typically a low-viscosity and / or volatile siloxane. In some embodiments, the silicone fluid is a low-viscosity organopolysiloxane, a volatile methylsiloxane, a volatile ethylsiloxane, a volatile methylethylsiloxane, or a combination thereof. Typically, the silicone fluid has a viscosity of 1 to 1,000 mm at 25°C. 2Viscosities in the range of / s. Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecylpentasiloxane, tetradecylmethylhexasiloxane, hexadecylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3-bis{(trimethylsilyl)oxy}trisiloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, octylpolymethylsiloxane, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexylpolytrimethylsiloxane, etc., and their derivatives, modifiers, and combinations thereof. Additional examples of suitable silicone fluids include those with suitable vapor pressures (such as 5 × 10⁻⁶). -7 m 2 / s to 1.5×10 -6 m 2 Polyorganosiloxane ( / s).

[0084] In some embodiments, the carrier medium comprises an organic fluid, which typically includes organic oils containing volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. General examples of such organic fluids include volatile hydrocarbon oils, such as C6-C... 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isodecane, isohexadecane, etc.), C8-C 16 Branched esters (e.g., isohexyl neopentanoate, isodecanyl neopentanoate, etc.), and their derivatives, modifiers, and combinations thereof. Other examples of suitable organic fluids include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, aromatic halides, and combinations thereof having more than three carbon atoms. Hydrocarbons include isododecane, isohexadecane, and Isopar L(C 11 -C 13 ), Isopar H(C 11 -C 12Hydrogenated polydecene. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, distearate, dioctyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), octadecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dioctanoate / propylene glycol didecanoate, octyl ether, octyl palmitate, and combinations thereof. It should be recognized that some examples of the above organic fluids (e.g., glycol ethers) may overlap in description with polyether alcohol compounds (B) that can themselves be used as carrier media, or be combined with another carrier media described herein. In some embodiments, the method is carried out with organic fluids that do not, and alternatively substantially do not, satisfy the description of polyether alcohol compounds (B) (i.e., not polyether alcohol compounds (B) themselves).

[0085] In some embodiments, the carrier medium comprises an organic solvent. Examples of organic solvents include solvents comprising: alcohols, such as methanol, ethanol, isopropanol, butanol, and n-propanol; ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; 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; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; petroleum solvents; solvent oils; naphtha; N-methylpyrrolidone; and so on, as well as derivatives, modifiers, and combinations thereof. In some embodiments, the carrier medium comprises a polar organic solvent, such as a water-compatible solvent. Specific examples of such polar organic solvents used in some embodiments include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-butanone, tetrahydrofuran, acetone, and combinations thereof. Other carrier media may be used in lieu of, or in combination with, those described herein. In some embodiments, the carrier media include, alternatively, aliphatic and / or aromatic hydrocarbon solvents such as xylene, siloxane solvents such as hexamethylenedisiloxane (HMDSO), D4 or D5 cyclic compounds, or other such siloxanes, or combinations thereof. In other embodiments, the method is carried out in a manner substantially free of certain solvents. For example, in some embodiments, the method is carried out in a manner free of, alternatively substantially free of, hexamethylenedisiloxane (HMDSO), D4 cyclic compounds, and / or D5 cyclic compounds. In these or other embodiments, the method is carried out in a manner free of, alternatively substantially free of, benzene, toluene, ethylbenzene, and xylene (i.e., BTEX solvents). In these or other embodiments, the method is carried out in a manner free of, alternatively substantially free of aromatic solvents.

[0086] In some embodiments, the solid silicone resin is combined with a carrier medium before being combined with the polyether alcohol compound (B) and optionally the aminosilicone compound (C). However, in other embodiments, the polyether alcohol compound (B) is combined with the carrier medium before being combined with the solid silicone resin (and optionally the aminosilicone compound (C)), or alternatively, the components are combined substantially simultaneously to obtain a mixture. Parameters related to the conditions of combining these components (e.g., temperature, pressure, etc.) can also be controlled. However, the method can be carried out under ambient conditions. Typically, the solid silicone resin, polyether alcohol compound (B), optionally the aminosilicone compound (C), and carrier medium are combined at a temperature below 45°C (i.e., cold processing) to obtain a mixture. However, in some embodiments, the solid silicone resin, polyether alcohol compound (B), optionally the aminosilicone compound (C), and carrier medium are combined at a temperature below 40°C, alternatively below 35°C, alternatively below 30°C, or alternatively at approximately ambient temperature.

[0087] In some embodiments, the method includes reacting a solid silicone resin with a polyether alcohol compound (B) to prepare a polysiloxane (A) in the mixture. In these or other embodiments, where the method utilizes an aminosilicone compound (C), the method may further include reacting a solid silicone resin or a reaction intermediate formed by reacting a solid silicone resin with the polyether alcohol compound (B) with the aminosilicone compound (C) to prepare the polysiloxane (A). Typically, the aminosilicone compound (C) is hydrolyzed and condensed to yield a T-silyloxy unit having an amino functional group in the polysiloxane (A). As described above, the reaction of this method can generally be defined or otherwise characterized as a condensation reaction, and certain parameters and conditions of the reaction can be selected by those skilled in the art based on the specific components utilized. For example, in some such embodiments, the method includes placing a catalyst (i.e., a condensation catalyst) in the mixture. Condensation catalysts, such as those based on tin (e.g., tin octoate) or bases (e.g., NaOAc, KOH, etc.), are known in the art and will be selected based on the method components utilized. However, in other embodiments, the method is carried out in the absence of any tin catalyst, for example to provide a composition as a tin-free product, and thus avoids the limitations associated with tin being carried into the final composition.

[0088] When implemented in this method, the catalyst can be used in any amount, selected by those skilled in the art based on factors such as the specific catalyst chosen, the concentration / amount of its active catalytic material, the properties / type of the chosen solid silicone resin and / or polyether alcohol compound (B), the reaction parameters employed, and the scale of the reaction (e.g., the total amount of method components utilized). The molar ratio of the catalyst to the method components can affect the rate and / or amount of condensation in the mixture to prepare polysiloxane (A). Therefore, the amount of catalyst and the molar ratio between them can vary compared to the method components. Typically, these relative amounts and molar ratios are selected to maximize the reaction of the method components while minimizing the catalyst loading (e.g., to increase the economic efficiency of the reaction, increase the ease of purification of the formed reaction products, etc.).

[0089] In some embodiments, the catalyst is used in amounts from 0.000001 wt% to 50 wt% (i.e., weight / weight) based on the total amount of solid silicone resin utilized. For example, the catalyst may be used in amounts from 0.000001 wt% to 25 wt%, alternatively from 0.00001 wt% to 10 wt%, or alternatively from 0.0001 wt% to 5 wt% based on the total amount of solid silicone resin utilized. In some embodiments, the catalyst is used in amounts sufficient to provide a ratio of catalyst tin to the hydrolyzable groups of the solid silicone resin compound of 1:10 to 1:1,000,000, alternatively from 1:50 to 1:1,000, or alternatively from 1:100 to 1:500. Such a ratio may be a weight ratio (i.e., weight / weight) or alternatively, a molar ratio between components. It should be understood that amounts and ratios outside the ranges listed above may also be used. For example, the catalyst can be used in stoichiometry (i.e., supercatalytic amount) based on, for example, the total amount of polyether alcohol compound (B) used in the mixture.

[0090] The catalyst can be prepared or otherwise obtained (i.e., as a compound to be prepared). Methods for preparing condensation catalysts (e.g., tin catalysts, acetate catalysts, etc.) are known in the art, using compounds commercially available from various suppliers. Thus, the catalyst can be prepared prior to the reaction of a solid silicone resin with a polyether alcohol compound (B) (and optionally an aminosilicone compound (C)), or in situ (i.e., during the reaction of those components, for example by combining the catalyst components with a mixture comprising a solid silicone resin and a polyether alcohol compound (B)). Therefore, in some embodiments, the catalyst is prepared as part of a preparation method, i.e., the preparation method includes the preparation of the catalyst.

[0091] When a condensation reaction is desired, the method will typically also include exposing the mixture to one or more condensation conditions, such as elevated temperature, reduced pressure, reflux, etc. Thus, the vessel or reactor can be heated or cooled in any suitable manner, such as by jackets, shrouds, exchangers, baths, coils, etc., to allow the reaction to proceed at elevated or reduced temperatures, pressures, etc., as described below. For example, based on the nature of the condensation reaction, condensation conditions may include heating the mixture to elevated temperatures such as 100°C, for example, to promote the condensation of the polyether alcohol compound (B) and the solid silicone resin (and optionally the aminosilicone compound (C)). Similarly, condensation conditions may include evacuating the reactor used to subject the mixture to reduced pressure (e.g., from 35 mbar to 300 mbar). When combined, reduced pressure and elevated temperature can be used to distill water from the reactants, thereby driving condensation toward complete reaction by preventing reverse reaction. Those skilled in the art will recognize that the specific temperatures and pressures used will be selected based on the method components and the carrier medium present in the mixture, for example, to provide effective reflux conditions without overheating the mixture. For example, in various embodiments, the reaction is carried out at reaction / condensation temperatures ranging from 23°C to 200°C, such as above ambient temperature (e.g., above 25°C) to 200°C, alternatively above 25°C to 180°C, alternatively above 25°C to 165°C, alternatively above 25°C to 150°C, alternatively above 30°C to 150°C, alternatively above 50°C to 150°C, alternatively above 70°C to 150°C, alternatively above 60°C to 150°C, alternatively above 85°C to 150°C, alternatively above 100°C to 150°C, and alternatively above 110°C to 150°C. In some embodiments, the reaction temperature is selected and / or controlled based on the boiling point of any solvent or volatile diluent, such as when reflux conditions are used. Additionally, a co-solvent such as toluene can be used to remove water from the mixture via azeotropic dehydration.

[0092] Typically, the reaction rate of the components in the mixture (i.e., the condensation of the polyether alcohol compound (B) and the solid silicone resin and optionally the aminosilicone compound (C)) increases with i) increasing reaction temperature and ii) removing water from the reaction system. Therefore, the necessary reaction time will be selected based on the specific characteristics of the mixture being reacted. In exemplary embodiments, the reaction time (i.e., the condensation / capping time, which can be monitored by visual inspection, spectroscopic methods (e.g., NMR, FT-IR, etc.) or other methods known in the art) can be approximately 1 to several hours, such as 1 to 10 hours, alternatively 2 to 10, alternatively 3 to 10, alternatively 4 to 10, alternatively 4 to 8, alternatively 4 to 6 hours. However, longer and shorter reaction times can be selected, for example, depending on the size / scale of the reaction and any particular component used in the mixture.

[0093] In some embodiments, the method includes dissolving a solid silicone resin in a carrier medium (i.e., a solvent) to obtain a silicone resin solution, and combining the silicone resin solution with a polyether alcohol compound (B) to form a mixture. As described above, when the method uses an aminosilicone compound (C), the aminosilicone compound (C) can be combined with the silicone resin and / or with the mixture. In these embodiments, such as when a carrier medium is used, the method typically also includes removing the carrier medium from the mixture once the polysiloxane (A) is prepared therein. More specifically, in such embodiments, liquefying the mixture includes solvent exchange of the solid silicone resin from the solvent / carrier medium to the polyether alcohol compound (B) to prepare the composition. Solvent exchange is not particularly limited and may simply involve removing the carrier medium from the reactor (e.g., by distillation). For example, in some embodiments, the method includes heating the mixture under reduced pressure (i.e., ~35 mbar) to a temperature of 60°C to 150°C to remove the solvent and obtain the composition.

[0094] As will be appreciated from the above description and examples herein, the compositions prepared by this method provide a liquefied combination of a polysiloxane (A) and a polyether alcohol compound (B) and optionally a residual aminosilicone compound (C) (if used and not completely consumed). The polysiloxane (A) may comprise the condensation product of a solid silicone resin and the polyether alcohol compound (B) (and optionally an aminosilicone compound), or alternatively, may simply be a liquefied form of a solid silicone resin (e.g., when no end-capping / condensation with the polyether alcohol compound (B) is performed).

[0095] The following examples illustrating embodiments of this disclosure are intended to be illustrative and not limiting of the invention. Unless otherwise stated, all reactions were carried out in air, and all solvents, substrates, and reagents were purchased from or otherwise obtained from various commercial suppliers (e.g., Gelest, Acros, Sigma-Aldrich) and used as is.

[0096] Equipment and characterization parameters

[0097] The following equipment and characterization procedures / parameters were used to evaluate the various physical properties of the compounds and compositions prepared in the following examples.

[0098] Gel permeation and size exclusion chromatography (GPC / SEC)

[0099] SEC Instruments

[0100] SEC was performed using a Waters 2695 LC pump and autosampler at a flow rate of 1 mL / min and an injection volume of 100 μL. SEC separation was performed on two Agilent Plgel Mixed-D columns using a Shodex RI-201 differential refractive index detector, each maintained at 35 °C.

[0101] Sample preparation

[0102] Prepare the sample in THF eluent to a concentration of ~5 mg / mL polymer / resin. Shake the solution on a plate shaker at ambient temperature for approximately 2 hours, then filter it through a 0.45 μm PTFE injection filter before injection.

[0103] Data processing

[0104] Agilent GPC software Cirrus version 3.3 was used for data collection and data simplification. Molecular weight calibration was performed using a total of 16 linear narrow molecular weight polystyrene (PS) standards with Mp values ​​ranging from 3752 kg / mol to 0.58 kg / mol from Agilent. A third-order polynomial was used for calibration curve fitting, and all molecular weight averages, distributions, and molecular weight references are provided as PS equivalent values.

[0105] FT-IR analysis

[0106] Details of the FT-IR instrument are listed in Table 1 below.

[0107] Table 1: FT-IR Instruments

[0108] Detector: DTGS KBr Beam splitter: Csl scanning: 64 Collection length: 77.18 seconds Resolution: 4.000

[0109] Sample preparation

[0110] Sample Spectroscopy: Weigh the sample into a 1 cm IR quartz cuvette with a stopper. Add a specific volume of CCl4 to the cuvette and thoroughly mix the sample by shaking. Then measure the sample by IR using the spectral parameters listed below.

[0111] Reference Spectrum: After sample measurement, add approximately 0.5 mL of D₂O to the cuvette and vigorously mix the sample for approximately 30 seconds before allowing phase separation. Remove the top D₂O layer and repeat the addition / mixing procedure to ensure complete D₂O exchange. Allow the sample phase to separate again, leaving the D₂O in place. Then measure the sample again by IR (deuterated sample).

[0112] Data processing

[0113] Spectral subtraction: Subtracting the deuterated sample spectrum from the original sample spectrum to remove invariant features. If the subtraction result shows an effect on 3610 cm⁻¹... -1 If there is identifiable interference with the water signal at the location (i.e., the presence of little to no -COH), then the spectrum of water in CCl4 is subtracted from the original subtraction.

[0114] After subtraction, the measurement is 3690cm. -1 The maximum peak height of the band was determined, and the result was used in the following calculations to determine the ppm OH of the silanol signal:

[0115]

[0116] Viscosity measurement

[0117] Brookfield Instruments

[0118] The Brookfield DV3T cone / plate rheometer, maintained at 25°C by water recirculation, was used for measurements along with a CPA-40Z rotor and a 0.50 mL material volume.

[0119] Sample preparation and procedures

[0120] The method based on ASTM D 4287 is used with a level viscometer. For each series of samples, enter the desired parameters for the digital viscometer and adjust the position of the sample cup relative to the rotor (cone) according to the manufacturer's specifications to maintain the required clearance. Remove the sample cup and add 0.5 mL of sample to the center of the cup using a 1 mL syringe to remove all air bubbles from the material. Allow the sample to equilibrate at 25 ± 0.1 °C. Start the motor at the specified speed and record the digital viscosity reading. Before using the sample, calibrate the instrument using a standard 200 fluid (if possible, with a viscosity close to the sample) as a control.

[0121] 29 Si NMR

[0122] for 29 For Si NMR, 2.5 g to 3 g of each prepared product and approximately 5 g of solvent (CDCl3 + Cr(acac)3) were placed in a 16 mm silicon-free NMR tube, and spectra were obtained according to the conditions and instruments in Table 2 below:

[0123] Table 2: 29 Si NMR instrument

[0124]

[0125] Material

[0126] A summary is provided in Table 3 below, which describes information about certain abbreviations, acronyms, and components used in the embodiments.

[0127] Table 3: Materials Used

[0128]

[0129] Example 1

[0130] 246.7 g of silicone resin 1 and 79.93 g of polyether alcohol 1 were placed in a 1000 mL four-necked flask. 0.15 g of condensation catalyst 1 was added, and the content was adjusted to 50 wt% solids (SR+PA) (total weight = 506.7 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 1800 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~68%.

[0131] Example 2

[0132] 226.0 g of silicone resin 1 and 93.75 g of polyether alcohol 2 were placed in a 1000 mL four-necked flask. 0.15 g of condensation catalyst 1 was added, and the content was adjusted to 50 wt% solids (SR+PA) (total weight = 506.1 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 1386 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~63%.

[0133] Example 3

[0134] 760.5 g of silicone resin 2 and 223.7 g of polyether alcohol 1 were placed in a 1500 mL four-necked flask. 0.3 g of condensation catalyst 1 was added, and the content was adjusted to 75 wt% solids (SR+PA) (total weight = 1018.5 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 63,500 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~70%.

[0135] Example 4

[0136] 702.5 g of silicone resin 2 and 263.8 g of polyether alcohol 2 were placed in a 1500 mL four-necked flask. 0.3 g of condensation catalyst 1 was added, and the content was adjusted to 75 wt% solids (SR+PA) (total weight = 1017.1 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 15,600 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~65%.

[0137] Example 5

[0138] 330.5 g of silicone resin 1 and 122.2 g of polyether alcohol 4 were placed in a 1000 mL four-necked flask. 0.15 g of condensation catalyst 1 was added, and the content was adjusted to 70 wt% solids (SR+PA) (total weight = 508.9 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by vacuum rotary evaporation at 100 °C. The obtained product was clear and had a Brookfield viscosity of 1762 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~65%.

[0139] Example 6

[0140] 322.7 g of silicone resin 1 and 127.3 g of polyether alcohol 5 were placed in a 1000 mL four-necked flask. 0.15 g of condensation catalyst 1 was added, and the content was adjusted to 70 wt% solids (SR+PA) (total weight = 508.8 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 46,400 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~64%.

[0141] Example 7

[0142] 58.5 g of silicone resin 1, 57.4 g of polyether alcohol 3, and 25.6 g of polyether alcohol 6 were placed in a 500 mL four-necked flask. 0.19 g of condensation catalyst 1 was added, and the content was adjusted to 70 wt% solids (SR+PA) (total weight = 141.8 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 185 cps. The sample was analyzed by GPC, Si NMR, and FT-IR. The obtained product had a resin content of ~41%.

[0143] Example 8

[0144] 436 g of silicone resin 1 and 2574.9 g of polyether alcohol 7 were placed in a 5000 mL four-necked flask. 0.9 g of condensation catalyst 1 was added, and the content was adjusted to 45 wt% solids (SR+PA) (total weight = 3013.5 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 80 °C for 15 min. A Dean-Stark water separator was connected to the flask, and the contents were refluxed at 140 °C for 4 h, collecting the water from the reaction. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear to cloudy with a Brookfield viscosity of 185 cps. The sample was analyzed by GPC, Si NMR, and FT-IR. The obtained product had a resin content of ~10%.

[0145] Example 9

[0146] 291 g of silicone resin 1 and 716.6 g of polyether alcohol 7 were placed in a 2000 mL four-necked flask. No condensation catalyst was added. The content was adjusted to 90 wt% solids (SR+PA) (total weight = 1007.6 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm, and then heated to 60 °C for 15 min. The flask was cooled to room temperature and the xylene was removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 185 cps. The sample was analyzed by GPC, SiNMR, and FT-IR. The obtained product had a resin content of ~20%.

[0147] Example 10

[0148] 246.8 g of silicone resin 1 and 704.1 g of polyether alcohol 8 were placed in a 2000 mL four-necked flask. No condensation catalyst was added. The content was adjusted to 90 wt% solids (SR+PA) (total weight = 950.8 g) by adding xylene. The flask was mixed with a top stirrer at 200 rpm and then heated to 60 °C for 15 min. The flask was cooled to room temperature and removed by rotary evaporation under vacuum at 100 °C. The obtained product was clear and had a Brookfield viscosity of 185 cps. The sample was analyzed by GPC, Si NMR, and FT-IR. The obtained product had a resin content of ~20%.

[0149] GPC and FT-IR analyses of Examples 1-10

[0150] The results of GPC and FT-IR analyses of the initial MQ resin and the compositions obtained in Examples 1-10 are shown in Tables 4-6 below.

[0151] The GPC composition was obtained by deconvolution of the GPC spectra and calibration of free MQ resin (SR) and free alcohol compounds (PA).

[0152] Based on the calculated amount of free alcohol (PA), it is assumed that the remaining alcohol reacts (terminated) onto the MQ resin (SR), and the MQ-OR is estimated by assuming a molar terminology for termination onto the MQ resin. For FTIR results, it is assumed that the decrease in Si-OH is due to alcohol termination, and the MQ-OR is overestimated compared to GPC. Based on this assumption, in each case, the SiOH ppm from the spectrum is normalized to the initial MQ resin SiOH signal to estimate the decrease in the SiOH signal in response to the reaction with the alcohol compound.

[0153] Table 4: GPC data of the initial MQ resins in Examples 1-10

[0154]

[0155]

[0156] Table 5: GPC data for the compositions of Examples 1-10

[0157]

[0158] Table 6: FT-IR data of the compositions in Examples 1-10

[0159]

[0160] Referring to Tables 4-6 above, all compositions contain >10% to 70% by weight of MQ resin (SR), which is dissolved or partially grafted (terminated) with an alcohol / capping agent (PA) to obtain a liquid silicone resin composition.

[0161] Examples 11-13

[0162] Three compositions were prepared according to the procedures of Examples 1-10 above. Examples 11-13 were prepared using silicone resin 2 and various alcohols / capping agents (PA). Details of these compositions and the Brinell viscosity of the resulting compositions are shown in Table 7 below.

[0163] Table 7: Components and Viscosities of Examples 11-13

[0164]

[0165] pass 29 Si NMR analysis of the end-capping percentage of the composition is shown in Table 8 below, where "I" represents the initial sample and "F" represents the final prepared composition. In Table 8, M represents M-siloxane-oxygen units; D represents D-siloxane-oxygen units; T represents T-siloxane-oxygen units; Q represents Q-siloxane-oxygen units; and Z is independently H or alkyl. OZ represents the SiOZ group replacing the siloxane bond.

[0166] Table 8: Examples 11-13 29 Si NMR analysis

[0167] 11-I 33.7 0.4 14.8 41.4 14.8 0.8 - 11-F 37.8 -0.1 17.5 38.7 17.5 1.0 0 12-I 40 -0.2 8.9 47.3 8.9 0.8 - 12-F 44.9 0.1 11.9 44.3 3.8 1.0 68.3 13-I 42.1 0.6 13.2 43 13.2 1.0 - 13-F 47 0 13.5 42.7 5.5 1.1 58.9

[0168] The compositions of Examples 11-13 were also analyzed by GPC against polystyrene standards, and the results are shown in Table 9 below, where "I" represents the initial sample and "F" represents the final composition prepared.

[0169] Table 9: GPC Analysis of Examples 11-13

[0170]

[0171]

[0172] Examples 14-18

[0173] Five compositions were prepared according to the procedures of Examples 1-10 above. Examples 14-18 were prepared using various MQ resins (SR) and capping agents (PA). Details of these compositions and the viscosity of the resulting compositions are shown in Table 10 below.

[0174] Table 10: Components and Viscosities of Examples 14-18

[0175]

[0176] Example 19

[0177] 291.7 g of silicone resin 2 and 140 g of polyether alcohol 9 were placed in a 2000 mL four-necked flask. No condensation catalyst was added. The flask was rotary evaporated at 60 °C under a vacuum of 2–5 mm Hg to remove 81.68 g of xylene. The obtained product was clear and had a Brookfield viscosity of 1230 cps. The sample was analyzed by GPC, Si NMR, and FT-IR. The obtained product had a resin content of ~60%.

[0178] Example 20

[0179] 100g of the product formed in Example 19 and 6g of aminosilicone compound were cold-blended at 60 rpm for 3 hours at room temperature to obtain a resin loading of 10% aminosilicone compound based on the product formed in Example 19.

[0180] Example 21

[0181] 100g of the product formed in Example 19 and 6g of aminosilicone compound were blended at 60 rpm for 3 hours and heated in a rotary evaporator at 80°C under a vacuum of 300 mm Hg.

[0182] Example 22

[0183] 100g of the product formed in Example 19 and 12g of aminosilicone compound were blended at 60 rpm for 3 hours and heated in a rotary evaporator at 80°C under a vacuum of 300 mm Hg.

[0184] The results of GPC and FT-IR analyses of the product compositions obtained in Examples 19-22 are shown in Table 11 below.

[0185] Table 11: Mw and PD in Examples 19-22

[0186] 19 8219 2.25 20 4865 1.799 21 5530 1.882 22 4197 1.6923

[0187] pass 29Si NMR analysis of the silanoxy unit content of the products of Examples 19-22 is shown in Table 12 below. In Table 12, Z represents H or alkyl; Me represents methyl; neopentyl represents (CH3)3CCH2; ASC represents aminosilane compounds; X represents H independently, a hydrocarbon group R having 1 to 30 carbon atoms, or a polyether moiety formed from polyether alcohol 9; and T' represents H2NCH2CH2CH2SiO3 / 2 silanoxy unit. The values ​​in Table 12 are mole fractions.

[0188] Table 12: Silyoxyl unit content in Examples 19-22

[0189] <![CDATA[Me3SiOZ]]> 0 0.11 0 0.25 0 <![CDATA[Me3SiO1 / 2]]> 42.15 40.47 40.36 39.74 0 <![CDATA[Neopentyl Me2SiO 1 / 2 > 1.51 1.88 1.75 1.62 0 <![CDATA[R’Si(OZ)3]]> 0 0.25 0 0.75 97.07 <![CDATA[CH3(OZ)2SiO 1 / 2 ]]> 0 0.82 0.59 1.46 2.93 <![CDATA[CH3(OZ)SiO 2 / 2 ]]> 0 1.49 1.51 1.7 0 T’ 0 1.72 2.96 3 0 <![CDATA[(OX)SiO 3 / 2 ]]> 13.41 7.56 8.05 5.84 0 <![CDATA[SiO 4 / 2 ]]> 42.93 45.69 44.79 45.65 0

[0190] The invention has been described by way of example, and it should be understood that the terminology used is intended to be descriptive rather than restrictive. Clearly, many modifications and variations of the invention are possible in accordance with the teachings above. The invention may be practiced in ways other than those specifically described.

Claims

1. A liquid silicone resin composition, said composition comprising: (A) Polysiloxane, which has the following formula: (R 1 3SiO 1 / 2 ) a (R 2 2SiO 2 / 2 ) b (R’R 2 SiO 2 / 2 ) b’ (R 2 SiO 3 / 2 ) c (R’SiO 3 / 2 ) c’ (SiO 4 / 2 ) d , where the subscripts a, b, b', c, c' and d are each a mole fraction such that a+b+b'+c+c'+d=1, with the provisos that 0<a<1, 0≤b<0.2, 0≤b'≤0.1, 0<c<0.2, 0≤c'≤0.1, 0<d<1, and 0≤b'+c'≤0.1, and the ratio of subscript a to subscript d is from 0.5 to 1.5 (a:d); each R 1 is independently selected from a hydrocarbyl group having 1 to 30 carbon atoms, -OH and H; each R 2 is independently selected from R 1 and -OX, where each X is independently H, a hydrocarbyl group R having 1 to 30 carbon atoms, or a group of the general formula -Y-R 3 (-[Y] j -Z) i polyether moiety, with the proviso that at least one R 2 has -OX, where X is said polyether moiety, where R 3 is a substituted or unsubstituted hydrocarbyl segment, each Y is an independently selected oxyalkylene segment of the general formula (C n H 2n O) m where the subscript m is 1 to 50 and the subscript n is independently selected from 2 to 4 in each moiety represented by subscript m, each Z is independently H or a resin organosilicon moiety, the subscript i is 0 to 8, and the subscript j is independently 0 or 1 in each moiety represented by subscript i; and each R' comprises an independently selected amino group; and (B) Possesses the general formula HO-YR 3 (-[Y] j -H) i Polyether alcohol compounds, wherein each Y, R 3 Subscripts i and j are as defined above; in, Polysiloxane (A) is the product of a condensation reaction of a solid silicone resin, a polyether alcohol compound (B), and optionally an aminosilicone compound, wherein the solid silicone resin has the following formula: (R 1 3SiO 1 / 2 ) a (R 4 2SiO 2 / 2 ) b (R 4 SiO 3 / 2 ) c (SiO 4 / 2 ) d , Each R 4 Independently selected from R 1 And -OR, the condition is R 4 In at least one T-methoxy unit denoted by the subscript c, the group is selected from -OH and -OR, and each R 1 R and the subscripts a, b, c and d are as defined above.

2. The liquid organosilicon resin composition according to claim 1, wherein: (i) The ratio of M siloxy units represented by subscript a to Q siloxy units represented by subscript d is 0.7 to 1.2 a:d; (ii) Subscript a is 0.3 to 0.6; (iii) The sum of subscripts b and c is less than 0.2; (iv) Subscript d is 0.4 to 0.7; (v) The polysiloxane (A) contains a weight-average molecular weight (Mw) of 2,000 to 30,000; or (vi) Any combination of (i) to (v).

3. The liquid organosilicon composition according to claim 1 or 2, wherein in the polysiloxane (A): (i) in each R siloxy unit indicated by the subscript c, 2 (ii) Each R of formula -OX is independently of the formula -OX; 2 The polyether portion in; (iii) each R 1 Independently selected from alkyl and aryl groups containing 1-30 carbon atoms and H; or any combination of (iv) (i) to (iii).

4. The liquid silicone resin composition according to claim 1 or 2, wherein in the polysiloxane (A): (i) each R 2 Independently selected from R 1 (ii) the hydroxyl group of formula -OR; 1 (iii) Each R is independently selected from alkyl and aryl groups containing 1 to 30 carbon atoms, -OH and H; (iv) Each R' independently has the formula -(CH2). g N(H) f R 2-f , where each g is independently 1 to 30, f is 0, 1 or 2, and R is independently chosen and defined above; or any combination of (v) (i) to (iv).

5. The liquid silicone resin composition according to claim 1 or 2, wherein: (i) The hydrocarbon segment R 3 It contains branched hydrocarbon groups having 3 to 16 carbon atoms; (ii) subscripts i are 1 to 8; (iii) subscript j is 1 in each part represented by subscript i; (iv) each oxidized alkene segment Y independently has the formula (C2H4O). x (C3H6O) y (C4H8O) z , wherein the subscript x is 1 to 50, the subscript y is 0 to 50, and the subscript z is 0 to 50, and wherein the unit represented by the subscripts x, y, and z is in random or block form in the oxidized olefin segment; or any combination of (v) (i) to (iv).

6. The liquid silicone resin composition according to claim 1 or 2, wherein: (i) Each subscript i is 0, and each hydrocarbon segment R 3 (ii) Each subscript i is 1, and each hydrocarbon segment R 3 Independently comprising at least one group selected from: straight-chain or branched hydrocarbon groups having 3 to 30 carbon atoms, phenols, tetrahydrofurans, alkylamines, and alkoxy groups; or (iii) each subscript i is at least 2, and each hydrocarbon segment R 3 It independently contains at least one group selected from the following: straight-chain or branched hydrocarbon groups having 3 to 30 carbon atoms, alkylamines, polyamines, polyamides, polyaziridines, polyphenols, and polyesters.

7. A method for preparing the liquid organosilicon resin composition according to claim 1 or 2, the method comprising: A solid silicone resin and the polyether alcohol compound (B) are combined to obtain a mixture comprising the polysiloxane (A) and the polyether alcohol compound (B), wherein the solid silicone resin has the following formula: (R 1 3SiO 1 / 2 ) a (R 4 2SiO 2 / 2 ) b (R 4 SiO 3 / 2 ) c (SiO 4 / 2 ) d , Each R 4 Independently selected from R 1 And -OR, the condition is R 4 In at least one T-methoxy unit denoted by the subscript c, the group is selected from -OH and -OR, and each R 1 R and the subscripts a, b, c and d are as defined above; and The mixture is liquefied to prepare the liquid silicone resin composition.

8. The method according to claim 7, further comprising subjecting the solid silicone resin and the polyether alcohol compound (B) to a condensation reaction to prepare the polysiloxane (A) in the mixture.

9. The method of claim 7, wherein the method further comprises combining the (C) aminosilicone compound with the solid organosilicon resin and the polyether alcohol compound (B), and / or wherein the method further comprises combining the (C) aminosilicone compound with the mixture before and / or after liquefying the mixture.

10. The method of claim 7, wherein the liquid silicone resin composition is: (i) tin-free; (ii) cyclic siloxane-free; (iii) contains less than 1% by weight of solvent based on the total weight of the composition; or (iv) any combination of (i) to (iii).

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