Silicon glycans and methods for their preparation

Abstract

Silicon glycans are provided. The silicon glycans comprise a glycoside moiety, an independently selected organosilicon moiety, and an amide moiety linking the organosilicon moiety to the glycoside moiety. The glycoside moiety comprises an independently selected sugar moiety, which may be substituted with a substituted or unsubstituted hydrocarbyl group, an ether moiety, and / or an amine moiety. A method for preparing silicon glycans is also provided. The method comprises reacting (A) an aminoethyl polysaccharide with (B) an anhydride-functional organosilicon compound to obtain the silicon glycan. The method may comprise preparing the aminoethyl polysaccharide (A) by reacting (A1) a hydroxyl-functional polysaccharide with (A2) an aziridinium halide compound to obtain the aminoethyl polysaccharide (A).

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 62 / 937440, filed November 19, 2019. U.S. Provisional Patent Application No. 62 / 937440 is incorporated herein by reference.

[0002] The present invention relates generally to functional polymers, and more specifically to silicon glycans and methods for their preparation. [Background technology]

[0003] Compounds exhibiting rheology-modifying properties are used in various industrial compositions, such as drilling fluids. Silicone polymers and carbohydrate-based polymers (e.g., cellulose ethers) are two classes of such compounds. Silicone polymers and cellulose ethers are non-toxic compounds widely used in industrial compositions, but they have more or less antagonistic properties. Silicone polymers are synthetically prepared and are typically flexible, elastic, and nonpolar. Silicone polymers generally exhibit high spreading and wetting behavior associated with low surface tension and low surface energy. As a comparative example, cellulose ethers are typically rigid, hydrophilic, water-soluble polymers derived from natural sources and are frequently utilized as rheology modifiers. Summary of the Invention

[0004] Silicon glycans are provided, the silicon glycans having the formula: [ka] wherein each A is an independently selected sugar moiety; each W is independently selected from the group consisting of an amide moiety and an imide moiety; each Y comprises an independently selected organosilicon moiety; each R is independently selected from a substituted or unsubstituted hydrocarbyl group, an ether moiety, an amine moiety, and H; and each R 1are independently selected from substituted or unsubstituted hydrocarbyl groups and H; each Z is an independently selected ether moiety; each subscript o is independently 0 or 1; subscripts x and y are each independently ≧0 to <1; and subscript z is >0 to 1, provided that x+y+z=1; and the moieties represented by subscripts x, y, and z can be in a randomized or block form in the silicon glycan.

[0005] A method for preparing a silicon glycan is also disclosed, which comprises reacting (A) an aminoethyl polysaccharide with (B) an anhydride-functional organosilicon compound to obtain the silicon glycan. DETAILED DESCRIPTION OF THE INVENTION

[0006] Silicon glycans have the following general formula (I): [ka] wherein each A is an independently selected sugar moiety; each W is independently selected from the group consisting of an amide moiety and an imide moiety; each Y comprises an independently selected organosilicon moiety; each R is independently selected from a substituted or unsubstituted hydrocarbyl group, an ether moiety, an amine moiety, and H; and each R 1 are independently selected from substituted or unsubstituted hydrocarbyl groups and H; each Z is an independently selected ether moiety; each subscript o is independently 0 or 1; subscripts x and y are each independently ≧0 to <1; and subscript z is >0 to 1, provided that x+y+z=1; and the moieties represented by subscripts x, y, and z can be in a randomized or block form in the silicon glycan.

[0007] Generally, the silicon glycans comprise a glycoside (i.e., at least two sugars linked together via a glycosidic bond) represented by the moiety of general formula (I) corresponding to the following moiety (i.e., "glycoside moiety"): [ka] In the formula, each sugar moiety A comprises or consists essentially of a sugar, and the subscripts x, y, and z each represent the mole fraction of a particular sugar moiety A within the glycoside moiety. In other words, each sugar moiety A is linked (e.g., via a glycosidic bond) to at least one other sugar moiety A, such that each sugar moiety A is a component of, and collectively forms, a glycoside of a silicon glycan. Furthermore, each sugar moiety A, denoted by the subscripts x, y, and z, can be in a randomized or block form within the silicon glycan. As described in further detail herein, Z and R represent substituents unique to or otherwise attached to each sugar moiety A within the glycoside moiety of the silicon glycan.

[0008] It should be understood that the term "sugar" can be used synonymously with the term "carbohydrate" in general contexts, and with terms such as "sugar" in more specific contexts. The nomenclature of a particular sugar is not exclusive to the composition of the silicon glycan as a whole, or to the sugar moiety A in particular. Rather, as will be understood by those skilled in the art, each sugar moiety A can comprise or be any moiety that can be described as a sugar, carbohydrate, sugar, starch, cellulose, etc., or a derivative or modification thereof, or a combination thereof. Similarly, any combination of two or more A's within a silicon glycan can be described in more descriptive terms. For example, the term "polysaccharide" can be used synonymously with the term "glycoside," and both terms generally refer to a combination of two or more sugar moieties A in a silicon glycan (e.g., a combination of sugar moieties A linked to each other via glycosidic bonds and collectively forming a glycosidic moiety). Those skilled in the art will understand that terms such as "starch" and "cellulose" may be used to refer to such combinations of sugar moieties A under certain circumstances (e.g., when the combination of two or more A's in a silicon glycan A conforms to a structure known in the art as "starch" or "cellulose," etc.).

[0009] As introduced above, the subscripts x, y, and z each represent the mole fraction of a particular sugar moiety A within the glycoside portion of the silicon glycan. Thus, the value of x + y + z = 1. More specifically, as represented by formula (I), not all sugar moieties A within the glycoside portion of the silicon glycan need be identically substituted. Therefore, the glycoside portion of the silicon glycan can be described in various ways, for example, in terms of the overall composition using the mole fractions x, y, and z, in terms of the average number of substitutions per sugar moiety A (i.e., the degree of substitution (DS) as understood by those skilled in the art), or a combination thereof.

[0010] Generally, the subscript x is a mole fraction from ≧0 to <1. In certain embodiments, the subscript x is a mole fraction from 0 to 0.99, e.g., from 0.1 to 0.99, alternatively from 0.3 to 0.99, alternatively from 0.5 to 0.99, alternatively from 0.6 to 0.99, alternatively from 0.7 to 0.99, alternatively from 0.7 to 0.99, alternatively from 0.7 to 0.9, alternatively from 0.7 to 0.85. Generally, the subscript y is a mole fraction from ≧0 to <1. In certain embodiments, the subscript y is a mole fraction from 0 to 0.9, e.g., from 0.001 to 0.7, alternatively from 0.001 to 0.5, alternatively from 0.002 to 0.5, alternatively from 0.002 to 0.4, alternatively from 0.002 to 0.3, alternatively from 0.005 to 0.3, alternatively from 0.01 to 0.25. Generally, the subscript z is a mole fraction >0 to 1. In certain embodiments, the subscript z is a mole fraction from 0.00001 to 0.9, e.g., from 0.00001 to 0.7, alternatively from 0.00001 to 0.5, alternatively from 0.00001 to 0.3, alternatively from 0.00001 to 0.2, alternatively from 0.00001 to 0.15, alternatively from 0.000015 to 0.15, alternatively from 0.00002 to 0.15, alternatively from 0.00002 to 0.1, alternatively from 0.00005 to 0.09, alternatively from 0.0001 to 0.09, alternatively from 0.0005 to 0.09, alternatively from 0.001 to 0.09.

[0011] Generally, silicon glycans have an average degree of substitution of organosilicon moieties per sugar moiety A of 0.00001 to 0.99. For example, in certain embodiments, the degree of substitution of organosilicon moieties on silicon glycans is 0.00001 to 0.5, alternatively 0.00001 to 0.2, alternatively 0.00001 to 0.15, alternatively 0.0001 to 0.5, alternatively 0.0001 to 0.2, alternatively 0.0001 to 0.15.

[0012] The degree of aminoethyl substitution of the aminoethyl polysaccharide (A) can be determined by various techniques known to those skilled in the art. For example, the nitrogen content of the aminoethyl polysaccharide (A) (e.g., as determined by the Kjeldahl method) can be used directly or adjusted (e.g., based on the nitrogen content of the hydroxyl-functional polysaccharide (A1)) to determine the degree of aminoethyl substitution of the aminoethyl polysaccharide (A).

[0013] Regardless of the specific ratios described by the subscripts x, y, and z, the total number of sugar moieties A in the silicon glycan (e.g., its degree of polymerization) can vary and is generally between 10 and 10,000. For example, in certain embodiments, the silicon glycan contains a total of 10 to 10,000 sugar moieties A, e.g., 100 to 8,000, alternatively 250 to 6,000, alternatively 600 to 6,000, alternatively 400 to 3,600 sugar moieties A.

[0014] Each sugar moiety A can be the same or different from the other sugar moieties A in the silicon glycan. For example, in certain embodiments, each sugar moiety A is the same (e.g., comprises or consists essentially of the same sugar). In other embodiments, the silicon glycan includes at least one sugar moiety A that is different (e.g., with respect to its sugar) from at least one other sugar moiety A. General examples of specific sugars suitable for the sugar moiety A include those traditionally referred to as monosaccharides and / or carbohydrates. Such monosaccharides include pentoses (i.e., furanoses) such as ribose, xylose, arabinose, lyxose, fructose, etc., and hexoses (i.e., pyranoses) such as glucose, galactose, mannose, gulose, idose, talose, allose, and altrose. Thus, one skilled in the art will understand that the glycoside portion of a silicon glycan can include and / or be defined as a disaccharide (e.g., sucrose, lactose, maltose, trehalose, etc.), an oligosaccharide (e.g., maltodextrin, raffinose, stachyose, maltooligosaccharides such as fructooligosaccharides), a polysaccharide (e.g., cellulose, hemicellulose, pectin, glycogen, hydrocolloids, starches such as amylose, amylopectin, modified starches, etc.), or the like, or combinations thereof.

[0015] In certain embodiments, the silicon glycan comprises at least one sugar moiety A that is a hexose. In some such embodiments, the hexose has the general formula: [ka] As will be understood by those skilled in the art, this includes both internal and terminal monomers of the glycoside moiety formed therefrom. In such embodiments, each R is independently selected and as described herein. In certain embodiments, the glycoside moiety of the silicon glycan may comprise, or may consist essentially of, glucose monomers, and thus correspond to the general formula: [ka] This includes both internal and terminal monomers of the glycosidic moiety formed therefrom, as will be understood by those of skill in the art. In certain such embodiments, each R is independently selected and described herein.

[0016] In some embodiments, the glycoside portion of the silicon glycan may comprise and / or be defined as a polysaccharide selected from pullulan, mannan, galactomannan, xyloglucan, xanthan, hydroxyethyl cellulose, carboxymethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, and the like, and combinations thereof.

[0017] In certain embodiments, the glycoside moiety of the silicon glycan comprises a derivative (e.g., a modified and / or altered version) of one of the oligosaccharides or polysaccharides defined above. For example, the glycoside moiety can be a hydrophobically modified polysaccharide, a cationic modified polysaccharide, a hydrophilically modified polysaccharide, a copolymeric polysaccharide, or a combination thereof. Such modifications generally alter the sugar moiety A in the glycoside by adding a substituent thereto (e.g., via a natural hydroxyl moiety, such as one at the C2, C3, and / or C6 position, if the sugar moiety A comprises a hexose). In particular, as introduced and illustrated above with respect to Formula (I), the sugar moiety A designated by subscript x in the silicon glycan contains the substituents R and, optionally, Z, as described below. For example, R can be H in any sugar moiety A designated by subscript x in the glycoside moiety. R is generally H of each natural (i.e., naturally occurring and / or unsubstituted) sugar of any particular sugar moiety A, such that the particular sugar moiety A has at least one free hydroxyl substituent.

[0018] When the glycoside portion of the silicon glycan comprises a polysaccharide derivative as described above, at least one R is selected from substituted or unsubstituted hydrocarbyl groups, ether moieties, and amine moieties. However, as will be understood by those skilled in the art in light of the description herein, the silicon glycan can contain any number of substituents R as defined above, limited only by the sugar portion A of the glycoside portion, the sugar portion D of the glycoside portion, etc.

[0019] With respect to the hydrocarbyl groups of R, the term "substituted" describes a hydrocarbon moiety in which one or more hydrogen atoms have been replaced with atoms other than hydrogen (e.g., halogen atoms such as chlorine, fluorine, bromine, or iodine), or a carbon atom in the hydrocarbon chain has been replaced with an atom other than carbon (i.e., R includes one or more heteroatoms in the chain, such as oxygen, sulfur, nitrogen, or phosphorus), or both. Thus, it will be understood that R includes a hydrocarbon moiety that can have substituents within and / or on (i.e., attached to and / or integral with) its carbon chain / backbone, such that R can include or be an ether, amine, etc.

[0020] Generally, suitable hydrocarbyl groups for R can be independently linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. Common examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, modifications, and combinations thereof. Examples of suitable alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, dodecyl, hexadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the above-mentioned alkyl groups in which one or more hydrogen atoms are replaced with a halogen atom, such as F or Cl.Specific 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, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, and their derivatives.Examples of halogenated aryl groups include the above-mentioned aryl groups in which one or more hydrogen atoms are replaced with halogen atoms, such as F or Cl.Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0021] In certain embodiments, R has the average formula -(OC n H 2n ) m -, where subscript n is independently selected from 2 to 4 in each moiety designated by subscript m, and subscript m is 1 to 200. Those skilled in the art will readily appreciate that additional and / or alternative groups may be present in the ether moiety without substantially diminishing the utility or properties of the glycoside portion of the silicon glycan. In certain embodiments, R is a group of formula -(OCH) q (OC3H6) r (OC4H8) s-, where the subscripts q, r, and s are each independently 0 to 200, with the proviso that 1≦q+r+s≦600, and the units denoted by the subscripts q, r, and s can be in random or block form in the polyether. In certain embodiments, the subscripts q, r, and s are each independently 0 to 100, alternatively 0 to 50, alternatively 0 to 20. In certain embodiments, the subscripts q, r, and s are each independently selected such that 1≦q+r+s≦300, alternatively 1≦q+r+s≦200, or alternatively 1≦q+r+s≦60. Those skilled in the art will understand that the moieties denoted by the subscripts m, q, r, and s above are oxyalkylene units such that when any two or more such moieties are present therein, R comprises a polyoxyalkylene. Thus, R can be selected from polyoxyalkylene groups, i.e., moieties comprising multiple oxyalkylene units. In certain embodiments, each oxyalkylene unit, denoted by the subscripts q, r, and s, when present in R, can independently be branched or linear.

[0022] In certain embodiments, R can include an amine moiety, such as a tertiary amine moiety, a quaternary ammonium moiety (e.g., a trimethylammonium moiety), or a combination thereof. Tertiary amines have the formula -NR', where each R' is independently selected from substituted and unsubstituted hydrocarbyl groups and ether moieties (e.g., any of the hydrocarbyl groups and ether moieties described herein), or each R' is part of a cyclic moiety, such that the amine moiety includes a heterocycle (e.g., an N-substituted piperidine, morpholine, etc.), and together form a cyclic moiety. The cation of such a tertiary amine moiety is its protonated or alkylated form and has the general formula -[N(R')H] + or -[N(R')3] +wherein each R' is independently selected and defined above. In such embodiments, depending on the particular R' selected, the glycoside portion of the silicon glycan may comprise and / or be defined as N,N-diethylaminoethyl hydroxyethyl cellulose, N,N-dimethylaminoethyl hydroxyethyl cellulose, N,N-diisopropylaminoethyl hydroxyethyl cellulose, N,N-dimethylaminopropyl hydroxyethyl cellulose, N-ethylpiperidine hydroxyethyl cellulose, N-ethylmorpholine hydroxyethyl cellulose, N-ethylpyrrolidine hydroxyethyl cellulose, or a combination thereof.

[0023] It should be understood that each R may be the same or different from the other R in the silicon glycan. Furthermore, each R may contain the same or different functional moieties therein. For example, in certain embodiments, each R is selected from H and an alkyl group, and each alkyl group is optionally substituted (e.g., terminally and / or pendantly) with one or more tertiary amino moieties and / or the polyoxyalkylene groups described above. In these embodiments, each R can be said to be selected from substituted or unsubstituted hydrocarbyl groups, ether moieties, amine moieties, and H, and those skilled in the art will understand, in light of this description, that suitable substituted hydrocarbyl groups for R may contain ether and / or amine moieties. In certain embodiments, each R is selected from H, C1-C6 18 It is independently selected from a hydrocarbyl group, a polyoxyalkylene group, and a tertiary amino group.

[0024] The silicon glycan may include a substituent Z. More specifically, with reference to Formula (I), each subscript o is independently 0 or 1, such that each sugar moiety A denoted by subscripts x, y, and z can be independently substituted with a substituent Z. This is described in more detail below. In certain embodiments, the silicon glycan includes at least one sugar moiety A denoted by subscript x, where subscript o is 1. In these or other embodiments, the silicon glycan includes at least one sugar moiety A denoted by subscript x, where subscript o is 0. In these or other embodiments, the silicon glycan includes at least one sugar moiety A denoted by subscript y, where subscript o is 1. In some such embodiments, subscript o is 1 in each moiety denoted by subscript y. In these or other embodiments, as will be understood in light of the description herein, subscript o is 1 in each moiety denoted by subscript z.

[0025] Generally, each Z is a divalent linking group containing an ether moiety (hereinafter "ether moiety Z"). More specifically, each ether moiety Z is independently selected and can be any ether moiety containing at least one, or alternatively at least two, ether groups. Each ether moiety Z can be the same as any other ether moiety Z. Generally, the ether group of each ether moiety Z has the formula -(C t H 2t O) uwhere the subscript t is independently selected from 2 to 4 in each moiety designated by the subscript u, and the subscript u is 1 to 50. In certain embodiments, the subscript u is 1 to 25, alternatively from 1 to 10, alternatively from 1 to 5. In certain embodiments, the subscript t is 2 and the subscript u is 1, such that each ether moiety Z comprises an ethyl ether, and the glycoside portion of the silicon glycan may comprise and / or be defined as hydroxyethyl cellulose. In some embodiments, the subscript o and the ether moiety Z may be collectively selected such that the glycoside portion of the silicon glycan may comprise or be defined as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc., or combinations thereof. In view of these examples, one skilled in the art will understand that the ether moiety Z may comprise groups in addition to ether groups, such as divalent hydrocarbon linking groups (e.g., alkylene groups such as methylene, ethylene, or propylene linking groups).

[0026] The glycoside moiety of the silicon glycan can include an aminoethyl saccharide moiety. In particular, with reference to formula (I), the silicon glycan can include a sugar moiety A, denoted by the subscript y, each of which has the subformula -CH2CH2N(H)R 1 wherein R 1 is a hydrocarbyl group or H. More specifically, each R 1 is independently selected from substituted or unsubstituted hydrocarbyl groups and H. Examples of suitable hydrocarbyl groups include those described above for the substituent R. In certain embodiments, each R 1 is R 1 When R is alkyl, the aminoethyl moiety is independently selected from H and alkyl groups, as further defined as an N-alkylaminoethyl moiety. 1 are the same as each other. For example, in some such embodiments, each R 1is H or a C1-C4 hydrocarbyl group. In certain embodiments, each R 1 is H. In some embodiments, each R 1 is ethyl or methyl.

[0027] In certain embodiments, some of the aminoethyl moieties are protonated, thus representing the subformula —CHCH—[N(H)R 1 ] + The proportion of protonated aminoethyl moieties in the silicon glycan is limited only by the degree of aminoethyl substitution and can be selected by those skilled in the art (e.g., during the preparation of the silicon glycan, after the preparation of the silicon glycan by combining it with an acid, etc.).

[0028] With continued reference to formula (I), as introduced above, the sugar moiety A, designated by subscript z, comprises a moiety of the subformula -CHCH-WY, where each W is independently selected from the group consisting of amide and imide moieties derived from the reaction of a siloxane-bonded anhydride functional group with a polysaccharide-bonded amino functional group (hereinafter "amide moiety W"), and Y comprises an organosilicon moiety (hereinafter "organosilicon moiety Y").

[0029] Each amide moiety W is [ka] wherein R 4 is selected from the group consisting of a hydrogen atom and an alkyl group, and R 5 is a divalent hydrocarbon group, ** indicates the point of attachment to the carbon atom, and * indicates the point of attachment to the organosilicon moiety Y. 4The alkyl groups of R are exemplified by methyl, ethyl, propyl (including isopropyl and / or n-propyl), butyl (including iso-butyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (including iso-pentyl, neopentyl, and / or tert-pentyl), hexyl, dodecyl, and hexadecyl (including branched saturated hydrocarbon groups having 6 to 18 carbon atoms). 5 The divalent hydrocarbon groups of R are exemplified by alkylene groups such as methylene, ethylene, or propylene, arylene groups such as phenylene, xylylene, or tolylene, and alkylene-arylene groups such as methylenephenylene or ethylenephenylene. 5 Alternatively, the amide moiety W can be: [ka] Alternatively, the amide moiety W may comprise a group selected from the group consisting of: [ka] may be selected from the group consisting of:

[0030] Each organosilicon moiety Y is independently selected so that each organosilicon moiety Y can be the same as any one or any of the other organosilicon moieties Y. In certain embodiments, each organosilicon moiety Y is the same as at least one, or each, other organosilicon moiety Y. The organosilicon moiety Y is generally not limited in terms of structure and / or composition and can be any moiety containing at least one, or at least two, organosilicon groups. For example, the organosilicon moiety Y can include an organosilyl group, an organosiloxane group, or a combination thereof. In certain embodiments, the organosilicon moiety Y is itself considered an organosilicon group.

[0031] In some embodiments, at least one, alternatively at least two, or each organosilicon moiety Y comprises or is a silane moiety. In such embodiments, the silane moiety generally has the general formula: [ka] In the formula, each R 2 are independently selected from substituted or unsubstituted hydrocarbyl groups, alkoxy groups, and siloxy groups.

[0032] Each R 2 is independently selected and can be linear, branched, cyclic, or a combination thereof. 2 R is independently selected from substituted or unsubstituted hydrocarbyl groups, alkoxy, and siloxy groups, but may include combinations thereof, such as combinations of hydrocarbyl and siloxy groups, as will be understood from the description herein. 2 Examples of substituted or unsubstituted hydrocarbyl groups suitable for use as are described above with respect to R in general formula (I). Examples of suitable alkoxy groups include those having the general formula -OR, where R is defined above. Specific examples of suitable alkoxy groups include methoxy, ethoxy, propoxy, butoxy, phenoxy, and the like. Examples of suitable siloxy groups include [M], [D], [T], and [Q] units, each of which represents an individual functional structural unit present in an organopolysiloxane, as understood in the art. More specifically, as shown in the following general structural portion, [M] is a group of the general formula R 3 3SiO 1 / 2 [D] represents a monofunctional unit of the general formula R 3 2SiO 2 / 2 [T] represents a difunctional unit of the general formula R 3 SiO 3 / 2 [Q] represents a trifunctional unit of the general formula SiO 4 / 2 represents a tetrafunctional unit of [ka]

[0033] In these general structural moieties, each R 3 are independently monovalent or polyvalent substituents. As is understood in the art, each R 3 Specific substituents suitable for can be, but are not limited to, monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, and combinations thereof.

[0034] Usually each R 3 R is independently selected from hydrocarbyl groups and siloxy groups. 3 The hydrocarbyl groups represented by, when present, can be substituted or unsubstituted and can be aliphatic, aromatic, cyclic, alicyclic, etc., as described above with respect to examples of suitable hydrocarbyl groups for R; 3 Similar examples are suitable for use with R 3 The siloxy groups represented by, when present, can be substituted or unsubstituted, or can include any combination of [M], [D], [T], and [Q] units (i.e., the silane portion can include branched and / or dendrimeric siloxanes).

[0035] In some embodiments, at least one, or at least two, or each organosilicon moiety Y of the silicon glycan comprises or is an organopolysiloxane. In such embodiments, the organopolysiloxane generally has the formula: [R 3’ 3SiO 1 / 2 ] a [R 3’ 2SiO 2 / 2 ] b [R 3’ SiO 3 / 2 ] c [SiO 4 / 2 ] d、 In the formula, each R 3’ is R as defined above 3and a covalent bond to the amide moiety W, with the proviso that at least one R 3’ is a bond to the amide or imide moiety W, and the subscripts a, b, c, and d are each mole fractions such that a+b+c+d=1, with the proviso that a+b+c>0.

[0036] As introduced and explained above, it will be understood by those skilled in the art that the siloxy moieties designated by the subscripts a, b, c, and d correspond to [M], [D], [T], and [Q] siloxy units, respectively. In some embodiments, the organopolysiloxane includes repeating [D] units, i.e., subscript b>0. In these embodiments, subscript b is typically a value of 0.3 to 1 (e.g., 0.3≦b≦1), e.g., 0.3 to 0.9999, alternatively 0.3 to 0.999, alternatively 0.3 to 0.99, alternatively 0.3 to 0.9, alternatively 0.5 to 0.999, alternatively 0.6 to 0.999, alternatively 0.7 to 0.99, alternatively 0.8 to 0.99, alternatively 0.85 to 0.99, alternatively 0.9 to 0.99. The subscript a is typically a value between 0 and 0.1 (0≦a≦0.1), for example, between 0 and 0.099, alternatively between 0 and 0.09, alternatively between 0 and 0.085, alternatively between 0 and 0.08, alternatively between 0 and 0.075, alternatively between 0 and 0.07, alternatively between 0 and 0.065, alternatively between 0 and 0.06, alternatively between 0 and 0.055, alternatively between 0 and 0.05, alternatively between 0.001 and 0.05, alternatively between 0.002 and 0.05, alternatively between 0.005 and 0.01. Subscripts c and d are typically each independently selected values ​​from 0 to 0.1 (e.g., 0≦c≦0.1 and 0≦d≦0.1), e.g., from 0 to 0.09, alternatively from 0 to 0.075, alternatively from 0 to 0.05, alternatively from 0 to 0.025, alternatively from 0 to 0.009, alternatively from 0 to 0.001, alternatively from 0 to 0.0001. In certain embodiments, the organopolysiloxane comprises linear siloxane segments, wherein subscript b is from 0.9 to 1, subscript a is from 0 to 0.1, and subscripts c and d are each 0. When the organopolysiloxane comprises repeating [D] units, the number of particular [D] units (i.e., degree of polymerization, DP) in any one siloxane segment is not limited. Typically, such siloxane segments contain from 1 to 700 repeating [D] units, for example, from 2 to 600, alternatively from 2 to 500, alternatively from 5 to 400, alternatively from 5 to 300, alternatively from 10 to 250, alternatively from 10 to 200, alternatively from 15 to 150, alternatively from 15 to 100, alternatively from 15 to 50 repeating [D] units.

[0037] With respect to both the silane moiety and organopolysiloxane described above (i.e., when either or both are utilized in or as the organosilicon moiety Y), the presence and proportion of [M], [D], [T], and [Q] units are determined by the respective R of each silyl substituent of each silane moiety. 3 as specific substituents of, as well as each R of any specific siloxy unit (e.g., those designated by subscripts a, b, and c). 3are independently selected as specific substituents of . The ratio of [T] and [Q] units at or near 0 is generally selected to enhance the linearity of the organopolysiloxane, for example, when the organopolysiloxane is a linear organopolysiloxane. Such organopolysiloxanes are generally linear or substantially linear, but may contain some branching due to [T] and / or [Q] units (e.g., when c + d > 0). Conversely, when the organopolysiloxane is a resin, the ratio of [T] and / or [Q] units is selected to be greater than 0. Thus, one skilled in the art will select the composition of the siloxane segment to control the composition of the organopolysiloxane, and thus the silicone glycan, based on, for example, the desired properties of a particular organopolysiloxane and the desired / intended properties and / or characteristics (e.g., physical, chemical, aesthetic, etc.) of the silicone glycan, the particular phase of the emulsion prepared therewith (e.g., the non-aqueous phase, the continuous phase, and / or the silicone phase), and / or the emulsion itself, formulations containing the silicone glycan, coatings formed from such formulations, and combinations thereof. For example, it may be desirable for the silicone glycan to have a high melting point and / or softening point, or for the formulation prepared therewith to be in a particular form (e.g., a solid, a gel, etc.), and selecting the composition of the organopolysiloxane of the silicone glycan may enable one skilled in the art to achieve such a range of desired properties. Generally, when linear siloxane segments are utilized in the organosilicon moiety Y, layers or coatings formed from compositions comprising silicon glycans according to the present disclosure generally have improved feel (e.g., comfortable deposition) and flexibility compared to embodiments in which the organopolysiloxane comprises increased branching due to [T] and / or [Q] units. When resinous organopolysiloxanes are used in or as the organosilicon moiety Y, products formed from compositions comprising silicon glycans according to the present disclosure generally exhibit increased hardness and migration resistance compared to embodiments in which more linear siloxane segments are utilized.

[0038] A method for preparing silicon glycans is also provided, hereinafter generally referred to as the "preparation method." The preparation method includes reacting (A) an aminoethyl polysaccharide with (B) an anhydride-functional organosilicon compound to obtain silicon glycans.

[0039] As will be understood by those skilled in the art in light of the present disclosure, the aminoethyl polysaccharide (A) utilized in the preparation method forms part of a silicon glycan corresponding to the glycoside moiety described above. Similarly, the anhydride-functional organosilicon compound (B) utilized in the preparation method forms part of a silicon glycan corresponding to the organosilicon moiety Y. As described in more detail below, the amide moiety W is generally formed by the reaction of components (A) and (B).

[0040] The aminoethyl polysaccharide (A) has the following general formula (II): [ka] In the formula, each A, Z, R, R 1 and the subscript o are independently selected and are defined above with respect to formula (I), the subscript x is ≧0 to <1, and the subscript y′ is >0 to 1, provided that x+y′=1, and the moieties represented by the subscripts x and y′ can be in a randomized or blocked form in the aminoethyl polysaccharide (A).

[0041] The aminoethyl polysaccharide (A) is not particularly limited and generally corresponds to the glycoside moiety of formula (I) above. For example, as described above for the sugar moiety A designated by subscript y in formula (I), each R of the aminoethyl polysaccharide (A) of formula (II) 1 is independently selected from a hydrocarbyl group and H. Similarly, in certain embodiments, at least one R 1 is an alkyl group (eg, a C1-C4 alkyl group) such that the aminoethyl polysaccharide (A) may be further defined as an N-alkylaminoethyl polysaccharide.

[0042] In certain embodiments, some of the aminoethyl moieties of the aminoethyl polysaccharide (A) (i.e., the sub-formula -CHCHN(H)R of the general formula (II) above) may be 1 is protonated and therefore has the subformula -CHCH-[N(H)R 1 ] + The proportion of protonated aminoethyl moieties in the aminoethyl polysaccharide (A) is limited only by the degree of aminoethyl substitution and can be selected by one skilled in the art (e.g., by limiting the amount of neutralization during preparation of the aminoethyl polysaccharide (A), or by combining with an acid after preparation of the aminoethyl polysaccharide (A)).

[0043] Each of components (A) and (B) may be obtained or formed. In certain embodiments, the preparation method includes preparing an aminoethyl polysaccharide (A). In particular, the preparation method may include reacting (A1) a hydroxyl-functional polysaccharide with (A2) an aziridinium halide compound to obtain the aminoethyl polysaccharide (A). In such embodiments, the aminoethyl polysaccharide (A) may be defined as or otherwise considered to be an intermediate in the preparation method of silicon glycans.

[0044] As will be understood by those skilled in the art in light of the present disclosure, the hydroxyl-functional polysaccharide (A1) forms the polysaccharide portion of the aminoethyl polysaccharide (A), ultimately forming the glycoside portion of the silica glycocan. Therefore, the above discussion regarding the glycoside portion equally applies to the hydroxyl-functional polysaccharide (A1), just as the hydroxyl-functional polysaccharide (A1) can include any of the oligosaccharides or polysaccharides described above. For example, the hydroxyl-functional polysaccharide (A1) can comprise, or consist essentially of, cellulose, hemicellulose, pectin, glycogen, hydrocolloid, starch, modified starch, etc., or a combination thereof. In some embodiments, the hydroxyl-functional polysaccharide (A1) comprises a hydroxyalkyl cellulose ether. In such embodiments, the hydroxyl-functional polysaccharide (A1) can comprise a single type of hydroxyalkyl group, or two or more types of hydroxyalkyl groups. For example, the hydroxyl-functional polysaccharide (A1) can comprise 2-hydroxyethyl groups, 2-hydroxypropyl groups, 3-hydroxypropyl groups, etc., or a combination thereof. In certain embodiments, the hydroxyl-functional polysaccharide (A1) comprises or is pullulan, mannan, galactomannan, xyloglucan, xanthan, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, and the like, as well as combinations thereof.

[0045] The hydroxyl-functional polysaccharide (A1) can include or be a modification / derivative (e.g., a modified and / or altered version) of one of the oligosaccharides or polysaccharides defined above, such as a hydrophobically modified polysaccharide, a cationic modified polysaccharide, a hydrophilically modified polysaccharide, a copolymerized polysaccharide, or a combination thereof. Specific examples of such polysaccharides include N,N-diethylaminoethyl hydroxyethyl cellulose, N,N-dimethylaminoethyl hydroxyethyl cellulose, N,N-diisopropylaminoethyl hydroxyethyl cellulose, N,N-dimethylaminopropyl hydroxyethyl cellulose, N-ethylpiperidine hydroxyethyl cellulose, N-ethylmorpholine hydroxyethyl cellulose, N-ethylpyrrolidine, hydroxyethyl cellulose, and the like, as well as derivatives, modifications, and combinations thereof.

[0046] In certain embodiments, the hydroxyl-functional polysaccharide (A1) is hydroxyethyl cellulose. In such embodiments, the hydroxyl-functional polysaccharide A1 can be modified to be cationic, hydrophobic, and / or hydrophilic, for example, via hydrocarbon moieties, polyoxyalkylene moieties, and / or amine moieties attached thereto.

[0047] The degree of substitution of the hydroxyl-functional polysaccharide (A1) (e.g., with respect to hydroxyl functionality, number of hydroxyalkyl groups, number of quaternary ammonium groups, etc. per sugar moiety A therein) is determined by analysis of the hydroxyl-functional polysaccharide (A1). As will be understood by those skilled in the art, such analysis may include, for example, determining ethoxyl and / or hydroxyethoxyl substitution (e.g., when the hydroxyl-functional polysaccharide (A1) is a cellulose ether) via Zeisel gas chromatography (GC) techniques outlined in ASTM Test Method D4794-94 (2017), determining methoxyl and / or hydroxypropoxyl substitution (e.g., when the hydroxyl-functional polysaccharide (A1) is a cellulose ether) via Zeisel GS techniques outlined in ASTM Test Method D3876-96 (2013), or a combination thereof. Such techniques are known in the art and are independently selected by the skilled artisan based on, for example, the type of hydroxyl-functional polysaccharide (A1) utilized, the functional groups attached thereto, its degree of substitution, etc.

[0048] In certain embodiments, the hydroxyl-functional polysaccharide (A1) is a hydroxyl alkyl cellulose ether having an average degree of substitution per sugar moiety A of 0.50 to 4.0 C1-C6 alkyl ether groups, for example, 0.5 to 2.5, alternatively 0.5 to 3.5, alternatively 1.0 to 2.5, alternatively 1.5 to 2.5.

[0049] The hydroxyl-functional polysaccharide (A1) generally has a weight average molecular weight (M) of at least about 2500. w In certain embodiments, the hydroxyl-functional polysaccharide (A1) has an M of at least 2500, alternatively at least 5000, alternatively at least 10,000, alternatively at least 25,000, alternatively at least 50,000, alternatively at least 75,000. w In these or other embodiments, the hydroxyl-functional polysaccharide (A1) has an M of 70,000 to 3,000,000, e.g., 100,000 to 1,500,000, or 150,000 to 1,000,000.w The weight average molecular weight can be readily determined using gel permeation chromatography (GPC) with multi-angle light scattering (MALLS) detection technology, as described in W. Gao, X. Liu, and R. A. Gross, Polym. Int., 58, 1115-1119 (2009).

[0050] The halogenated aziridinium compound (A2) has the general formula: [ka] In the formula, R 1 is defined above, and -X is chloride or bromide. As will be understood by those skilled in the art, the halide aziridinium compound (A2) can be prepared by reacting the aminoethyl polysaccharide (A) with the sub-formula -CHCHN(H)R 1 Thus, R 1 The above statements regarding the scope and limitations of are equally applicable with respect to the halogenated aziridinium compound (A2). In certain embodiments, the halogenated aziridinium compound (A2) is selected from chloride and / or bromide salts of a cation selected from aziridinium, N-methylaziridinium, N-ethylaziridinium, N-propylaziridinium, N-butylaziridinium, and combinations thereof. In certain embodiments, the halogenated aziridinium compound (A2) comprises or is aziridinium chloride or N-methylaziridinium chloride.

[0051] The halogenated aziridinium compound (A2) can be prepared by any method known to those skilled in the art or can be obtained by other methods. For example, the halogenated aziridinium compound (A2) can be formed in situ by neutralizing the halide salt of the corresponding beta-haloethylamine with a stoichiometric amount of base (e.g., NaOH, KOH, etc.).

[0052] The hydroxyl-functional polysaccharide (A1) and the halogenated aziridinium compound (A2) can be reacted in various amounts to form the aminoethyl polysaccharide (A). Generally, component (A2) is utilized in a stoichiometric ratio of at least 1:1, based on the number of hydroxyl groups in (A1) to be alkylated. Thus, the amount of halogenated aziridinium compound (A2) is generally selected based on the amount, degree of polymerization, and / or degree of substitution of the hydroxyl-functional polysaccharide (A1), as will be understood by those skilled in the art. To maximize the degree of aminoethyl substitution in the aminoethyl polysaccharide (A), an excess or total excess of component (A2) can be utilized. For example, components (A1) and (A2) can be utilized in a stoichiometric ratio (A1:A2) of 1:≥1, even when the degree of free hydroxyl substitution of component (A1) is ≤1. Higher or lower ratios can also be utilized.

[0053] The hydroxyl-functional polysaccharide (A1) and the halogenated aziridinium compound (A2) can be reacted under a variety of conditions, independently selected (e.g., taking into consideration the particular hydroxyl-functional polysaccharide (A1) and / or halogenated aziridinium compound (A2) being utilized, the particular aminoethyl polysaccharide (A) being formed, etc.). For example, the temperature and / or atmosphere of the reaction of components (A1) and (A2) can be independently selected. More specifically, components (A1) and (A2) can be reacted under ambient conditions, under a controlled atmosphere (e.g., under N, argon, etc.), at elevated temperatures (e.g., >25°C, e.g., 30-150°C, alternatively, 30-100°C, alternatively, 50-100°C, alternatively, 70-100°C, alternatively, 50-85°C, etc.), or combinations thereof. In certain embodiments, the reaction of components (A1) and (A2) is carried out for a period of 30 minutes to 24 hours, e.g., 1-12 hours, alternatively, 2-6 hours. However, as will be appreciated by those skilled in the art, the specific times utilized may vary from these ranges and will be selected based on the size / scale of the reaction, the particular components being reacted, and other reaction conditions utilized.

[0054] Components (A1) and (A2) can be reacted in the presence of a carrier liquid (e.g., a solvent, diluent, vehicle, or combination thereof) so that the reaction occurs in a solution, emulsion, suspension, slurry, two-phase mixture, or combinations thereof. The particular solvent, carrier, and / or diluent utilized, and the respective amounts used, are independently selected by those skilled in the art based on, for example, the particular hydroxyl-functional polysaccharide (A1) and / or halogenated aziridinium compound (A2) utilized, the particular aminoethyl polysaccharide (A) formed, etc. For example, those skilled in the art will understand that the reaction of the polysaccharide can be carried out heterogeneously, for example, with the polysaccharide suspended but not dissolved in a polar organic diluent. However, the various components of the reaction can be used as a homogeneous mixture (i.e., before forming a heterogeneous reaction mixture therewith).

[0055] Examples of components suitable for use in or as a carrier liquid, such as in or as a diluent in the reaction of components (A1) and (A2), generally include water-soluble polar organic solvents. In certain embodiments, the diluent comprises methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-butanone, tetrahydrofuran, acetone, or a combination thereof. However, additional and / or alternative carrier liquids and / or diluents, such as any of those described in more detail herein, may also be utilized.

[0056] The content of certain solvents (e.g., water, protonated solvents, etc.) in the reaction can be adjusted to result in swelling of the polysaccharide, particularly when a diluent is used (e.g., in a heterogeneous reaction). Thus, the amount of diluent, water, etc. in the reaction is selected in consideration of the specific components (e.g., components (A1), (A2), base, etc.) to achieve sufficient swelling of the hydroxyl-functional polysaccharide (A1) so that its alkylation with the aziridinium halide compound (A2) can proceed accordingly.

[0057] The degree of aminoethyl substitution of the aminoethyl polysaccharide (A) can vary and can be selected and / or controlled, for example, by the degree of hydroxyl substitution of the hydroxyl-functional polysaccharide (A1), the equivalent of the halogenated aziridinium compound (A2) utilized, the conditions under which (A1) and (A2) are reacted, etc. Typically, the aminoethyl polysaccharide (A) has an average degree of substitution of aminoethyl groups per sugar moiety A of 0.05 to 1, e.g., 0.075 to 0.75, alternatively 0.075 to 0.6, alternatively 0.09 to 0.6, alternatively 0.1 to 0.6, alternatively 0.1 to 0.5, or alternatively 0.15 to 0.45. The degree of aminoethyl substitution of the aminoethyl polysaccharide (A) can be determined by various techniques known in the art. For example, the nitrogen content of the aminoethyl polysaccharide (A) (e.g., as determined by the Kjeldahl method) can be used directly or adjusted (e.g., based on the nitrogen content of the hydroxyl-functional polysaccharide (A1)) to determine the degree of aminoethyl substitution of the aminoethyl polysaccharide (A).

[0058] The anhydride-functional organosilicon compound (B) is [ka] Alternatively, the anhydride-functional organosilicon compound has a formula selected from the group consisting of: [ka] Alternatively, the anhydride-functional organosilicon compound may have the formula [ka] The group R of the anhydride-functional organosilicon compound (B) may have 4 and R 5 , and the organosilicon moiety Y are each a group R of a silicon glycan. 4 and R 5and the organosilicon moiety Y, i.e., as described above with respect to formula (I). Thus, the organosilicon moiety Y of the anhydride-functional organosilicon compound (B) can include a silyl moiety, an organopolysiloxane moiety, or both. For example, when Y is a silyl moiety, the anhydride-functional organosilicon compound (B) can have the formula [ka] and In the formula, each R 2 are independently selected and are as defined above, and R6 is [ka] wherein R is an anhydride moiety selected from the group consisting of 4 and R 5 is as above, with * indicating the point of attachment of the organosilicon moiety Y to the silicon atom; or R 6 teeth, [ka] Alternatively, R may be an anhydride moiety selected from the group consisting of 6 teeth, [ka] It could be.

[0059] Alternatively, the anhydride-functional organosilicon compound (B) may be a compound of the formula [R 3 3SiO 1 / 2 ] a [R 3 2SiO 2 / 2 ] b [R 3 SiO 3 / 2 ] c [SiO 4 / 2 ] d wherein the subscripts a, b, c, and d and each R 3 are independently selected and are as defined above, with the proviso that a+b+c>0, and at least one R 3As shown above, the anhydride moiety R 6 Alternatively, the anhydride-functional organosilicon compound (B) can have 1 to 20 anhydride moieties per molecule, or alternatively 1 to <20 anhydride moieties per molecule.

[0060] While not wishing to be bound by a particular synthetic process, anhydride-functional organopolysiloxanes suitable for use herein can be prepared by known methods such as those disclosed in U.S. Pat. No. 5,015,700. 6 Me2SiO 1 / 2 (wherein Me represents a methyl group, R 6 This patent discloses bisanhydride-terminated polydiorganosiloxanes, such as polydimethylsiloxanes terminated with groups (wherein represents an anhydride functional group), as well as organopolysiloxanes with pendant anhydride functionality, such as trimethylsiloxy-terminated poly(methyl, anhydride-functional)siloxanes and trimethylsiloxy-terminated poly(methyl, anhydride-functional / dimethyl)siloxanes, and equivalent organopolysiloxanes with both terminal and pendant anhydride functionality. Other anhydride-functional linear siloxanes, such as tetrahydrophthalic anhydride-terminated polydiorganosiloxanes, and methods for their preparation are known, for example, from U.S. Pat. No. 5,117,001.

[0061] Anhydride-functional silicone resins suitable for use herein and methods for preparing them are disclosed in U.S. Patent Nos. 7,727,595 and 7,807,012, column 5, line 45 to column 6, line 59. For example, anhydride-functional silicone resins can be prepared by first preparing a SiH-functional resin intermediate, followed by hydrosilylation of the SiH-functional resin intermediate with 2-methyl-3-butyn-2-ol, dehydration to form diene functionality, and Diels-Alder addition of maleic anhydride. Anhydride-functional silsesquioxane resins and methods for preparing them are also disclosed in U.S. Patent Application No. 2008 / 0071017, which is incorporated herein by reference.

[0062] Other examples of suitable methods for preparing anhydride-functional organopolysiloxanes include the hydrosilylation reaction of an aliphatic unsaturated anhydride compound (such as carboxylic anhydride, maleic anhydride, or allyl succinate anhydride) with an intermediate containing a silicon-bonded hydrogen atom in the presence of a platinum catalyst, or the radical reaction of an organopolysiloxane having an unsaturated group (e.g., alkenyl group) with an unsaturated anhydride compound in the presence of a free radical initiator or photoinitiator. Examples of anhydride-functional organopolysiloxanes produced by the radical-initiated reaction of an organopolysiloxane having an unsaturated group (e.g., alkenyl group) with an unsaturated anhydride compound in the presence of a free radical initiator or photoinitiator can be prepared as described in U.S. Provisional Patent Application No. 62 / 703995, filed July 27, 2018, which is incorporated herein by reference.

[0063] The aminoethyl polysaccharide (A) and the anhydride-functional organosilicon compound (B) can be reacted in various amounts to form silicon glycans. Typically, component (B) is used in a 1:1 ratio, or a stoichiometric ratio of 1:1 to 1:0.1, based on the number of ethylamino groups in component (A), for example, via a ring-opening addition of the ethylamino amine group of component (A) to the anhydride functional group of component (B), thereby forming the amide moiety W described above. Therefore, as will be understood by those skilled in the art, the amount of anhydride-functional organosilicon compound (B) is typically selected based on the amount, degree of polymerization, and / or degree of substitution of the aminoethyl polysaccharide (A). To maximize the degree of silicon substitution of the silicon glycan, an excess or total excess of component (B) can be used. For example, components (A) and (B) can be used in a stoichiometric ratio (A:B) of 1:≥1, even if the degree of aminoethyl substitution of component (A) is ≤1. Higher or lower ratios can also be used. For example, in some embodiments, components (A) and (B) can be utilized in a stoichiometric ratio (A:B) of ≧1:1 to, for example, increase the relative grafting efficiency of the anhydride-functional organosilicon compound (B) onto the aminoethyl polysaccharide (A).

[0064] The aminoethyl polysaccharide (A) and the anhydride-functional organosilicon compound (B) can be reacted under a variety of conditions, as will be understood by those skilled in the art, which can be independently selected (e.g., taking into consideration the particular compounds (A) and / or (B) utilized, the particular silicon glycan to be formed, the size of the reaction, etc.). For example, the temperature and / or atmosphere for the reaction of components (A) and (B) can be independently selected. More specifically, components (A) and (B) can be reacted under ambient conditions, under a controlled atmosphere (e.g., under N2, argon, etc.), at elevated temperatures (e.g., >25°C, e.g., 30-100°C, alternatively, 50-100°C, alternatively, 50-90°C, alternatively, 60-80°C), or combinations thereof. The reaction temperature is selected based on the particular components of the reaction and, therefore, can be selected to minimize evaporative losses (e.g., of volatile components), achieve reflux (i.e., if conducted in a suitable reactor), drive off volatile components, or a combination thereof (e.g., via the use of elevated temperatures). For example, the reaction is carried out at ambient and / or room temperature (e.g., 20 to about 30, alternatively 22 to 28, alternatively 24 to 26°C). Alternatively, the reaction can be carried out at 60 to 100°C.

[0065] The aminoethyl polysaccharide (A) and the anhydride-functional organosilicon compound (B) can be reacted for any time, such as between 30 minutes and 100 hours. For example, in certain embodiments, the reaction of components (A) and (B) is carried out for 4 hours to 48 hours, e.g., 5, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, or 47 hours. In some embodiments, a reaction time of 48 to 100 hours, such as 50, 60, 70, 80, or 90 hours, is utilized. However, as will be understood by those skilled in the art, the specific time used may vary from these ranges and will be selected based on the size / scale of the reaction, the specific components (A) and (B) used, and other reaction conditions selected. In certain embodiments, the reaction of components (A) and (B) is carried out for 0.5 to 24 hours, e.g., 1 to 18 hours, or 1 to 12 hours, or 1 to 6 hours.

[0066] Components (A) and (B) can be reacted under heterogeneous conditions, such as a multiphase (e.g., biphasic) reaction. Typically, components (A) and (B) are reacted heterogeneously in the presence of a diluent, which may be a multicomponent diluent. Generally, the diluent is selected to swell but not dissolve the aminoethyl polysaccharide (A), to function as a carrier for component (B), or for both purposes. Therefore, the specific components of the diluent are selected based on the specific aminoethyl polysaccharide (A) utilized (e.g., depending on its solubility, swelling, and / or reactivity) and / or the specific organosilicon compound (B) utilized (e.g., the solubility and / or functionality of its organosilicon moieties).

[0067] The diluent usually includes an organic solvent. Examples of organic solvents include 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; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and methylene chloride; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran; white spirits; mineral spirits; naphtha; n-methylpyrrolidone, and the like, as well as their derivatives, modifications, and combinations thereof. Generally, the organic solvent is a polar organic solvent, such as a solvent compatible with water. Specific examples of such polar organic solvents utilized in certain embodiments include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-butanone, tetrahydrofuran, acetone, and combinations thereof.

[0068] In some embodiments, the diluent comprises a silicone fluid. In such embodiments, the silicone fluid is generally a low viscosity and / or volatile siloxane, such as a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methylethyl siloxane, or the like, or a combination thereof. Typically, the silicone fluid has a viscosity of 1 to 1,000 mm at 25°C. 2 In some embodiments, the silicone fluid has a viscosity in the range of 1 / 2 s / sec. 4 R 5 SiO) e wherein each R 4 and R 5 are independently selected from H and substituted or unsubstituted hydrocarbyl groups, and the subscript e is 3 to 8. Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexademethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis {(trimethylsilyl)oxy}trisiloxane pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone, and the like, as well as derivatives, modifications, and combinations thereof. Further examples of suitable silicone fluids include 5x10 -7 ~1.5x10 -6 m 2Examples of suitable diluents include polyorganosiloxanes having a suitable vapor pressure, such as 1 / sec. The diluent typically further comprises a polar component, typically water or another polar compound (e.g., dimethylacetamide, hexamethylphosphoramide, hexafluoroisopropanol, dimethyl sulfoxide, etc.). The specific content of the polar component in the diluent is adjusted to result in swelling of the polysaccharide of component (A). Thus, the amount of diluent, the ratio of polar to nonpolar or other organic solvent in the diluent, and the ratio of polar component to components (A) and / or (B), etc., within the reaction are independently or collectively selected to achieve sufficient swelling of the aminoethyl polysaccharide (A) to facilitate grafting of the organosilicon compound (B) thereto. Similarly, the diluent may contain one or more additives, which may be independently selected to increase and / or decrease the solubility and / or compatibility of any component of the reaction with the diluent. In certain embodiments, the polar component comprises water. In these or other embodiments, the polar component comprises dimethylacetamide, hexamethylphosphoramide, hexafluoroisopropanol, and / or dimethylsulfoxide.

[0069] In certain embodiments, the diluent may include an aprotic organic solvent. Examples of aprotic organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and n-propanol. The aprotic organic solvent is miscible with water. Specific examples of such aprotic organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, and combinations thereof. The diluent may further include water. Alternatively, the diluent may include alcohol, water, or a combination of both alcohol and water.

[0070] In certain embodiments, the reaction mixture may be free of polar aprotic solvents, i.e., "free of polar aprotic solvents" means that the reaction mixture contains 0-1% polar aprotic solvents, or an undetectable amount to 1% polar aprotic solvents (e.g., methyl isobutyl ketone).

[0071] Without wishing to be bound by theory, it is believed that the choice of solvent can affect the silicon content of the silicon glycan product produced by the method described herein.Aprotic organic solvents can be used to provide silicon glycans with higher silicon content than when polar aprotic solvents are used in this method.Alternatively, a mixture of solvents can be used in this method.

[0072] In certain embodiments, the diluent may include an aprotic organic solvent. Examples of aprotic organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and n-propanol. The aprotic organic solvent is miscible with water. Specific examples of such aprotic organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, and combinations thereof. The diluent may further include water. Alternatively, the diluent may include alcohol, water, or a combination of both alcohol and water.

[0073] In certain embodiments, the reaction mixture may be free of polar aprotic solvents, i.e., "free of polar aprotic solvents" means that the reaction mixture contains 0-1% polar aprotic solvents, or an undetectable amount to 1% polar aprotic solvents (e.g., methyl isobutyl ketone).

[0074] Without wishing to be bound by theory, it is believed that the selection of diluent can affect the silicon content of the silicon glycan product produced by the method described herein.Aprotic organic solvents can be used to provide silicon glycans with higher silicon content than when polar aprotic solvents are used in this method.Alternatively, a mixture of diluents can be used in this method.

[0075] In certain embodiments, a reaction product containing silicon glycans is obtained by reacting an aminoethyl polysaccharide (A) with an anhydride-functional organosilicon compound (B), and the preparation method includes isolating the silicon glycans from the reaction product. In such embodiments, any suitable isolation technique and / or protocol can be utilized. Examples of suitable isolation techniques include decantation, distillation, evaporation, extraction, filtration, lyophilization, ion exchange chromatography (e.g., adsorption), simulated moving bed chromatography, partitioning, phase separation, stripping, and washing. As will be understood by those skilled in the art, many of these techniques can be used in combination (i.e., sequentially) to isolate silicon glycans. It should be understood that isolation can include purifying silicon glycans and can therefore be referred to as purifying silicon glycans. As used herein, isolating silicon glycans is generally defined as increasing the relative concentration of silicon glycans compared to other compounds combined with them. Therefore, as understood in the art, isolation / purification can include removing other compounds from such a combination (i.e., reducing the amount of impurities mixed with the silicon glycan) and / or removing the silicon glycan itself from the mixture. Regardless of the specific technique selected, purification of the silicon glycan can be performed sequentially (i.e., in series) with the reaction itself and thus can be automated. In another example, purification can be an independent procedure to which the reaction product containing the silicon glycan is subjected.

[0076] In certain embodiments, isolating the silicon glycan involves altering the solubility profile of the diluent, for example, by adding additional organic solvent (e.g., acetone) to partition and / or phase separate the reaction product. In these or other embodiments, isolating the silicon glycan involves filtering out other components of the reaction product (i.e., if the silicon glycan is present in the residue / solid). In these or other embodiments, isolating the silicon glycan involves washing the other components of the reaction product away from the silicon glycan (e.g., with an organic and / or aqueous solvent). In certain embodiments, isolating the silicon glycan involves stripping the solvent and / or other volatile components from it, including drying the silicon glycan (e.g., when the water is removed).

[0077] As will be appreciated in light of the examples herein, silicon glycans can be used in industrial compositions, such as drilling fluids, to modify their rheology. Alternatively, silicon glycans can be used in personal care products.

[0078] Personal Care Products Silicon glycan can be incorporated into personal care products.Generally, if there is no material that is solid at room temperature, such products can be prepared at room temperature using a simple propeller mixer, a Brookfield counter-rotating mixer, or a homogenizing mixer.No special equipment or processing conditions are typically required.Depending on the type of form to be prepared, the preparation method varies, and such methods are known in the art.

[0079] Personal care products can be functional, cosmetic, therapeutic, or some combination thereof, depending on the body part to which they are applied. Traditional examples of such products include, but are not limited to, antiperspirants and deodorants; skin care creams; skin care lotions; moisturizers; facial treatments such as acne or wrinkle removers; personal and facial cleansers; bath oils; perfumes; colognes; scented bags; sunscreens; pre- and post-shave lotions, shaving soaps, and shaving foams; hair shampoos; hair conditioners (leave-on or rinse-off); hair colorants; hair relaxers; hair styling aids such as sprays, fixatives, mousses, and / or gels; permanents, depilatories, and cuticle coats; makeup; color cosmetics; foundations; concealers; blushers; lipsticks; eyeliners; mascaras; oil removers; color cosmetics removers; powders; medicated creams; pastes or sprays that can be preventative and / or therapeutic (including dental hygiene, antibiotics, healing promoters, and / or nutritional effects). Generally, personal care products can be formulated with a carrier that allows for application in any conventional form, including, but not limited to, liquids, rinses, lotions, creams, pastes, gels, foams, mousses, ointments, sprays, aerosols, soaps, sticks, soft solids, solid gels, and gels. What constitutes a suitable carrier will be apparent to those skilled in the art.

[0080] Silicon glycans can be used in a variety of personal, household, and healthcare applications. In particular, silicon glycans can be used in personal care products such as those disclosed in U.S. Patent No. 6,051,216 to Barr et al., U.S. Patent No. 5,919,441 to Mendolia et al., U.S. Patent No. 5,981,680 to Petroff et al., U.S. Patent Application No. 2010 / 0098648 to Yu, and WO 2004 / 060101 to Yu; in sunscreen compositions such as those disclosed in U.S. Patent No. 6,916,464 to Hansenne et al.; in cosmetic compositions that also contain film-forming resins, such as those disclosed in WO 2003 / 105801 to Yu; in U.S. Patent Application No. 2003 / 0235553 to Lu; in U.S. Patent Application No. 2003 / 0072730 to Tornilhac; in U.S. Patent Application No. 2003 / 0072730 to Ferrari et al. 170188, EP 1,266,647 to Tornilhac, EP 1,266,648 to Ferrari et al., EP 1,266,653 to Ferrari et al., WO 2003 / 105789 to Lu, WO 2004 / 000247 to Lu, and WO 2003 / 106614 to Lu, as an additional agent to that disclosed in WO 2004 / 054523 to Tournilhac, in long-wear cosmetic compositions such as those disclosed in U.S. Patent Application Publication No. 2004 / 0180032, and in transparent or translucent care and / or makeup compositions such as those discussed in WO 2004 / 054524, all of which are incorporated herein by reference.

[0081] Alternatively, silicon glycans can be used as part of a color or fixative composition, applied as a pre-treatment, during, or after the hair coloring or perming process, with goals that can range from color retention and color enhancement to reconditioning colored hair fibers. Examples include patent publications U.S. Patent Application Publication No. 2003 / 0152534 to Legrand et al., U.S. Patent Application Publication No. 2003 / 0152541 to Legrand et al., U.S. Patent Application Publication No. 2003 / 0147840 to Legrand, U.S. Patent No. 6,953,484 to Devin-Baudoin et al., U.S. Patent No. 6,916,467 to Devin-Baudoin et al., U.S. Patent Application Publication No. 2004 / 0045098 to Devin-Baudoin et al., U.S. Patent Application Publication No. 2003 / 0126692 to Devin-Baudoin et al., PCT Publication No. 2007 / 071684 to Audousset, and U.S. Patent Application Publication No. 2008 / 0282482 to Audousset et al. by L'Oreal and Noxell No. 7,335,236 to McKelvey, Inc., all of which are incorporated herein by reference.

[0082] The personal care products according to the present invention can be used by standard methods, such as applying them to the human body, for example, to the skin or hair, using an applicator, a brush, applying them by hand, pouring them onto or into the body, and / or optionally rubbing or massaging the product. For example, the removal methods for color cosmetics are also well-known standard methods, including washing, wiping, and peeling. For use on the skin, the personal care products according to the present invention can be used in a conventional manner, for example, to condition the skin. For this purpose, an effective amount of the product is applied to the skin. Such an effective amount is generally 1 mg / cm. 2 ~3mg / cm 2The range is typically 0.01 to 0.01. Application to the skin typically involves working the composition onto the skin. This method of applying to the skin involves contacting the skin with an effective amount of the composition and then rubbing the composition into the skin. These steps can be repeated as many times as necessary to achieve the desired benefits.

[0083] The application of the personal care product according to the present invention to hair can be performed using conventional methods for conditioning hair. An effective amount of product for conditioning the hair is applied to the hair. Such an effective amount generally ranges from 0.5 g to 50 g, or alternatively from 1 g to 20 g. Application to the hair typically involves working the composition through the hair so that most or all of the hair comes into contact with the product. This method for conditioning hair involves applying an effective amount of a hair care product to the hair and then working the composition through the hair. These steps can be repeated as many times as necessary to achieve the desired conditioning benefits.

[0084] Non-limiting examples of additives that may be incorporated into personal care products in addition to silicon glycans include (i) additional silicones, (ii) anti-acne agents, (iii) anti-caries agents, (iv) anti-dandruff agents, (v) antioxidants, (vi) biocides, (vii) botanicals, (viii) cleansing agents, (ix) color agents, (x) conditioning agents, (xi) deposition agents such as cationic deposition aids, (xii) electrolytes, (xiii) emollients, (xiv) exfoliants, (xv) foam boosters, (xvi) fragrances, (xvii) moisturizers, (xvii) and the like. (viii) occlusive agents, (xix) oils, (xx) pediculicides, (xxi) pH control agents, (xxii) pigments, (xxiii) preservatives, (xxiv) rheology modifiers, (xxv) solvents, (xxvi) stabilizers, (xxvii) stabilizing agents, (xxviii) sunscreens, (xxix) surfactants, (xxx) suspending agents, (xxxi) tanning agents, (xxxii) thickeners, (xxxiii) vitamins, (xxxiv) waxes, (xxxv) wound healing promoters, and (xxxvi) any two or more of (i)-(xxxv).

[0085] It is understood that the scope of the appended claims is not limited to the language in the "Description of the Invention" and the specific compounds, compositions, or methods described therein, and may vary among specific embodiments within the scope of the appended claims. With respect to any Markush group relied upon herein to describe particular features or aspects of various embodiments, different, special, and / or unexpected results may be obtained from each member of the respective Markush group independent of all other Markush members. Each member of a Markush group may be relied upon individually and / or in combination to provide adequate support for specific embodiments within the scope of the appended claims.

[0086] Furthermore, any ranges and subranges relied upon in describing various embodiments of the present invention are understood to be individually and collectively included in the appended claims, describing and contemplated ranges including their whole and / or fractional values, even if such values ​​are not expressly written herein. Those skilled in the art will readily recognize that the recited ranges and subranges fully describe and enable various embodiments of the present invention, and that such ranges and subranges may be further elaborated into related halves, thirds, quarters, fifths, etc. As merely an example, a range "from 0.1 to 0.9" may be further elaborated into a lower third, i.e., 0.1 to 0.3, a middle third, i.e., 0.4 to 0.6, and an upper third, i.e., 0.7 to 0.9, which are individually and collectively within the appended claims and may be relied upon individually and / or collectively to provide appropriate support for specific embodiments of the appended claims. Additionally, with respect to terms defining or modifying a range, such as "at least," "greater than," "less than," "less than or equal to," etc., it is understood that such terms include subranges and / or upper or lower limits. As another example, the range "at least 10" inherently includes subranges of at least 10 to 35, at least 10 to 25, 25 to 35, etc., each of which may be relied upon individually and / or collectively to provide appropriate support for specific embodiments of the appended claims. Finally, individual numbers within the disclosed ranges may be relied upon to provide appropriate support for specific embodiments of the appended claims. For example, the range "1 to 9" includes various individual integers, such as 3, as well as individual numbers containing a decimal point (or fraction), such as 4.1, which may be relied upon to provide appropriate support for specific embodiments of the appended claims. [Example]

[0087] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the present invention in any way. Starting materials used in the examples were as follows: heavy water (99% D), deuterated chloroform (CDCl), and cis-5-norbornene-endo-2,3-dicarboxylic acid (carboxylic anhydride), maleic anhydride, and benzoyl peroxide were purchased from Sigma-Aldrich and used as received. 2-Propanol (IPA), acetone, m-xylene, and toluene were purchased from Fisher Scientific and used as received. Number average structure M Vi -D9-M Vi Vinyl-terminated polydimethylsiloxane (PDMS) oligomers with (4-2764 INT), MD'M (3-7010), and Karstedt's catalyst were obtained from Dow Silicones Corporation and used as received. 10 D'M and MD 40 Copolymers with D'M were prepared according to conventional procedures. Bu D 10 D'M was obtained from Gelest and used without further purification. In the above formula, M is a compound of the formula (MeSiO 1 / 2 ) and M Vi is the formula (Me2ViSiO 1 / 2 ) and M Bu is the formula (MeBuSiO 1 / 2 ) units, and D represents the formula (MeSiO 2 / 2 ) and D' represents a unit of formula MeHSiO 2 / 2 ) units, in which Me represents a methyl group, Vi represents a vinyl group, and Bu represents a butyl group.

[0088] X-ray fluorescence (XRF): All samples are analyzed using a Rigaku Primus I wavelength dispersive X-ray fluorescence (WDXRF) spectrometer ("XRF instrument").

[0089] Full scan - relative abundance The XRF instrument is equipped with a 4 kW Rh target X-ray source with a primary beam filter, Ni400 for the Rh K-line overlap (Ru, Rh, Pd, Ag, Cd, In, and Sn K-lines), Al25 for the Rh L-line overlap (Ru, Rh, Pd, Ag, Cd, In, and Sn L-lines), and Be30 for X-ray tube protection for delicate samples. Crystallographic analysis includes LiF200 (KU), PET (Al-Si), Ge (P-Cl), RX25 (F-Mg), RX35 (O), RX45 (N), RX61F (C), and RX75 (B). Detectors include a scintillation counter (SC) for Ti-U and a gas (flow) proportional counter for B-Ca.

[0090] Unless otherwise specified, samples are loaded into sample cups containing 6 μm thin polypropylene windows and analyzed using a 30 mm sample mask under a helium environment. The relative abundance of each element detected in the sample is calculated against a one-point calibration using the specified matrix compound. Film impurities specified by the manufacturer include Al, P, Ca, Ti, Fe, Cu, Zn, and Zr. Samples are analyzed in vacuum using a 30 mm sample mask and the conditions described above.

[0091] Attenuated Total Reflection Infrared (ATR-IR): All samples are analyzed using a Thermo Scientific Nicolet 6700 Fourier Transform Infrared (FTIR) spectrometer.

[0092] The samples were analyzed by IR spectroscopy using a single bounce attenuated total reflection attachment with a diamond crystal (4 cm -1 The penetration depth during surface analysis is 1000 cm -1 It is estimated to be around 2 microns.

[0093] Rheology Rheological measurements are performed using a TA Instruments DHR-3 rheometer equipped with a cup and bob sensor using a 40 mm cone and plate at 25°C.

[0094] Each sample (0.2 g) was dissolved in HO (9.8 g) to give a 2% solution, which was stirred at 70° C. for 18 hours and then allowed to cool. If the sample was insoluble in HO, it was heated to 85° C. for several hours. If the sample remained insoluble, acetic acid (1 equivalent) was added to the solution, which was then allowed to stand for 24 hours.

[0095] The solution is then sheared (ultrasonic sonicator; power 100 W for 60 seconds). The sample is pre-sheared (shear rate 1 s -1 The viscosity is measured at 1 second intervals over a 40 second period. -1 Report in mPa·s as the average of all data points measured at a shear rate of

[0096] solubility The solubility of the material as a 2% aqueous solution is tested by attempting to dissolve the material in water. If the material is insoluble, heat it to 85°C for several hours.

[0097] Reference Example 1 - Preparation of an Anhydride-Functional Siloxane Starting hydridosiloxane M BuD9M' (858 g / mol) is weighed (75 g, 0.087 mol, 1 equivalent) into a 500 ml three-neck round-bottom flask equipped with a Teflon-coated magnetic stir bar. Toluene (30 g, 34.5 ml) is added to the reaction mixture along with 150 μl (15 ppm) of a 1% solution of Karstedt's catalyst in toluene. The reaction mixture is warmed to 80°C, and carboxylic anhydride is added slowly over 1 hour. The reaction mixture is stirred at 90°C for 4 hours, then allowed to cool naturally and left overnight. At this point, a large amount of solid, insoluble carboxylic anhydride is present in the solution. The solution is warmed to 80°C, and then 50 μl (5 ppm) of the catalyst solution is added in one portion. No significant exotherm is observed. The reaction mixture is cooled to 60°C, and then 300 μl (30 ppm) of the catalyst solution is added in one portion. The reaction mixture is warmed to 90°C and stirred at that temperature for 8 hours, after which the solution is allowed to cool naturally to room temperature and left overnight. The solution is still a heterogeneous mixture containing a significant amount of solid carboxylic anhydride. After warming the solution to 60°C, 1 ml (100 ppm) of the catalyst solution is added all at once. A slight (2°C) exotherm is observed. The reaction mixture is stirred at that temperature for an additional 6 hours and then allowed to cool naturally to room temperature. At this point, the solution is completely homogeneous, and IR spectroscopy reveals that the reaction is complete. The reaction mixture is transferred to a single-neck round-bottom flask and volatiles are removed by rotary evaporation. The material is further stripped at 110°C under full vacuum for 1 hour. The resulting liquid (73 g) is stored under nitrogen and analyzed by NMR spectroscopy, which reveals the compound of formula M Bu D9M * The formation of an anhydride-functional siloxane of the formula M * is the formula (CAMe2SiO 1 / 2 ) where CA is the unit of the formula [ka] where * indicates the point of attachment of the group to the silicon atom.

[0098] Reference Example 2: Preparation of pseudo-monofunctional anhydride-functional siloxane formula md 10The starting hydridosiloxane D'M (75 g, 0.077 mol, 1 eq.) is placed in a 250 ml three-necked round-bottom flask equipped with a mechanical stirrer and nitrogen inlet. Toluene (25 ml) is added, followed by Karstedt's catalyst as a 1 wt. % solution in toluene (50 μL, 5 ppm). The reaction mixture is warmed to reaction temperature (90°C). Solid carbonic anhydride (12.6 g, 0.077 mol, 1 eq.) is added slowly in approximately 1 g portions. Upon addition of the anhydride, a delayed exotherm is observed (approximately 3°C per gram of anhydride added). After approximately half of the anhydride has been added, the temperature is increased to 100°C. Once all the anhydride has been added, the temperature is increased to 110°C and the reaction mixture is stirred for 1 hour. The temperature is then returned to 100°C, and an additional 100 μL (10 ppm) of platinum catalyst solution is added. After all the anhydride has been added and heating at 110°C for 30 minutes, the Si-H content is 500 ppm. 2.5 ml (250 ppm) of platinum catalyst solution is then added in 500 μl portions over 2 hours. The reaction mixture is then refluxed for 6 hours. The solvent is removed by rotary evaporation, and the product is then filtered through Celite™ and a 5 μm filter to filter the activated carbon. The final product is a yellowish liquid (40 g), which, when analyzed by NMR, has the formula MD 10 It was found that the sigma has D*M.

[0099] Reference Example 3 - Preparation of pseudo-monofunctional anhydride-functional siloxane* formula md 40D'M hydridosiloxane (160 g, 0.05 mol, 1 equiv.) is placed in a 250 ml three-neck round-bottom flask equipped with a mechanical stirrer and nitrogen inlet. Toluene (40 ml) is added, followed by Karstedt's catalyst as a 1 wt. % solution in toluene (500 μl, 31 ppm). The reaction mixture is warmed to reaction temperature (90°C). Solid carboxylic anhydride (7.3 g, 0.05 mol, 1 equiv.) is added slowly in 200-300 mg portions per 3 minutes. Platinum catalyst solution (2.5 ml) is then added in 500 μl portions over 2 hours (156 ppm). The reaction mixture is then refluxed for 6 hours. The solvent is removed by rotary evaporation, and the product is then filtered through Celite™ and a 5 μm filter to remove activated carbon. The final product is a yellowish liquid (120 g). The product is analyzed by NMR, revealing the formula MD 40 D*M, where D * is the formula (CAMeSiO 2 / 2 ) where CA is the unit of the formula [ka] where * indicates the point of attachment of the group to the silicon atom.

[0100] Reference Example 4 - Hydrosilylation of carboxylic anhydride with MD'M The starting hydridosiloxane MD'M is weighed (50 g, 0.21 mol, 1 eq) into a 500 mL three-neck round-bottom flask equipped with a Teflon-coated magnetic stir bar. Toluene (200 g) is added to the reaction mixture. The reaction mixture is warmed to 80 °C and 10% carboxylic acid anhydride is added all at once. A 1% solution of Karstedt's catalyst in toluene (200 μL) is added all at once. Half of the carboxylic acid anhydride (34 g total, 0.2 mol, 0.95 eq) is added in 100 mg portions over 1 h. The reaction mixture is then allowed to react at 90 °C for 30 min. Analysis of the reaction mixture by IR spectroscopy indicates that most of the Si-H has been consumed. An additional load of catalyst (50 μL) is added, and the remaining carboxylic acid anhydride is added in the same manner. The reaction mixture is then allowed to react at 90 °C for an additional 4 h. The reaction mixture is then allowed to cool to room temperature. The next morning, the reaction mixture is completely homogeneous at room temperature, but the conversion is not complete (250 ppm Si-H remaining). The reaction mixture is warmed to 100°C, and then catalyst (100 μL) is added. The reaction mixture is stirred at that temperature for 2 hours and then allowed to cool to room temperature. The next morning, IR analysis reveals a Si-H concentration of 57 ppm, indicating the reaction is complete. The reaction mixture is filtered on a glass frit containing a first layer of Celite™ and a layer of activated carbon. The filter cake is washed twice with 100 ml of toluene. The collected solution is stripped to dryness on a rotary evaporator and then further stripped under full vacuum at 120°C to remove residual Si-H and carboxylic anhydride. A white solid (70 g, 90% yield) is collected and analyzed by NMR spectroscopy with C6D6 and ATR-IR. The solid is found to have the formula MD*M.

[0101] Reference Example 5 - Stability of MD*M In 2-propanol: Formula MD prepared as described above in Reference Example 4 *The anhydride-functional siloxane M (200 mg) was placed in a scintillation vial and suspended in 20 ml of IPA. The reaction mixture was stirred at 80°C for 4 hours, and the solvent was removed by rotary evaporation. The white solid residue was analyzed by NMR spectroscopy with C6D6. No significant signals attributed to isopropyl groups were identified in the NMR spectrum.

[0102] 2-propanol / water: Formula MD * M anhydride-functional siloxane (0.53 g) was placed in a scintillation vial and dissolved in 5 g of a 90 / 10 IPA / water mixture. The reaction mixture was stirred at 80 °C for 4 h, and the solvent was removed by rotary evaporation. The white solid residue was analyzed by NMR spectroscopy with CD6. Growing carboxylic acid peaks and at least a second set of signals were observed. The concentration of "open" anhydride appears to be approximately 33% based on integration of the new Si-Me resonance.

[0103] Preparation Example A: Preparation of a general aminoethyl polysaccharide (aminoethyl-modified hydroxyethyl cellulose) Preparation: A 2000 mL four-neck round-bottom flask was fitted with a stirring paddle and motor, a rubber serum cap, a nitrogen inlet, and a Claisen adapter. The Claisen adapter was fitted with a ground thermocouple connected to a J-KEM controller and a Friedrichs condenser connected to a mineral oil bubbler. The flask was charged with a hydroxyl-functional polysaccharide (134.7 g of CELLOSIZE™ HEC AM-103, Dow Chemical Company, Midland, MI; 120.1 g HEC content, 0.48 mol, DS 2.0), an aziridinium halide precursor (2-aminoethyl chloride hydrochloride; 48.16 g, 0.415 mol), and a mixture of isopropyl alcohol (IPA) (672 g) and deionized water (76 g) to form a slurry. The slurry was stirred (stir motor set at 70 rpm) for 1 hour while purging with nitrogen (approximately 1 bubble per second) to remove entrained oxygen.

[0104] A base (50% aqueous sodium hydroxide; 32.78 g, 0.410 mol) is added dropwise (via a plastic syringe) to the stirring slurry under nitrogen over 1 minute. The slurry is stirred for 5 minutes, then heated to 80°C (via a heating mantle connected to a J-KEM controller set at 80°C) and held for 4 hours. The heating mantle is then removed, and the slurry is cooled in a cold water bath while maintaining positive nitrogen pressure in the flask. At ambient temperature, the slurry is neutralized by adding acid (glacial acetic acid; 6.0 g) to yield a reaction mixture containing the aminoethyl polysaccharide. The aminoethyl polysaccharide was isolated from the reaction mixture as a solid by vacuum filtration through a Büchner funnel (metal, coarse frit). It was then washed in the Büchner funnel with the following washes: once with a mixture of 1200 g acetone and 400 g deionized water; three times with a mixture of 1200 g acetone and 320 g deionized water; once with a mixture of 1200 g acetone and 160 g deionized water; and twice with pure acetone (1200 g). The second acetone wash contained 0.80 g of 40% aqueous glyoxal solution and 0.20 g of glacial acetic acid. The aminoethyl polysaccharide was then vacuum dried overnight at 50 °C to yield the isolated and dried aminoethyl polysaccharide (aminoethyl-modified hydroxyethyl cellulose) as an off-white powder (136.46 g).

[0105] analysis The aminoethyl polysaccharide was manually ground (mortar and pestle), screened (#30 US Standard Sieve), and analyzed according to the above procedure with the following results: Volatile matter content: 3.08%. Ash content: 5.85% (as sodium chloride). Kjeldahl nitrogen content: 1.936%, corresponding to an aminoethyl substitution degree of 0.389. 2.0% solution viscosity: 6.31s -1 479 mPa·s at a shear rate of 25.0°C (corrected for volatiles and ash).

[0106] Preparation Example B: Preparation of a general aminoethyl polysaccharide (aminoethyl-modified hydroxyethyl cellulose) Preparation: The same method as described in Preparative Example A was used, except CELLOSIZE™ HEC AM-103 was replaced with 148.56 g (containing 120.1 g) of CELLOSIZE™ HEC QP-4400H to yield 148.56 g of aminoethyl-modified hydroxyethyl cellulose as an off-white solid.

[0107] analysis The aminoethyl polysaccharide was manually ground (mortar and pestle), screened (#30 US Standard Sieve), and analyzed according to the above procedure with the following results: Volatile matter content: 0.95%. Ash content: 3.24% (as sodium chloride). Kjeldahl nitrogen content: 1.653%, corresponding to an aminoethyl substitution degree of 0.326. 2.0% solution viscosity: 6.31s -1 5543 mPa·s at a shear rate of 25.0°C (corrected for volatiles and ash).

[0108] Preparation Example C: Preparation of a general aminoethyl polysaccharide (aminoethyl-modified hydroxyethyl cellulose) Preparation: A 1000 ml four-neck round-bottom flask was fitted with a stirring paddle and motor, a rubber serum cap, a nitrogen inlet, and a Claisen adapter. The Claisen adapter was fitted with a ground thermocouple connected to a J-KEM controller and a Friedrichs condenser connected to a mineral oil bubbler. The flask was charged with a hydroxyl-functional polysaccharide (67.45 g of CELLOSIZE™ HEC AM-103, Dow Chemical Company, Midland, MI; 60.1 g HEC content, 0.24 mol, DS 2.0), an aziridinium halide precursor (2-aminoethyl chloride hydrochloride; 12.38 g, 0.107 mol), and a mixture of isopropyl alcohol (IPA) (336 g) and deionized water (39 g) to form a slurry. The slurry was stirred (stir motor set at 70 rpm) for 1 hour while purging with nitrogen (approximately 1 bubble per second) to remove entrained oxygen.

[0109] A base (50% aqueous sodium hydroxide; 8.27 g, 0.103 mol) is added dropwise (via a plastic syringe) to the stirring slurry under nitrogen over 1 minute. The slurry is stirred for 5 minutes, then heated to 80°C (via a heating mantle connected to a J-KEM controller set at 80°C) and held for 4 hours. The heating mantle is then removed, and the slurry is cooled in a cold water bath while maintaining positive nitrogen pressure in the flask. At ambient temperature, the slurry is neutralized by adding acid (glacial acetic acid; 3.0 g) to yield a reaction mixture containing the aminoethyl polysaccharide.

[0110] The aminoethyl polysaccharide was isolated from the reaction mixture as a solid by vacuum filtration through a Büchner funnel (metal, coarse frit). It was then washed in the Büchner funnel with the following washes: once with a mixture of 600 g acetone and 200 g deionized water; three times with a mixture of 600 g acetone and 160 g deionized water; once with a mixture of 600 g acetone and 80 g deionized water; and twice with pure 600 g acetone. The second acetone wash contained 0.40 g of 40% aqueous glyoxal solution and 0.10 g of glacial acetic acid. The aminoethyl polysaccharide was then vacuum dried overnight at 50 °C to yield the isolated and dried aminoethyl polysaccharide (aminoethyl-modified hydroxyethyl cellulose) as an off-white powder (66.21 g).

[0111] analysis The aminoethyl polysaccharide was manually ground (mortar and pestle), screened (#30 US Standard Sieve), and analyzed according to the above procedure with the following results: Volatile matter content: 1.31%. Ash content: 6.23% (as sodium chloride). Kjeldahl nitrogen content: 0.914%, corresponding to an aminoethyl substitution degree of 0.172. 2.0% solution viscosity: 6.31s -1 587 mPa·s at a shear rate of 25.0°C (corrected for volatiles and ash).

[0112] Preparation Examples 2-4: Neutralized aminoethyl polysaccharide (aminoethyl-modified hydroxyethyl cellulose) Preparation of aminoethyl polysaccharides Three aminoethyl polysaccharide HCl salts (Preparation Examples 2-4) are prepared according to the procedure of Preparative Example 1 above using various aziridinium halide precursors, as listed in Table 2 below. [Table 1]

[0113] Each of the aminoethyl polysaccharide HCl salts of Preparation Examples A to C is then subjected to the following neutralization procedure to prepare three neutralized aminoethyl polysaccharides.

[0114] Neutralization The aminoethyl polysaccharide HCl salt is suspended in an 80:20 IPA / H2O mixture (200 g) in a three-neck flask equipped with a reflux condenser and a nitrogen inlet. The mixture is flushed with nitrogen gas for 1 hour. Then, NaOH solution (50 wt% in water; 1 equivalent based on Kjeldahl nitrogen value) is added all at once. The solution mixture is heated and maintained at 70°C for 4 hours, then allowed to cool naturally. The reaction mixture is vigorously stirred at room temperature for 18 hours.

[0115] The solution is filtered (Buchner funnel with Whatman™ #44 filter paper), and the solid is removed and placed back into the three-neck flask. The solid is then stirred with 200 ml of an 80:20 IPA / HO mixture for 1-4 hours. The solid is then filtered again (Buchner funnel with Whatman™ #44 filter paper), rinsed with 200 ml of an 80:20 IPA / HO mixture, then 200 ml of a 90:10 IPA / HO mixture, and then 200 ml of pure IPA. The solid is then air-dried in a fume hood for 72 hours, followed by further drying in a vacuum oven at 50°C for 4 hours. The solid is then finely ground (mortar and pestle) to obtain the neutralized aminoethyl polysaccharide as a powder.

[0116] Table 3 below shows the parameters utilized for neutralizing the aminoethyl polysaccharide HCl salts of Preparative Examples A through C to prepare neutralized aminoethyl polysaccharides (AN through CN). [Table 2]

[0117] Reference Example D - General Procedure for Preparation of Silicon Glycans The neutralized aminoethyl-hydroxyethyl cellulose compound is weighed into a 20 ml scintillation vial equipped with a magnetic stir bar. The anhydride-functional siloxane (prepared as described above) is added all at once, and the reaction mixture is suspended in the selected solvent mixture. The solution is placed in a 70 °C heating block and stirred for various periods of time. The sample is allowed to cool to room temperature.

[0118] Acetone (10 ml) is added to the reaction mixture, and the reaction mixture is filtered through a Buchner funnel using Whatman™ #44 filter paper. The solid is then washed with toluene (20 ml), an 80 / 20 (by weight) IPA / H2O mixture (20 ml), a 90 / 10 IPA / H2O mixture (20 ml), IPA (20 ml), toluene (20 ml), and finally acetone (2 x 20 ml). The sample is dried in the Buchner funnel for 5 minutes, and then the solid is collected in a tared glass vial and dried in a vacuum oven at 55°C for 4 hours. The sample is then analyzed by ATR-IR and then X-ray fluorescence (XRF). The solubility of the material as a 2% aqueous solution is tested by attempting to dissolve the material in water. If the material is insoluble, it is heated to 85°C for several hours. If the material remains insoluble, acetic acid (1 equivalent) is added to the solution, and the solution is allowed to stand for 24 hours. The successful grafting of silicone moieties and the formation of linkages (W) is

number

[0119] Samples were prepared according to the procedure of this Reference Example D using the ingredients and amounts shown in the table below. [Table 3]

[0120] All of Samples 1 to 6 in Table D-1 were water-soluble. [Table 4]

[0121] All Samples 1-4 in Table D-2 were water soluble. Samples 3 and 4 demonstrated that under the conditions tested, the use of aprotic solvent mixtures (such as isopropyl alcohol and water) in the methods described herein increased the amount of silicon incorporated into the resulting silicon glycans compared to Samples 1 and 2, which used a polar aprotic solvent (methyl isobutyl ketone) in the methods. [Table 5]

[0122] Samples 1 to 5 in Table D-3 were water-soluble. [Table 6] [Table 7] [Table 8]

[0123] All samples 1-17 in Tables D-3, D-4, and D-6 were water soluble.

[0124] The viscosity profile is obtained at 25°C using an Anton Paar MCR302 rheometer. A 25 mm cone-plate with a 2° cone angle is used as the measurement geometry. The solution is introduced into the measurement geometry and then equilibrated at the measurement temperature for 3 minutes. The solution is then sheared at a specified shear rate while monitoring the change in viscosity. Once the viscosity reaches a steady state, the viscosity value at each shear rate is determined. The shear rate is varied from 0.01 to 100 s. -1 The viscosity profile is obtained by changing

[0125] A 2% aqueous solution (uncorrected for ash and volatiles) of the working example (Table D-4, Sample 3) gave a 6.31s -1A comparative 2% aqueous solution (unmodified for ash and volatiles) (Table D-5, Sample 8), which had a viscosity of 10,655 mPa s at a shear rate of 6.31 s, but which was subjected to the same chemical treatment but in which no silicon incorporation occurred, had a viscosity of 1,117 mPa s at a shear rate of 6.31 s. The dramatic difference in viscosity highlights the utility of examples of the present invention as rheology modifiers for use, for example, as drilling fluids.

[0126] Solutions of unmodified CELLOSIZE™ HEC AM103 (1.5 wt %) in deionized water and silicon glycan (1.5 wt %) in deionized water from the working examples described in Table D-5, entries 6 and 8, were separately drawn down onto Mylar membranes with a 6-mil bar film applicator. The membranes were allowed to dry overnight at room temperature. All solutions yielded clear / transparent coatings. Contact angle data were obtained on the membranes using a Kruss DSA100 instrument. Six drops of water were placed separately on each membrane and measurements were taken at time zero and approximately 200 seconds. Data are reported as the mean and standard deviation of six measurements. Precision of the measurements was determined using a t-test of six measurements with a 95% confidence interval. [Table 9]

[0127] The above experiments demonstrate that the working examples in which the polysaccharides are modified with siloxanes provide the desirable benefit of forming a water-repellent film, further demonstrating the utility of the silicon glycans of the present invention as hydrophobic film-forming agents useful in personal care applications such as skin care or hair care, where the formation of such a film provides long-lasting benefits to the formulation.

[0128] The invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

1. A silicon glycan having the formula: 【Chemistry 1】 wherein each A is an independently selected sugar moiety; each W is independently selected from the group consisting of an amide moiety and an imide moiety; each Y comprises an independently selected organosilicon moiety; each R is independently selected from a substituted or unsubstituted hydrocarbyl group, an ether moiety, an amine moiety, and H; and each R １ is independently selected from a substituted or unsubstituted hydrocarbyl group and H; each Z is an independently selected ether moiety; each subscript o is independently 0 or 1; subscript x is ≧0 to <1; subscript y is >0 to <1; and subscript z is a mole fraction of 0.00001 to 0.9, with the proviso that x+y+z=1; and the moieties represented by subscripts x, y, and z can be in a randomized or block form in said silicon glycan.

2. (i) each sugar moiety A is a hexose, or (ii) each R １ But H or C １ ~C ４ (iii) the subscript o is 1 in each moiety designated by the subscript y; (iv) the subscript o is 1 in each moiety designated by the subscript z; or (v) in each moiety where o is 1, said ether moiety Z is of the formula -(C ｔ H ２ｔ O) ｕ -, where subscript t is independently selected from 2 to 4 in each moiety designated by subscript u, and subscript u is 1 to 50; or (v) each R is selected from H, C １ ~C １８ 2. The silicon glycan of claim 1, wherein the silicon glycan is a hydrocarbyl group, a polyoxyalkylene group, or a tertiary amino group, or (vi) any combination of (i) to (v).

3. 3. The silicon glycan of claim 1 or 2, wherein each sugar moiety A is a component of hydroxyethyl cellulose, carboxymethyl cellulose, ethyl hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, or a combination thereof.

4. Each amide moiety W is 【Chemistry 2】 wherein R ４ is selected from the group consisting of a hydrogen atom and an alkyl group, and R ５ 2. The silicon glycan of claim 1, wherein: is a divalent hydrocarbon group; ** indicates the point of attachment to a carbon atom; and * indicates the point of attachment to the organosilicon moiety Y.

5. 2. The silicon glycan of claim 1, wherein each organosilicon moiety Y is independently selected from a silyl moiety and an organopolysiloxane.

6. At least one organosilicon moiety, Y, is said silyl moiety, said silyl moiety having the formula: 【Transformation 3】 In the formula, each R ２ is independently selected from substituted or unsubstituted hydrocarbyl groups, siloxy groups, silyl groups, H, and alkylene oxide groups.

7. At least one organosilicon moiety, Y, is said organopolysiloxane, said organopolysiloxane having the formula: [R ３ ３ SiO １／２ ] ａ [R ３ ２ SiO ２／２ ] ｂ [R ３ SiO ３／２ ] ｃ [SiO ４／２ ] ｄ 、 In the formula, each R ３ are independently selected from substituted or unsubstituted hydrocarbyl groups and siloxy groups, provided that at least one R ３ is a bond to the amide or imide moiety W, and the subscripts a, b, c, and d are each at mole fractions such that a+b+c+d=1, with the proviso that a+b+c>0.

8. 2. The silicon glycan according to claim 1, wherein the degree of polymerization of the sugar moiety A in the silicon glycan is 10 to 10,000.

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