Acrylate-functional branched organosilicon compound, method of preparation thereof, and copolymer formed therefrom

Abstract

A method for preparing an acrylate-functional branched organosilicon compound ("compound") is provided, the method comprising the step of (C) reacting (A) a branched organosilicon compound and (B) an acrylate compound in the presence of a catalyst, wherein component (A) has the general chemical formula X-Si(R1)3, where X comprises a halogen-functional moiety, and each R1 is selected from R and -OSi(R4)3, provided that at least one R1 is -OSi(R4)3; each R4 is selected from R, -OSi(R5)3 and -[OSiR2]mOSiR3; each R5 is selected from R, -OSi(R6)3 and -[OSiR2]mOSiR3; each R6 is selected from R and -[OSiR2]mOSiR3; each R is an independently selected hydrocarbyl group; and 0 ≤ m ≤ 100; However, at least one of R4, R5 and R6 is -[OSiR2]mOSiR3. A compound prepared by the present method, a copolymer comprising a reaction product of said compound and a second compound, a method for forming said copolymer, and a composition comprising said copolymer are each also provided.

Description

Technology Field

[0001] Cross-reference with related applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 786,931 filed December 31, 2018, and all the advantages of this application, the contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present invention generally relates to organosilicon compounds, and more specifically to a method for preparing an acrylate-functional branched organosilicon compound, a copolymer prepared by the same, a method for preparing the same, and a composition comprising the same. Background Technology

[0005] Silicon is a polymer material used in numerous commercial applications primarily due to the significant advantages it possesses over its carbon-based analogues. More precisely, silicon, referred to as polymerized siloxane or polysiloxane, consists of an inorganic silicon-oxygen skeletal chain in which organic side groups are attached to silicon atoms. has

[0006] Organic side groups can be used to link two or more of these backbones together. By varying the -Si-O- chain length, side groups, and crosslinking, silicon can be synthesized with a wide variety of properties and compositions. These can vary in consistency, ranging from liquids to gels, rubbers, and rigid plastics. The most common siloxane is linear polydimethylsiloxane (PDMS), i.e., silicone oil. The second largest group of silicon materials is based on silicon resins formed by branched and cage-like oligosiloxanes.

[0007] Another group of silicon materials is silicon dendrimers. Dendrimers are polymers with a highly branched structure extending radially from a single core. Dendrimers are typically repeatedly branched molecules that are symmetric (or nearly symmetric) around the core and often adopt a spherical or elliptical three-dimensional morphology. Dendritic polymers can also be described as tree-like macromolecules composed of or formed by a unique branch-upon-branch-upon-branch structural configuration.

[0008] Dendritic silicon or macromolecules possess molecular shapes, sizes, and functionalities that offer many potential end applications. Therefore, there remains an opportunity to provide improved branched silicon-based compounds as well as improved methods for forming such compounds. Additionally, there remains an opportunity to provide improved copolymers based on or having such compounds and improved compositions.

[0009] A method for preparing an acrylate-functional branched organosilicon compound ("Method of Preparation") is provided. The Method of Preparation comprises the step of (C) reacting (A) a branched organosilicon compound having one halogen-functional moiety and (B) an acrylate compound in the presence of a catalyst to provide said acrylate-functional branched organosilicon compound. The branched organosilicon compound (A) has the following general chemical formula:

[0010] ;

[0011] In the above formula, X includes the halogen-functional moiety; and each R 1 is R and -OSi(R 4 Selected from )3, provided that at least one R 1 -OSi(R 4 )3 and; each R 4 is R, -OSi(R5 )3 and -[OSiR2] m Selected from OSiR3; each R 5 is R, -OSi(R 6 )3 and -[OSiR2] m Selected from OSiR3; each R 6 R and -[OSiR2] m Selected from OSiR3; each R is an independently selected substituted or unsubstituted hydrocarbyl group; 0 ≤ m ≤ 100; provided that R 4 , R 5 and R 6 At least one of them is -[OSiR2] m It is OSiR3.

[0012] An acrylate-functional branched organosilicon compound prepared according to the present method is also provided.

[0013] A copolymer is further provided. The copolymer comprises a reaction product of an acrylate-functional branched organosilicon compound and a second compound that is reactive with said acrylate-functional branched organosilicon compound.

[0014] A method for manufacturing a copolymer is further provided, wherein the method comprises the step of reacting an acrylate-functional branched organosilicon compound with a second compound reactive to said branched organosilicon compound to provide said copolymer.

[0015] A composition is also provided. The composition comprises at least one of an acrylate-functional branched organosilicon compound and a copolymer. Specific details for implementing the invention

[0016] A method for preparing an acrylate-functional branched organosilicon compound ("preparation method") is disclosed.

[0017] The synthesized acryloxy-functional organosilicon compounds can be used for various end-use applications. For example, acryloxy-functional organosilicon compounds can be used as starting components when preparing copolymers (e.g., silicon-organic hybrid materials) through copolymerization, grafting, etc. However, acryloxy-functional organosilicon compounds are not so limited and can be used for other compositions and end-uses.

[0018] The present manufacturing method includes the step of reacting an organosilicon compound with a functional compound in the presence of a hydrosilylation catalyst to provide a branched organosilicon compound.

[0019] The manufacturing method comprises the step of reacting (A) a branched organosilicon compound and (B) an acrylate compound in the presence of (C) a catalyst. The reaction of the branched organosilicon compound (A) and the acrylate compound (B) generally comprises the step of combining the branched organosilicon compound (A) and the acrylate compound (B) in the presence of the catalyst (C). In other words, generally, a proactive step for the reaction is not required other than combining the branched organosilicon compound (A) and the acrylate compound (B) in the presence of the catalyst (C).

[0020] Branched organosilicon compounds (A)

[0021] The branched organosilicon compound (A) is a branched organosilicon compound having one halogen-functional moiety. Specifically, the branched organosilicon compound (A) has the following chemical formula I:

[0022] [Chemical Formula I]

[0023]

[0024] In the above formula, X includes the halogen-functional moiety; and each R 1 is R and -OSi(R 4 Selected from )3, provided that at least one R1 -OSi(R 4 )3 and; each R 4 is R, -OSi(R 5 )3 and -[OSiR2] m Selected from OSiR3; each R 5 is R, -OSi(R 6 )3 and -[OSiR2] m Selected from OSiR3; each R 6 R and -[OSiR2] m Selected from OSiR3; each R is an independently selected substituted or unsubstituted hydrocarbyl group; 0 ≤ m ≤ 100; provided that R 4 , R 5 and R 6 At least one of them is -[OSiR2] m It is OSiR3.

[0025] Each R is selected independently and may be linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups as well as saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups may be monocyclic or polycyclic. Linear and branched hydrocarbyl groups may be independently saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. "Substituted" means that one or more hydrogen atoms may be replaced by atoms other than hydrogen (e.g., halogen atoms, e.g., chlorine, fluorine, bromine, etc.), or carbon atoms within the chain of R may be replaced by atoms other than carbon, that is, R may contain one or more heteroatoms within the chain, e.g., oxygen, sulfur, nitrogen, etc. Suitable alkyl groups are exemplified, but are not limited to, methyl, ethyl, propyl (e.g., iso-propyl 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, as well as branched saturated hydrocarbon groups of six carbon atoms. Suitable aryl groups are exemplified, but are not limited to, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Suitable alkenyl groups include vinyl, allyl, propphenyl, isopropphenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups. Suitable monovalent halogenated hydrocarbon groups include, but are not limited to, alkyl halogenated groups having 1 to 6 carbon atoms or aryl halogenated groups having 6 to 10 carbon atoms. Suitable alkyl halogenated groups are exemplified by, but are not limited to, the alkyl groups described above in which one or more hydrogen atoms are replaced by halogen atoms, such as F or Cl.For example, 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 are examples of suitable alkyl halide groups. Suitable aryl halide groups are exemplified by, but are not limited to, the aryl groups described above in which one or more hydrogen atoms are replaced by halogen atoms, such as F or Cl. For example, chlorobenzyl and fluorobenzyl are suitable aryl halide groups.

[0026] In certain embodiments, each R is an alkyl group having 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to 3, alternatively 1 or 2, or alternatively 1 carbon atom(s).

[0027] Each R 1 is R and -OSi(R 4 Selected from )3, provided that at least one R 1 -OSi(R 4 )3. In a given embodiment, at least two R 1 -OSi(R 4 )3. In a specific embodiment, all three R 1 -OSi(R 4 )3. A larger number of R 1 This -OSi(R 4 In the case of )3, organosilicon compounds have a greater level of branching. For example, each R 1 This -OSi(R 4)3 and in the case where the Si-X bond is a silicon-carbon bond, each R 1 This bonded silicon atom is a [T] siloxy unit. Alternatively, two R 1 This -OSi(R 4 )3 and in the case where the Si-X bond is a silicon-carbon bond, each R 1 This bonded silicon atom is a [D] siloxy unit.

[0028] Each R 4 As described in this specification, R, -OSi(R 5 )3, and -[OSiR2] m Selected from OSiR3, where 0 ≤ m ≤ 100. R 4 and R 5 Depending on the choice of, additional branching may exist in the branched organosilicon compound (A). For example, each R 4 If is R, each -OSi(R 4 )3 Moiety is a terminal [M] siloxy unit. In other words, each R 1 This -OSi(R 4 )3 and each R 4 If is R, each R 1 It can be written as -OSiR3, and each R 1 is a [M] siloxy unit. In such an embodiment, the branched organosilicon compound (A) comprises a [T] siloxy unit (to which X is bonded) capped with three [M] siloxy units. R 4 Ga -[OSiR2] m In the case of OSiR3, R 4 includes optional [D] siloxy units (i.e., such siloxy units within a moiety indicated by the subscript m), and [M] siloxy units (represented as -OSiR3). Thus, for example, each R 1 This -OSi(R 4 )3 and each R 4 Ga -[OSiR2] m In the case of OSiR3, each R1 [Q] includes the Silroksi unit. In such an embodiment, each R 1 The chemical formula is -OSi([OSiR2] m It is of OSiR3)3. When each m is 0, each R 1 is a [Q] siloxy unit terminally capped with 3 [M] siloxy units. If m is greater than 0, each R 1 It contains a linear moiety, where the degree of polymerization is attributed to m. When present, this linear moiety is generally a diorganosiloxane moiety.

[0029] The subscript m is 0 to 100 (including the end point), alternatively 0 to 80, alternatively 0 to 60, alternatively 0 to 40, alternatively 0 to 20, alternatively 0 to 19, alternatively 0 to 18, alternatively 0 to 17, alternatively 0 to 16, alternatively 0 to 15, alternatively 0 to 14, alternatively 0 to 13, alternatively 0 to 12, alternatively 0 to 11, alternatively 0 to 10, alternatively 0 to 9, alternatively 0 to 8, alternatively 0 to 7, alternatively 0 to 6, alternatively 0 to 5, alternatively 0 to 4, alternatively 0 to 3, alternatively 0 to 2, alternatively 0 or 1, alternatively 0. Typically, each subscript m is 0, and therefore the branched moiety of the branched organosilicon compound (A) does not have a [D] siloxy unit.

[0030] As described above, each R 4 is also -OSi(R 5 ) It can be 3. In such an embodiment, R 5 Depending on the choice of, additional branching may exist in the branched organosilicon compound (A). Each R 5 is R, -OSi(R 6 )3 and -[OSiR2] mSelected from OSiR3; each R 6 R and -[OSiR2] m Selected from OSiR3; where m is defined above.

[0031] R 4 , R 5 and R 6 At least one of them is -[OSiR2] m OSiR3, where m is defined above. R 1 This chemical formula -OSi(R 4 It is of )3 and R 4 chemical formula -OSi(R 5 In the case of )3, additional siloxane bonds and branching are present in the branched organosilicon compound (A). This is R 5 a -OSi(R 6 This is especially true in the case of 3.

[0032] In particular, each subsequent R moiety in a branched organosilicon compound (A) can impart additional branching. For example, R 1 The chemical formula is -OSi(R 4 It could be of )3, and R 4 The chemical formula is -OSi(R 5 It could be of )3, and R 5 is -OSi(R 6 )3 may be possible. Therefore, depending on the choice of each substituent, additional branching attributable to [T] and / or [Q] siloxy units may be present in the branched organosilicon compound (A).

[0033] Importantly, R, R 1 , R 4 , R 5 and R 6 Each of these is selected independently. As such, the above description regarding each of these substituents does not mean or imply that each substituent is identical. R 1 Any of the above descriptions regarding is limited to only one R in branched organosilicon compounds (A), etc.1 or any number of R 1 It may be related to.

[0034] Also, R, R 1 , R 4 , R 5 and R 6 Different choices of can lead to the same structure. For example, R 1 This -OSi(R 4 )3 and each R 4 a -OSi(R 5 )3 and each R 5 If is R, then R 1 It can be written as -OSi(OSiR3)3. Similarly, R 1 This -OSi(R 4 )3 and each R 4 Ga -[OSiR2] m In the case of OSiR3 (where m is 0), R 1 It can be written as -OSi(OSiR3)3. This is R 4 Based on different choices regarding R 1 It generates the same structure for . To do this, R 4 , R 5 and R 6 At least one of them is -[OSiR2] m OSiR3. However, when m is 0, this condition can essentially be satisfied through alternative choices. For example, as mentioned above, each R 4 a -OSi(R 5 )3 and each R 5 If is R, then R 1 It can be written as -OSi(OSiR3)3, which is R 1 This -OSi(R 4 )3 and each R 4 Ga -[OSiR2] mIt is the same as the case of OSiR3 (where m is 0). Even if an alternative choice could yield the same structure as required by the condition, the condition will be considered satisfied.

[0035] In a given embodiment, each R 1 -OSi(R 4 )3. Each R 1 This -OSi(R 4 In a specific embodiment of )3, at least one R 4 -[OSiR2] m OSiR3, where m is 0. Since m is 0, at least one R 4 is -OSiR3. This is at least one R 4 a -OSi(R 5 )3 and each R 5 It has the same structure as the case where is R. Both choices are at least one R 4 Makes it -OSiR3. Therefore, at least one R 4 a -OSi(R 5 )3 and each R 5 If is R, at least one R 4 -[OSiR2] m It will also be considered as OSiR3 (where m is 0).

[0036] This also applies to the formation of additional branching in branched organosilicon compounds (A). For example, R 4 and R 5 Just as different choices related to can lead to the same structure as above, R 5 and R 6 Different choices regarding it can lead to similarly identical structures.

[0037] In a given embodiment, each R 1 -OSi(R 4 )3. Each R 1 This -OSi(R 4 In a specific embodiment of )3 persons, one R4 is each -OSi(R 4 In )3, it is R, and therefore each R 1 -OSiR(R 4 )2 is. In additional specific embodiments, -OSiR(R 4 2 Rs in )2 4 are respectively -OSi(R 5 )3 moiety, and therefore branched organosilicon compound (A) has the following structure:

[0038] ;

[0039] In the above equation, respectively R and R 5 is selected independently and is defined above, and X is as defined above. In some such embodiments, each R 5 is R, and each R is methyl.

[0040] As mentioned above, branched organosilicon compounds (A) of the same structure can be obtained from different choices. For example, the same branched organosilicon compound (A) as exemplified above is produced by the following choices: each R 1 -OSi(R 4 )3, and here one R 4 is R and 2 Rs 4 -[OSiR2] m OSiR3, and m is 0. Therefore, in the structure exemplified above, R 4 , R 5 and R 6 At least one of them is -[OSiR2] m The condition for OSiR3 is R used to reach the generated structure 4 and R 5 It is satisfied regardless of the choice.

[0041] In a specific embodiment, one R 1 is R, and 2 Rs 1 -OSi(R 4 )3. 2 R 1This -OSi(R 4 In a specific embodiment of )3 persons, one R 4 is each -OSi(R 4 In )3, it is R, and therefore 2 R 1 -OSiR(R 4 )2 is. In additional specific embodiments, -OSiR(R 4 In )2, each R 4 is -OSi(R 5 )3, and therefore, the branched organosilicon compound (A) has the following structure:

[0042] ;

[0043] In the above equation, respectively R and R 5 is selected independently and is defined above, and X is as defined above. In a given embodiment, each R 5 is R, and each R is methyl. In some such embodiments, each R 5 is R, and each R is methyl.

[0044] As mentioned above, a branched organosilicon compound (A) of the same structure can be obtained from different choices. For example, a branched organosilicon compound (A) identical to that exemplified above is produced by the following choice: one R 1 is R; 2 Rs 1 -OSi(R 4 )3 and here each -OSi(R 4 One R in )3 4 is R, and 2 Rs 4 -[OSiR2] m OSiR3, and m is 0. Therefore, in the structure exemplified above, R 4 , R 5 and R 6 At least one of them is -[OSiR2] m The condition for OSiR3 is R used to reach the generated structure 4 and R5 It is satisfied regardless of the choice.

[0045] In another embodiment, 2 R 1 is R, and one R 1 -OSi(R 4 )3 is. One R 1 This -OSi(R 4 In a specific embodiment of )3 persons, one R 4 is -OSi(R 4 R in )3, and therefore this specific R 1 -OSiR(R 4 )2 is. In additional specific embodiments, -OSiR(R 4 In )2, each R 4 is -OSi(R 5 )3, and therefore, the branched organosilicon compound (A) has the following structure:

[0046] ;

[0047] In the above equation, respectively R and R 5 is selected independently and is defined above, and X is as defined above. In a given embodiment, each R 5 is R, and each R is methyl. In some such embodiments, each R 5 is R, and each R is methyl.

[0048] As mentioned above, a branched organosilicon compound (A) of the same structure can be obtained from different choices. For example, a branched organosilicon compound (A) identical to that exemplified above is produced by the following choice: 2 R 1 is R; one R 1 -OSi(R 4 )3 and here -OSi(R 4 One R in )3 4 is R, and 2 Rs 4 -[OSiR2] mOSiR3, and m is 0. Therefore, in the structure exemplified above, R 4 , R 5 and R 6 At least one of them is -[OSiR2] m The condition for OSiR3 is R used to reach the generated structure 4 and R 5 It is satisfied regardless of the choice.

[0049] In the exemplary structure described above, each R 5 is R, and each R is methyl. However, R 5 If is different from R, i.e., R 5 OSi(R 6 )3 and -[OSiR2] m OSiR3(where m is as defined above, and each R 6 R and -[OSiR2] m When selected from OSiR3, and m is selected from as defined above, additional branching can be introduced into the branched organosilicon compound (A).

[0050] As described above, X comprises a halogen-functional moiety. The halogen-functional moiety is not particularly limited and may be any halogen-functional moiety suitable for preparing an acrylate-functional branched organosilicon compound according to the method of the present invention. Generally, the halogen-functional moiety comprises a halogen atom. The specific halogen atom present in the halogen-functional moiety is not limited and may be selected from fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At). Typically, the halogen atom is selected from chlorine and bromine. In certain embodiments, the halogen atom is chlorine, and thus the halogen-functional moiety X comprises a chlorine-functional moiety, or alternatively, a chlorine-functional moiety.

[0051] Typically, the halogen-functional moiety X comprises an organohalide group, e.g., an alkyl halide group, or alternatively, such a group. Common examples of organohalides and alkyl halides include the hydrocarbyl group described above with respect to the substituent R, wherein such a hydrocarbyl group comprises one halogen substitution (e.g., instead of a carbon-bonded hydrogen atom).

[0052] In a given embodiment, the halogen-functional moiety X is of the general chemical formula -DR 3 It has, where D is an independently selected 2-valent unit and R 3 is a halogen atom. In some such embodiments, R 3 It is chlorine or bromine. Typically, D is selected from substituted and unsubstituted hydrocarbon groups. In certain embodiments, D is C1-C 18 Contains hydrocarbon groups, and alternatively C1-C 18 It is a hydrocarbon group. In some such embodiments, D is the general chemical formula -(CH2) n- It comprises an alkylene group having (wherein the subscript n is ≥ 1, e.g. 1 to 18, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 2 to 6), and alternatively is such a group. However, as one example, in a specific embodiment, the subscript n is 3, and R 3 chlorine is chlorine, and therefore the branched organosilicon compound (A) has the following chemical formula:

[0053] ;

[0054] In the above equation, each R 1 is independently selected and is as defined above.

[0055] The branched organosilicon compound (A) may be used in any form, for example, in a clean (neat) form (i.e., in the absence of a solvent, carrier vehicle, diluent, etc.), or may be placed in a carrier vehicle, for example, a solvent or a dispersant. If present, the carrier vehicle may comprise or be: an organic solvent (e.g., an aromatic hydrocarbon, e.g., benzene, toluene, xylene, etc.; an aliphatic hydrocarbon, e.g., heptane, hexane, or octane, etc.; a halogenated hydrocarbon, e.g., dichloromethane, 1,1,1-trichloroethane, chloroform, etc.; an ether, e.g., diethyl ether, tetrahydrofuran, etc.), a silicone fluid, an aqueous solvent (e.g., water), or a combination thereof. In a given embodiment, the branched organosilicon compound (A) is used in the absence of a carrier vehicle. In some such embodiments, the branched organosilicon compound (A) is used in the absence of a carrier vehicle / volatile substance and water that is reactive with the branched organosilicon compound (A) and / or the acrylate compound (B). For example, in a given embodiment, the method may include the step of stripping the branched organosilicon compound (A) of the volatile substance and / or solvent (e.g., organic solvent, water, etc.). Techniques for stripping the branched organosilicon compound (A) are known in the art and may include distillation, heating, application of reduced pressure / vacuum, azeotropy with a solvent, use of a molecular sieve, and combinations thereof.

[0056] The branched organosilicon compound (A) may be used in any amount selected by a person skilled in the art, depending on, for example, a specific acrylate compound (B) selected, reaction parameters used, reaction scale (e.g., the total amount of component (A) and / or component (B) to be reacted, and / or the total amount of acrylate-functional branched organosilicon compound to be produced).

[0057] Acrylate compound (B)

[0058] The acrylate compound (B) is not particularly limited and, as understood by those skilled in the art in light of the description in this specification, may be any compound suitable for substituting the halogen-functional moiety X with an acryloxy group (e.g., through substitution reactions, monosubstitution reactions, alkylation reactions, etc.).

[0059] Typically, the acrylate compound (B) comprises an acryloxide anion (e.g., an α,β-unsaturated carboxylate anion), and thus the acrylate compound (B) comprises an acryloxide salt, or alternatively, an acryloxide salt. Such an acryloxide salt will generally comprise a counterion (e.g., a cation, or a combination of cations), and such counterion may be selected from organic cations (e.g., quaternary ammonium cations, e.g., imidazolium, pyridinium, and pyrrolidinium cations; sulfonium cations; phosphonium cations, etc.), inorganic cations (e.g., metal cations), and combinations thereof. Specific examples of suitable cations include those of alkali metals (e.g., lithium (Li), sodium (Na), potassium (K), etc.) and alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), barium (Ba), etc.). It will be understood that other acrylates, i.e., those that are not salts, such as acrylate esters, acrylic acids, acrylic anhydrides, and combinations thereof, may also be used. Such other acrylates may be selected based on the selection of a specific catalyst (C), other additives used in the present method, etc., which will be readily understood by those skilled in the art.

[0060] In a given embodiment, the acrylate compound (B) has the following general chemical formula:

[0061] ;

[0062] In the above formula, M is an alkali metal, and R 7is selected from substituted or unsubstituted hydrocarbyl groups and H.

[0063] In a given embodiment, R 7 is H, and thus the acrylate compound (B) can generally be limited to an acrylate salt, and more specifically to a metal acrylate. In another embodiment, R 7 is selected from any of the substituted or unsubstituted hydrocarbyl groups described above, for example, with respect to substituent R. In some such embodiments, R 7 is an alkyl group, and thus the acrylate compound (B) can generally be limited to an alkyl acrylate salt, and more specifically to a metal alkyl acrylate. In certain embodiments, R 7 It is methyl, and therefore the acrylate compound (B) can generally be limited to a methacrylate salt, and more specifically to a metal methacrylate.

[0064] The alkali metal M may be any alkali metal. However, it should be understood that more than one alkali metal may be used, and thus the acrylate compound (B) may be a mixed salt. Typically, M is selected from lithium (Li), sodium (Na), potassium (K), and combinations thereof. In some embodiments, M comprises sodium, or alternatively, sodium. In certain embodiments, M comprises potassium, or alternatively, potassium.

[0065] Specific examples of compounds suitable for use as acrylate compounds (B) generally include sodium (meth)acrylate, potassium (meth)acrylate, sodium acrylate, potassium acrylate, and combinations thereof. In a given embodiment, the acrylate compound (B) comprises sodium (meth)acrylate, potassium (meth)acrylate, sodium acrylate, and / or potassium acrylate, alternatively these.

[0066] The acrylate compound (B) may be used in any form, for example, in a pure form (i.e., in the absence of a solvent, carrier vehicle, diluent, etc.), or may be placed in a carrier vehicle, for example, a solvent or a dispersant. If present, the carrier vehicle may comprise or be: an organic solvent (e.g., an aromatic hydrocarbon, e.g., benzene, toluene, xylene, etc.; an aliphatic hydrocarbon, e.g., heptane, hexane, or octane, etc.; a halogenated hydrocarbon, e.g., dichloromethane, 1,1,1-trichloroethane, chloroform, etc.; an ether, e.g., diethyl ether, tetrahydrofuran, etc.), a silicone fluid, or a combination thereof. Typically, the carrier vehicle comprises a high-boiling point solvent, e.g., dimethylformamide (DMF), butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), etc.

[0067] In a given embodiment, the acrylate compound (B) is used in the absence of a carrier vehicle. In some such embodiments, the acrylate compound (B) is used in the absence of a carrier vehicle / volatile substance and water that are reactive with the branched organosilicon compound (A) and / or the acrylate compound (B). For example, in a given embodiment, the method may include the step of stripping the acrylate compound (B) of the volatile substance and / or solvent (e.g., organic solvent, water, etc.). Techniques for stripping the branched acrylate compound (B) are known in the art and may include distillation, heating, application of reduced pressure / vacuum, azeotropy with a solvent, use of molecular sieves, etc., and combinations thereof.

[0068] In a given embodiment, the method comprises the step of using more than one acrylate compound (B), for example, two, three, four or more acrylate compounds (B). In such an embodiment, each acrylate compound (B) is selected independently and may be the same as or different from any other acrylate compound (B).

[0069] Methods for preparing compounds suitable for use as acrylate compounds (B) or as acrylate compounds (B) are well known in the art, and many of the compounds listed herein are available from various sources. As such, acrylate compounds (B) can be prepared as part of a method or otherwise obtained (i.e., as a prepared compound). The preparation of acrylate compounds (B) (e.g., carried out by mixing a suitable acrylic acid with a metal hydroxide and precipitating the salt formed thereby) is typically carried out within the same system ( in situ It is formed before the reaction of component (A) and component (B), rather than in (i.e., during the reaction of component (A) and component (B). However, if the preparation of the acrylate compound (B) is compatible with the reaction mixture described below, the acrylate compound (B) can be carried out in the same system, as will be readily determined by those skilled in the art.

[0070] The acrylate compound (B) may be used in any amount selected by a person skilled in the art, depending on, for example, a specific branched organosilicon compound (A) and / or acrylate compound (B) selected, reaction parameters used, reaction scale (e.g., the total amount of component (A) and / or component (B) to be reacted, and / or the total amount of acrylate-functional branched organosilicon compound to be produced), etc.

[0071] The relative amounts of the branched organosilicon compound (A) and the acrylate compound (B) used may vary based, for example, on a specific branched organosilicon compound (A) selected, a specific acrylate compound (B) selected, reaction parameters used, etc. As understood by those skilled in the art in light of the description in this specification, the reaction of the branched organosilicon compound (A) and the acrylate compound (B) to produce an acrylate-functional branched organosilicon compound occurs at a theoretical maximum molar ratio of 1:1 (A):(B). However, typically, one of the components is used in excess to completely consume either compound (A) or compound (B), for example, to simplify the purification of the reaction product formed. For example, in a given embodiment, compound (B) is used in relative excess to maximize the conversion rate of the branched organosilicon compound (A) to the acrylate-functional branched organosilicon compound.

[0072] In a specific embodiment, the branched organosilicon compound (A) and the acrylate compound (B) are reacted in a molar ratio of 0.1 to 20 (A):(B). For example, in a specific embodiment, the branched organosilicon compound (A) and the acrylate compound (B) are reacted in a molar ratio of 1:1 to 1:10, e.g. 1:1.1 to 1:10, alternatively 1:1.5 to 1:10, alternatively 1:2 to 1:10, alternatively 1:2.5 to 1:10, alternatively 1:3 to 1:10, alternatively 1:4 to 1:10, alternatively 1:5 to 1:10, alternatively 1:6 to 1:10 (A):(B). In some embodiments, the branched organosilicon compound (A) and the acrylate compound (B) are reacted in a molar ratio of (A):(B) of 1:1 to 10:1, e.g. 1.1:1 to 10:1, alternatively 1.5:1 to 5:1, or alternatively 2:1 to 5:1. It will be understood that ratios outside these ranges may also be used. For example, in a given embodiment, the acrylate compound (B) is used in a substantial excess (e.g., ≥ 10 times, alternatively ≥ 15 times, or alternatively ≥ 20 times the molar amount of the branched organosilicon compound (A).

[0073] Catalyst (C)

[0074] The catalyst (C) is not particularly limited and may be any compound suitable for promoting the substitution of the acryloxy group of the acrylate compound (B) with the halogen-functional moiety X of the branched organosilicon compound (A) (e.g., through substitution reactions, monosubstitution reactions, alkylation reactions, etc.) as understood by those skilled in the art in light of the description in this specification.

[0075] In a given embodiment, the catalyst (C) comprises an iodide catalyst (i.e., a compound containing a monovalent anionic iodine atom) and alternatively such an iodide catalyst. Such a catalyst, also known as an iodide compound, is well known in the art and comprises a salt containing an iodide anion and a counterion (e.g., a cation, or a combination of cations), wherein the counterion may be selected from organic cations (e.g., quaternary ammonium cations, e.g., imidazolium, pyridinium, and pyrrolidinium cations; sulfonium cations; phosphonium cations, etc.), inorganic cations (e.g., metal cations), and combinations thereof. Specific examples of suitable cations include those of alkali metals (e.g., lithium (Li), sodium (Na), potassium (K), etc.) and alkaline earth metals (e.g., beryllium (Be), magnesium (Mg), calcium (Ca), barium (Ba), etc.). It will be understood that other cations may also be used in place of, or in addition to, any of those exemplified herein. In certain embodiments, the catalyst (C) comprises sodium iodide, or alternatively, sodium iodide. In certain embodiments, the catalyst (C) comprises potassium iodide, or alternatively, potassium iodide.

[0076] In a given embodiment, the catalyst (C) comprises an acrylate-activating compound, that is, a compound that increases the reactivity of the acrylate compound (B). Examples of the activating compound generally include cationic counterions of the acryloxide salt, such as any of those described above with respect to the acrylate compound (B) (e.g., alkali metal M), which can solvate and / or coordinate to them. Such compounds include polar aprotic Brønsted bases, such as tertiary amines, tertiary amides (e.g., substituted ureas of the general formula R'2NC(O)NR'2, where each R' is an independently selected hydrocarbon group, N,N'-disubstituted cyclic urea, etc.), organically substituted phosphoramides (e.g., tris(disubstituted)amides of the general formula OP(NR''2)3, where each R' is an independently selected hydrocarbon group), as well as derivatives, modifiers, and combinations thereof.

[0077] For example, in a given embodiment, the catalyst (C) comprises a tertiary amide. In some such embodiments, the catalyst (C) comprises an N,N'-disubstituted urea, such as N,N′-dimethylpropylene urea (DMPU), N,N′-dimethylethylene urea (DMEU), tetramethyl urea (TMU), tetraethyl urea (TEU), etc., alternatively these. In a specific embodiment, the catalyst (C) comprises an N,N'-disubstituted cyclic urea, such as DMPU, DMEU, etc., or a combination thereof, alternatively these. In another embodiment, the catalyst (C) comprises a phosphoramide, such as a hexaalkylphosphoramide (e.g., hexamethylphosphoramide (HMPU), etc.), a cyclic phosphoramide (e.g., tripyrrolidinophosphine oxide, etc.), etc. In some such embodiments, the catalyst (C) comprises HMPU, and alternatively is HMPU.

[0078] In certain embodiments, the catalyst (C) comprises a phase-transfer compound. A phase-transfer compound, also known as a phase-transfer catalyst, is a compound that promotes the interphase transfer of reaction components (e.g., from an aqueous phase to an organic phase, from an organic phase to an aqueous phase, from a silicon phase to an aqueous phase, etc.). As such, the phase-transfer compound is typically selected based on specific reaction conditions used, such as whether heterogeneous or homogeneous conditions are selected, if present, a specific support vehicle used, the solubility and miscibility of the reaction components, etc.

[0079] Examples of phase-transfer compounds / catalysts include tetraalkylammonium and / or phosphonium salts, such as tetrabutylammonium bromide (TBA-Br), methyl tributylammonium chloride, benzyl triethylammonium chloride, methyl tricaprylammonium chloride, methyl tributylammonium chloride, methyl trioctylammonium chloride, tetrabutylphosphonium bromide, hexadecyl tributylammonium bromide, etc., as well as derivatives, modifiers, and combinations thereof.

[0080] In a specific embodiment, the method comprises the step of using more than one catalyst (C), e.g., two different catalysts (C). In such an embodiment, each catalyst (C) is selected independently and may be identical or different from any other catalyst (C) used. For example, in some embodiments, the catalyst (C) is a combination of sodium iodide and potassium iodide (i.e., a mixed-salt catalyst). In a specific embodiment, the catalyst (C) comprises at least one iodide compound, cyclic urea, or phosphoramide, and at least one phase-shift compound. For example, in some such embodiments, the catalyst (C) comprises at least one of N,N′-dimethylpropylene urea (DMPU), hexamethylphosphoramide (HMPA), and N,N′-dimethylethylene urea (DMEU), and also tetrabutylammonium bromide.

[0081] Methods for preparing compounds suitable for use in or as catalysts (C) are well known in the art, and many of the compounds listed herein are available from various sources. Thus, catalyst (C) can be prepared as part of a method or otherwise obtained (i.e., as a prepared compound).

[0082] The catalyst (C) may be used in any form, for example, in a pure form (i.e., in the absence of a solvent, carrier vehicle, diluent, etc.), or may be placed in a carrier vehicle, for example, a solvent or a dispersant (e.g., any of those listed above for the branched organosilicon compound (A)). In some embodiments, the catalyst (C) is used in the absence of a carrier vehicle / volatile substance and water that are reactive with the branched organosilicon compound (A), the acrylate compound (B), and / or the catalyst (C) itself (i.e., until combined with component (A) and component (B). For example, in a given embodiment, the method may include the step of stripping the catalyst (C) of the volatile substance and / or solvent (e.g., water, organic solvent, etc.). Techniques for stripping the catalyst (C) are known in the art and may include heating, drying, application of reduced pressure / vacuum, azeotropy with a solvent, use of a molecular sieve, etc., and combinations thereof.

[0083] The catalyst (C) may be used in any amount selected by a person skilled in the art, depending on, for example, the specific catalyst (C) selected, the reaction parameters used, the scale of the reaction (e.g., the total amount of component (A) and component (B), etc. The molar ratio of the catalyst (C) to component (A) and / or component (B) used in the reaction may affect the rate and / or amount of the reaction of component (A) and component (B) together to produce an acrylate-functional branched organosilicon compound. Thus, not only the amount of catalyst (C) relative to component (A) and / or component (B), but also the molar ratio between them may vary. Typically, these relative amounts and molar ratios are selected to maximize the coupling of component (A) and component (B) to produce an acrylate-functional branched organosilicon compound (e.g., to increase the economic efficiency of the reaction, increase the ease of purification of the reaction product formed, etc.).

[0084] In a given embodiment, the catalyst (C) is used in the reaction in an amount of 0.001 to 15 mol% based on the total amount of the component (A) used. For example, the catalyst (C) may be used in an amount of 0.01 to 15 mol%, alternatively 0.01 to 12 mol%, alternatively 0.01 to 10 mol%, alternatively 0.1 to 10 mol%, or alternatively 0.1 to 5 mol% based on the total amount of the component (A) used.

[0085] In a specific embodiment, the catalyst (C) is used in the reaction in an amount of 0.001 to 15 mol% based on the total amount of the component (B) used. For example, the catalyst (C) may be used in an amount of 0.01 to 15 mol%, alternatively 0.01 to 12 mol%, alternatively 0.01 to 10 mol%, alternatively 0.1 to 10 mol%, or alternatively 0.1 to 5 mol% based on the total amount of the component (B) used.

[0086] In a given embodiment, the branched organosilicon compound (A) and the acrylate compound (B) are reacted in the presence of a polymerization inhibitor (D). The polymerization inhibitor is not limited to radical scavengers, antioxidants, light stabilizers, UV absorbers, etc., or a combination thereof. Such compounds are known in the art and are chemical compounds or moiety that can generally interact with free radicals to render them inert, for example by forming covalent bonds with free radicals to remove them. The polymerization inhibitor (D) may also, or alternatively, be a polymerization retardant, i.e., a compound that reduces the rate of initiation and / or propagation of radical polymerization. For example, in some embodiments, the polymerization inhibitor (D) comprises oxygen gas, or alternatively, is oxygen gas. Generally, a polymerization inhibitor (D) is used to prevent and / or inhibit the formation of byproducts that may be formed through radical polymerization of an acrylate compound (B) and / or an acrylate-functional branched organosilicon compound.

[0087] The polymerization inhibitor (D) is not limited to phenolic compounds, quinone or hydroquinone compounds, N-oxyl compounds, phenothiazine compounds, disrupting amine compounds, or combinations thereof, and alternatively may be these.

[0088] Examples of phenolic compounds include phenol, alkylphenol, aminophenol (e.g., p-aminophenol), nitrosophenol, and alkoxyphenol. Specific examples of such phenol compounds include o-, m-, and p-cresols (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2,6-dimethylphenol or 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 4,4′-oxybiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, pyrocatechol (1,2-dihydroxybenzene), 2-(1′-methylcyclohex-1′-yl)-4,6-dimethylphenol, 2- or 4-(1′-phenyleth-1′-yl)phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert-butylphenol, nonylphenol, octylphenol, 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3′,5,5′-tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylpyrocatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, 1,3,5-Tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate or pentaerythrityl tetrakis[p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6-sec-butyl-2,4-dinitrophenol, octadecyl 3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, hexadecyl 3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, octyl 3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, 3-thi-1,5-pentanediol Bis[(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate], 4,8-dioxa-1,11-undecanediol bis[(3′-tert-butyl-4′-hydroxy-5′-methylphenyl)propionate], 1,9-nonandiol bis[(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate], 1,7-heptanediamine bis[3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionamide], 1,1-Methanediaminebis[3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionamide], 3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionic acid hydrazide, 3-(3′,5′-dimethyl-4′-hydroxyphenyl)propionic acid hydrazide, bis(3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl)methane, bis(3,5-di-tert-butyl-4-hydroxyphen-1-yl)methane, bis[3-(1′-methylcyclohex-1′-yl)-5-methyl-2-hydroxyphen-1-yl]methane, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)methane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)ethane, bis(5-tert-butyl-4-hydroxy-2-methylphen-1-yl)sulfide, bis(3-tert-butyl-2-hydroxy-5-methylphen-1-yl)sulfide, 1,1-bis(3,4-dimethyl-2-hydroxyphen-1-yl)-2-methylpropane, 1,1-bis(5-tert-butyl-3-methyl-2-hydroxyphen-1-yl)butane, 1,3,5-tris-[1′-(3Δ,5″-di-tert-butyl-4″-hydroxyphen-1″-yl)meth-1′-yl]-2,4,6-trimethylbenzene, 1,1,4-tris(5′-tert-butyl-4′-hydroxy-2′-methylphen-1′-yl)butane and tert-butylcatechol, p-nitrosophenol, p-nitroso-o-cresol, methoxyphenol (guajacol, pyrocatechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1-(4-hydroxy-3-methoxyphenyl)ethanone (acetovanillone), eugenol, dihydroeugenol, isoeugenol, tocopherol, e.g., α-, β-, γ-, δ- and ε-tocopherol, tocopherol, Includes α-tocopherol hydroquinone, 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycoumaran), etc.

[0089] Suitable quinones and hydroquinones include hydroquinone, hydroquinone monomethyl ether (4-methoxyphenol), methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 4-methylpyrocatechol, tert-butylhydroquinone, 3-methylpyrocatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, tetramethyl-p-benzoquinone, diethyl-1,4-cyclohexanedione, 2,5-Dicarboxylate, Phenyl-p-Benzoquinone, 2,5-Dimethyl-3-Benzyl-p-Benzoquinone, 2-Isopropyl-5-Methyl-p-Benzoquinone (Thymoquinone), 2,6-Diisopropyl-p-Benzoquinone, 2,5-Dimethyl-3-Hydroxy-p-Benzoquinone, 2,5-Dihydroxy-p-Benzoquinone, Embelin, Tetrahydroxy-p-Benzoquinone, 2,5-Dimethoxy-1,4-Benzoquinone, 2-Amino-5-Methyl-p-Benzoquinone, 2,5-Bisphenylamino-1,4-Benzoquinone, 5,8-Dihydroxy-1,4-Naphthoquinone, 2-Anilino-1,4-Naphthoquinone, Anthraquinone, N,N-dimethylindoaniline, N,N-diphenyl-p-benzoquinonediimine, 1,4-benzoquinone dioxime, coerulignone, 3,3′-di-tert-butyl-5,5′-dimethyldiphenoquinone, p-rosolic acid (aurine), 2,6-di-tert-butyl-4-benzylidenebenzoquinone, 2,5-di-tert-amylhydroquinone, etc. are included.

[0090] Suitable N-oxyl compounds (i.e., nitroxyl or N-oxyl radicals) are compounds having one or more NO● groups, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 4,4′,4″-tris(2,2,6,6-tetramethylpiperidine-N-oxyl)phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsilyloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl sebacate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl-benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl (4-tert-butyl)benzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) Succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)1,10-decanedioate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)n-butylmalonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl) Hexahydroterephthalate, N,N′-bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)dodecylsuccinimide, 2,4,Includes 6-tris[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]triazine, N,N′-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-N,N′-bisformyl-1,6-diaminohexane, 4,4′-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazine-3-one), etc.

[0091] Other compounds suitable for use in or as a polymerization inhibitor (D) include compounds having a structure similar to phenothiazine (PTZ), e.g., phenoxazine, promazine, N,N′-dimethylphenazine, carbazole, N-ethylcarbazole, N-benzylphenothiazine, N-(1-phenylethyl)phenothiazine, N-alkylated phenothiazine derivatives, e.g., N-benzylphenothiazine and N-(1-phenylethyl)phenothiazine. Of course, the polymerization inhibitor (D) may include any number of specific compounds that can be selected independently and may be identical or different from any other compound of the polymerization inhibitor (D).

[0092] When used, the polymerization inhibitor (D) may be added to the reaction as a separate component, or may be combined with another component (e.g., acrylate compound (B)) before the reaction of component (A) and component (B). The polymerization inhibitor (D) may be used in any amount selected by a person skilled in the art, depending on, for example, a specific polymerization inhibitor (D) selected, reaction parameters used, reaction scale (e.g., total amount of component (A) and / or component (B)), atmosphere of the reaction, temperature and / or pressure of the reaction, etc. In a given embodiment, the polymerization inhibitor (D) is present in the reaction in an amount of 50 to 2000 ppm, for example, 50 ppm, alternatively 100 ppm, alternatively 250 ppm, alternatively 500 ppm, alternatively 1000 ppm, alternatively 1500 ppm, alternatively 2000 ppm. However, those skilled in the art will readily understand that, for example, if the reaction scale and / or conditions require additional amounts of polymerization inhibitor (D), amounts outside these ranges and exemplary amounts may also be used. Furthermore, in addition to or alternative to the above amounts, oxygen may be added to the reaction as a separate component (e.g., instead of or in addition to a separate polymerization inhibitor (D) selected from the above compounds). In such cases, oxygen may be introduced into the reaction in the form of oxygen gas, optionally in the presence of another gas (e.g., in the form of air). If used, the amount of oxygen gas is selected such that the gas phase above the reaction mixture is kept below the explosion limit.

[0093] In certain embodiments, component (A) and component (B) are reacted in the presence of component (C) and component (D) and a carrier vehicle. In some such embodiments, component (C) comprises sodium iodide and / or potassium iodide, component (D) comprises butylated hydroxytoluene (BHT) and / or 4-methoxyphenol (MEHQ), and the carrier vehicle comprises dimethylformamide (DMF). In another such embodiment, component (C) comprises tetrabutylammonium bromide and at least one of N,N′-dimethylpropylene urea (DMPU), N,N′-dimethylethylene urea (DMEU), and hexamethylphosphoramide (HMPA), component (D) comprises butylated hydroxytoluene (BHT) and / or 4-methoxyphenol (MEHQ), and the carrier vehicle comprises propylene glycol monomethyl ether acetate (PGMEA).

[0094] Typically, the reaction of component (A) and component (B) for preparing an acrylate-functional branched organosilicon compound is carried out in a vessel or reactor. If the reaction is carried out at an elevated temperature as described below, the vessel or reactor may be heated in any suitable manner, for example, through a jacket, heating mantle, hot plate, coil, etc.

[0095] Components (A), components (B), and components (C), and optionally component (D) may be supplied to a container together or individually, or may be placed in a container in any order of addition and any combination. For example, in a given embodiment, components (B) and components (C) are added to a container containing component (A) and optionally component (D). In such an embodiment, components (B) and components (C) may be combined first before addition, or may be added to the container sequentially. Generally, the reference to "reaction mixture" in this specification generally refers to a mixture comprising components (A), components (B), and components (C) (e.g., obtained by combining such components as described above).

[0096] The method may further include a step of stirring the reaction mixture. Stirring can enhance mixing and contacting components (A), (B), and (C) together, for example, in their reaction mixture. Such contact can be achieved independently using different conditions with stirring (e.g., simultaneously or sequentially) or without stirring (i.e., regardless of stirring, or alternatively, instead of stirring). The other conditions may be tailored to enhance the contact between the acrylate compound (B) and the branched organosilicon compound (A), and the subsequent reaction (i.e., transesterification), to produce an acrylate-functional branched organosilicon compound. The other conditions may be result-effective conditions for improving the reaction yield or minimizing the amount of specific reaction byproducts included in the reaction product with the acrylate-functional branched organosilicon compound.

[0097] In some embodiments, the reaction is carried out at an elevated temperature. The elevated temperature will be selected and controlled according to a specific branched organosilicon compound (A) selected, a specific acrylate compound (B) selected, and, if present, a specific carrier and / or solvent used. Accordingly, the elevated temperature will be readily selected by a person skilled in the art in consideration of the selected reaction conditions and parameters and the description herein. The elevated temperature is typically above ambient temperature to 180°C, e.g., 30 to 170°C, alternatively 40 to 170°C, alternatively 40 to 160°C, alternatively 50 to 150°C, alternatively 50 to 135°C, alternatively 60 to 135°C, alternatively 70 to 130°C, alternatively 80 to 120°C.

[0098] It should also be understood that the temperature may differ from the range presented above. It should also be understood that reaction parameters may change during the reaction of component (A) and component (B). For example, temperature, pressure, and other parameters may be independently selected or changed during the reaction. Any of these parameters may independently be ambient parameters (e.g., room temperature and / or atmospheric pressure) and / or non-ambient parameters (e.g., reduced temperature or increased temperature and / or reduced or increased pressure). Any parameters may also change dynamically, in real time, i.e., during the method, or statically (e.g., during the reaction duration, or for any part thereof).

[0099] The time during which the reaction of component (A) and component (B) is carried out to produce an acrylate-functional branched organosilicon compound depends on the scale, reaction parameters and conditions, the composition of the specific component, etc. In a given embodiment, the time during which the reaction is carried out is greater than 0 hours to 48 hours, alternatively 1 to 36 hours, alternatively 2 to 24 hours, and alternatively 4 to 12 hours after combining component (A) and component (B) in the presence of component (C).

[0100] In a given embodiment, the method further comprises the step of isolating and / or purifying an acrylate-functional branched organosilicon compound from the reaction product. As used herein, isolation of an acrylate-functional branched organosilicon compound is typically defined as increasing the relative concentration of the acrylate-functional branched organosilicon compound relative to other compounds in combination with the acrylate-functional branched organosilicon compound (e.g., in the reaction product or its purified form). As such, as understood in the art, isolation / purification may include removing other compounds from such combination (i.e., reducing the amount of impurities combined with the acrylate-functional branched organosilicon compound in the reaction mixture) and / or removing the acrylate-functional branched organosilicon compound itself from the combination. Any suitable technique and / or protocol for isolation may be used. Examples of suitable isolation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, etc. As understood by those skilled in the art, any of these techniques may be used in combination (i.e., sequentially) with any other technique to isolate acrylate-functional branched organosilicon compounds. It should be understood that isolation may include purification of acrylate-functional branched organosilicon compounds and may be referred to as such. However, purification of acrylate-functional branched organosilicon compounds may include alternative and / or additional techniques compared to those used to isolate acrylate-functional branched organosilicon compounds. Regardless of the specific technique(s) selected, the isolation and / or purification of acrylate-functional branched organosilicon compounds may be performed sequentially (i.e., in series) with the reaction itself and thus may be automated.In other cases, purification may be a stand-alone procedure for processing a reaction product containing an acrylate-functional branched organosilicon compound.

[0101] Acrylate-functional branched organosilicon compounds

[0102] The acrylate-functional branched organosilicon compound prepared according to the present method has the following general chemical formula:

[0103] ;

[0104] In the above formula, each R, like the branched organosilicon compound (A) described above, 1 is R and -OSi(R 4 Selected from )3, provided that at least one R 1 -OSi(R 4 )3 and; each R 4 is R, -OSi(R 5 )3 and -[OSiR2] m Selected from OSiR3; each R 5 is R, -OSi(R 6 )3 and -[OSiR2] m Selected from OSiR3; each R 6 R and -[OSiR2] m Selected from OSiR3; where each R is an independently selected substituted or unsubstituted hydrocarbyl group; 0 ≤ m ≤ 100; provided that R 4 , R 5 and R 6 At least one of them is -[OSiR2] m It is OSiR3 and; here, As with the acrylate compound (B) described above, R 7 is selected from a substituted or unsubstituted hydrocarbyl group and H; D is a divalent linker.

[0105] As understood by those skilled in the art in light of the description in this specification, the branched organosilicon compound (A) used in the method has a sub-chemical formula (R 1 It forms part of an acrylate-functional branched organosilicon compound corresponding to a branched organosilicon moiety represented by )3Si-D-, and the acrylate compound (B) used in the present method is of the sub-formula -C(O)C(CH2)R 7 It forms part of an acrylate-functional organosilicon compound corresponding to the acrylate moiety. As such, where the chemical formula, structure, moiety, group, or other such motif is shared between the acrylate-functional branched organosilicon compound and compound (A) and compound (B), the above description of such shared motif can equally describe the acrylate-functional branched organosilicon compound.

[0106] As described above, D is an independently selected divalent group, such as a substituted or unsubstituted hydrocarbon group (e.g., C1-C 18 It is a hydrocarbon group). In some embodiments, D is the general chemical formula -(CH2) n- It comprises an alkylene group having (wherein the subscript n is ≥ 1, e.g. 1 to 18, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 2 to 6), and alternatively is such a group. In a specific embodiment, the subscript n is 3.

[0107] In a given embodiment, the acrylate-functional branched organosilicon compound has the following chemical formula:

[0108] ,

[0109] In the above equation, D is a 2-fold connector; and each R 5 is R, -OSi(R 6 )3 and -[OSiR2] mSelected from OSiR3; each R 6 R and -[OSiR2] m Selected from OSiR3; each R is an independently selected substituted or unsubstituted hydrocarbyl group; 0 ≤ m ≤ 100; and R 7 is selected from substituted or unsubstituted hydrocarbyl groups and H.

[0110] copolymer

[0111] A copolymer is also provided. The copolymer comprises a reaction product of an acrylate-functional branched organosilicon compound and a second compound (hereinafter, "reactive compound") that is reactive to said acrylate-functional branched organosilicon compound. As understood by those skilled in the art in light of the description herein, many different copolymers may be prepared, for example, depending on the specific acrylate-functional branched organosilicon compound used, the specific reactive compound used, the type of reaction performed, the ratio of the components used, etc. Typically, the reactive compound is typically acrylate functional.

[0112] Generally, the copolymer comprises a branched organosilicon moiety having the following chemical formula:

[0113] ,

[0114] This is formed from an acrylate-functional branched organosilicon compound used in a reaction with a reactive compound. As such, with respect to the branched organosilicon moiety of the copolymer, sub-formula R 1 The organosilicon moiety denoted by 3Si- is as defined above with respect to acrylate-functional branched organosilicon compounds and methods of their formation. Likewise, the sub-formula -D- represents the divalent linker defined above with respect to acrylate-functional branched organosilicon compounds and methods of their formation. Sub-formula -Y 2-As described in more detail below, is a moiety formed from an acryloxy moiety of an acrylate-functional branched organosilicon compound (i.e., during the reaction of an acrylate-functional branched organosilicon compound and a reactive compound).

[0115] Polymer moiety (of the copolymer)

[0116] The copolymer also comprises a polymer moiety. The polymer moiety is not particularly limited and may comprise any polymer or combination of polymers that can be grafted onto or reacted with the branched organosilicon compound, or alternatively, any such polymer or combination of polymers. Furthermore, the polymer moiety may be formed in the same system in the presence of the branched organosilicon compound; that is, the polymer moiety does not need to be formed prior to forming the copolymer. Examples of such polymers include polyethers, polyacrylates, polyesters, polycarbonates, etc., as well as combinations thereof. However, as understood from consideration of the description in this specification, the polymer moiety may be any moiety comprising at least one polymer group.

[0117] Specific examples of at least one polymer group include a polyether group, a polyacrylate group, a polyester group, a polycarbonate group, an alkylaluminoxan group, an alkylgermoxan group, a polythioester group, a polythioether group, a polyacrylonitrile group, a polyacrylamide group, an epoxy group, a polyurethane group, a polyurea group, a polyacetal group, a polyolefin group, a polyvinyl alcohol group, a polyvinyl ester group, a polyvinyl ether group, a polyvinyl ketone group, a polyisobutylene group, a polychloroprene group, a polyisoprene group, a polybutadiene group, a polyvinylidene group, a polyfluorocarbon group, a polychlorinated hydrocarbon group, a polyalkyne group, a polyamide group, a polyimide group, a polyimidazole group, a polyoxazole group, a polyoxazine group, a polyoxydiazole group, a polythiazole group, a polysulfone group, a polysulfide group, Polyketone groups, polyetherketone groups, polyanhydride groups, polyamine groups, polyimine groups, polyphosphazene groups, polysaccharide groups, polypeptide groups, polyisocyanate groups, cellulose groups, and combinations thereof are included.

[0118] In a given embodiment, the polymer moiety comprises a combination of polymers, that is, a copolymer moiety comprising at least two different polymer groups. In such an embodiment, each polymer group may be selected independently and may include any of the polymers or polymer groups described herein.

[0119] polyacrylate

[0120] In some embodiments, the polymer moiety comprises a polyacrylate moiety, or alternatively, a polyacrylate moiety. The polyacrylate moiety is not limited and may be formed from any acrylate compound as described in more detail below. As used herein, the term “polyacrylate moiety” means a moiety comprising at least two acrylate functional groups (e.g., alkyl acrylate groups, e.g., methyl, ethyl, or butyl acrylate groups; substituted acrylate groups, e.g., 2-ethylhexyl or hydroxylethyl groups; and others, e.g., methylolpropane acrylate groups). As understood from the description herein, the polyacrylate moiety may be a monomer, an oligomer, a polymer, an aliphatic, an aromatic, an aliphatic, etc. Furthermore, the copolymer may comprise a plurality of different polyacrylate moietys selected independently.

[0121] Methods for manufacturing polyacrylates (and polyacrylate moiety) are known in the art. For example, polyacrylates can be produced through the conventional radical polymerization of acrylate monomers. Such conventional methods are generally carried out by combining radically polymerizable monomers (e.g., acrylate monomers, comonomers, etc.) in the presence of radical initiators / generators, e.g., thermal, chemical, and / or photopolymerization initiators. For example, peroxide and aromatic initiators (e.g., phenol, benzoin, heterocyclic, e.g., imidazole, etc.) are commonly used. These conventional methods can be used to produce acrylate homopolymers and copolymers—including tertiary, quaternary, and higher-order copolymers. Additionally, as understood from consideration of the description of suitable acrylic monomers in this specification, difunctional and / or polyfunctional acrylic monomers may also be used, for example, to produce polyfunctional polyacrylates (and polyacrylate moiety).

[0122] Generally, a method for manufacturing polyacrylates (and polyacrylate moiety) utilizes at least one acrylic monomer having an acryloyloxy or alkylacryloyloxy group (i.e., acrylates, alkylacrylates, acrylic acids, alkylacrylic acids, etc., as well as derivatives and / or combinations thereof). Such acrylic monomers may be monofunctional or polyfunctional acrylic monomers.

[0123] Examples of specific monofunctional acrylic monomers suitable for preparing polyacrylates (and polyacrylate moiety) include (alkyl)acrylic compounds, such as methyl acrylate, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, polyoxyethylene-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, and 2,4,6-tribromophenoxyethyl (meth)acrylate. Polyoxyethylene-modified phenoxy(meth)acrylate, polyoxypropylene-modified phenoxy(meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamanthyl (meth)acrylate, 2-methyl-2-adamanthyl (meth)acrylate, 2-ethyl-2-adamanthyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclofentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,Nonyl (meth)acrylate, Decyl (meth)acrylate, Isodecyl (meth)acrylate, Undecyl (meth)acrylate, Dodecyl (meth)acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, Isostearyl (meth)acrylate, Benzyl (meth)acrylate, 1-Naphthylmethyl (meth)acrylate, 2-Naphthylmethyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Butoxyethyl (meth)acrylate, Ethoxydiethylene glycol (meth)acrylate, Poly(ethylene glycol) mono(meth)acrylate, Poly(propylene glycol) mono(meth)acrylate, Methoxyethylene glycol (meth)acrylate, Ethoxyethyl (meth)acrylate, Methoxypoly(ethylene glycol) (Meth)acrylates, methoxypoly(propylene glycol) (meth)acrylates, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, t-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, etc., as well as their derivatives are included.

[0124] Examples of specific polyfunctional acrylic monomers suitable for preparing polyacrylates (and polyacrylate moiety) include (alkyl)acrylic compounds having two or more acryloyl or methacryloyl groups, such as trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyoxyethylene-modified trimethylolpropane tri(meth)acrylate, polyoxypropylene-modified trimethylolpropane tri(meth)acrylate, polyoxyethylene / polyoxypropylene-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, phenylethylene glycol di(meth)acrylate, and poly(ethylene Glycol) di(meth)acrylate, poly(propylene glycol) di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonandiol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantandimethanol di(meth)acrylate, o-xylylene di(meth)acrylate, m-xylylene di(meth)acrylate, p-xylylene di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane Di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyoxyethylene-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, polyoxypropylene-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, and polyoxyethylene / polyoxypropylene-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane are included.

[0125] For the sake of simplicity, the above (alkyl)acrylic compounds are described only with respect to (meth)acrylate chemical species, and it should be understood that those skilled in the art will readily understand that other alkyl and / or hydride versions of such compounds may be used in the same way. For example, those skilled in the art will understand that the monomer "2-ethylhexyl (meth)acrylate" listed above exemplifies both 2-ethylhexyl (meth)acrylate and 2-ethylhexyl acrylate. Likewise, although the acrylic monomer is generally described as a propenoate (i.e., an α,β-unsaturated ester) in the above examples, it should be understood that the term "acrylate" used in these descriptions may equally refer to the acid, salt, and / or conjugate base of the esters exemplified. For example, those skilled in the art will understand that the monomer "methyl acrylate" listed above exemplifies acrylic acid, acrylate salts (e.g., sodium acrylate), as well as the methyl ester of acrylic acid. Furthermore, polyfunctional derivatives / modifications of the acrylic monomers described above may also be used. For example, the monomer "ethyl (meth)acrylate" listed above exemplifies functionalized derivatives, such as substituted ethyl (meth)acrylate and ethyl acrylate (e.g., hydroxyethyl (meth)acrylate and hydroxyethyl acrylate, respectively).

[0126] A comonomer (i.e., a monomer reactive with the acrylic monomer) may also be used to produce polyacrylates (and polyacrylate moiety). Such monomers are not limited and generally include compounds having radical polymerizable groups, such as alkenyl, acryloyl, and alkylacryloyl groups. Generally, the comonomer is selected by those skilled in the art, for example, to modify the properties of the copolymer comprising the polyacrylate moiety and / or polyacrylate moiety to be produced. For example, it is known in the art that styrene can be copolymerized with an acrylic monomer to produce polyacrylates (and polyacrylate moiety) having increased hardness compared to those in the absence of such a styrene comonomer. Likewise, comonomers, such as acrylonitrile, can be used to increase interchain polar interactions, thereby increasing the tensile strength and end elongation of the polyacrylate (and polyacrylate moiety), while also reducing the low-temperature flexibility of such polyacrylate (and polyacrylate moiety). Furthermore, those skilled in the art will readily select the ratio(s), order of addition, reaction length, and other factors of the monomers used to independently adjust various properties (e.g., flexibility, solubility, hardness, polarity, etc.) of the polyacrylate moiety, the copolymer comprising the polyacrylate moiety, and / or the composition and / or product prepared therefrom. Specific examples of suitable comonomers include styrene, acrylonitrile, vinylidene chloride, vinyl chloride, ethylene, propylene, butylene, chloroprene, isoprene, tetrafluoroethylene, etc., as well as derivatives thereof.

[0127] It should be understood that combinations of acrylic monomers can also be used to produce polyacrylates, and thus the polyacrylate (and polyacrylate moiety) may be a homopolymer or a copolymer with respect to any repeating segments therein. For example, the method described above may be used to produce polyfunctional polyacrylates by, for example, using monofunctional acrylic monomers and polyfunctional acrylic monomers. These different functional monomers are typically selected by those skilled in the art based, for example, on reactivity and interpolymeric and / or intrapolymeric interactions to alter the mechanical strength of the polyacrylate produced therefrom. For example, a cured product comprising a copolymer using a polyacrylate moiety comprising a combination of monofunctional acrylic monomers and polyfunctional acrylic monomers may be produced to have increased mechanical strength compared to those using a homopolymer polyacrylate moiety. Likewise, a cured product comprising a copolymer using a homopolymer polyacrylate moiety can be manufactured to have increased flexibility compared to those using a polyfunctional polyacrylate moiety.

[0128] In certain embodiments, the polyacrylate moiety of the copolymer is prepared from methyl (meth)acrylate, methyl acrylate, butyl (meth)acrylate, butyl acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl acrylate, hydroxyethyl (meth)acrylate, hydroxyethyl acrylate, methylacrylic acid, acrylic acid, and / or styrene monomer.

[0129] It will also be understood that the polyacrylate (and polyacrylate moiety) prepared as described above may be monofunctional or polyfunctional with respect to the non-acrylic functional groups present therein. For example, such methods may be used to prepare polyacrylate alcohols, diols, and / or polyols, which include preparation via the methods described above (e.g., by using hydroxyl-functional monomers) and via modifications thereof (e.g., by using post-polymerization functionalization techniques, such as terminal capping of a functional group-containing compound and / or grafting it onto a polyacrylate). Such functional group-containing compounds may contain alkoxysilyl groups, for example, the alkoxysilyl groups may be grafted onto the polyacrylate via hydrosilylation or other methods known in the art. For example, in a given embodiment, the polyacrylate moiety is prepared from a polyacrylate polyol. In these or other embodiments, the polyacrylate moiety is prepared from a polyacrylate compound comprising a dimethoxymethylsilyl group. In a specific embodiment, the polyacrylate moiety is prepared from a polyacrylate compound comprising at least one radical polymerizable group, such as an acryloyl functional group.

[0130] The specific polyacrylate moiety present in a copolymer depends on the copolymer's end-use application. For example, aliphatic polyacrylate moiety generally has greater flexibility and a smaller glass transition temperature (T) than aromatic polyacrylate moiety. g It provides ), and aromatic polyacrylate moiety typically has a larger glass transition temperature (T g It is more rigid while having ). Similarly, molecular weight and viscosity can be selected and controlled based on the desired properties of the copolymer.

[0131] Where present, each polyacrylate moiety typically has a number average molecular weight (Mn ) is at least 100. In a given embodiment, at least one polyacrylate is M n This is at least 100, alternatively at least 125, alternatively at least 150, alternatively at least 200, alternatively at least 250, alternatively at least 300. In these or other embodiments, each polyacrylate moiety is M n This is at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700, alternatively at least 1,000, alternatively at least 2,000, alternatively at least 4,000, alternatively at least 8,000. In a given embodiment, each polyacrylate moiety is at most M n This is 20,000, alternatively less than 19,000, alternatively less than 18,000, alternatively less than 17,000, alternatively less than 16,000, and alternatively less than 15,000. The number average molecular weight can be easily measured using gel permeation chromatography (GPC) technology based on polystyrene standards.

[0132] polyether

[0133] In some embodiments, the polymer moiety comprises a polyether moiety, or alternatively, a polyether moiety. As used herein, the term "polyether moiety" means a moiety comprising at least two ether functional groups. As understood from the description herein, the polyether moiety may be a monomer, an oligomer, a polymer, an aliphatic, an aromatic, an aromatic aliphatic, etc. Furthermore, it may comprise a plurality of different polyether moietys selected independently.

[0134] Each polyether moiety typically has the general chemical formula -O-(C n' H 2n' O) w'-It comprises a polyether having, wherein the subscript n' is independently selected from 2 to 4 in each moiety represented by the subscript w', and the subscript w' is 1 to 1000. In a given embodiment, the polyether moiety comprises a plurality of polyethers of such general formula, which may exist in a linear or branched form with other polyethers to form a polyether moiety comprising a plurality of oxyalkylene-based polyethers. In such an embodiment, the polyether moiety may comprise oxyethylene units (C2H4O), oxypropylene units (C3H6O), oxybutylene or oxytetramethylene units (C4H8O), or a combination thereof, which may be in a block form or randomized within the polyether moiety. The oxyalkylene units within the polyether moiety may independently be linear or branched. For example, the oxyethylene unit may be of the chemical formula -CH2CH2O- or the chemical formula -CHCH3O-, if present. Similarly, the oxypropylene unit may be of the chemical formula -CH2CH2CH2O-, -CH2CHCH3O-, or -CHCH3CH2O-.

[0135] For example, the polyether moiety has the general chemical formula -O-(C2H4O) x' (C3H6O) y' (C4H8O) z'- It may include a polyether having, wherein the subscript x' is 0 to 999; the subscript y' is 1 to 1000; the subscript z' is 0 to 999; and the unit represented by the subscripts x', y' and z' may be in a randomized or block form within the polyether moiety. In a given embodiment, x' and z' are each 0, and thus the polyether of the polyether moiety has the general formula -O-(C3H6O) y'- It has, where y' is defined above.

[0136] In some embodiments, the polyether moiety is formula -D 4- O-(C n' H 2n' O) w'- D 4- It comprises a polyether having . In such an embodiment, each D 4 is an independently selected divalent hydrocarbon group having 1 to 6 carbon atoms, alternatively 1 to 5 carbon atoms, alternatively 1 to 4 carbon atoms, or alternatively 1 or 2 carbon atoms. Each D 4 can be independently linear or branched. For example, D 4 In the case where ga has 2 carbon atoms, D 4 It has the chemical formula C2H4 and can be linear (CH2CH2) or branched (CHCH3). In a given embodiment, D 4 is linear. Any D 4 is an arbitrary specific D 4 It may be the same as or different from. In certain embodiments, each D 4 is CH2. Each subscript n' is independently selected from 2 to 4 in each moiety represented by the subscript w', and the subscript w' is defined above.

[0137] For example, in such an embodiment, the polyether moiety is of the formula -D 4- O-(C2H4O) x' (C3H6O) y' (C4H8O) z'- D 4- It may include a polyether having, wherein the subscript x' is 0 to 999; the subscript y' is 1 to 1000; the subscript z' is 0 to 999; and the units represented by the subscripts x', y' and z' may be in a randomized or block form within the polyether. In a given embodiment, x' and z' are each 0, and thus the polyether is of formula -D 4-O-(C3H6O) y'- D 4- has, where D 4 and y' are defined above. In a specific embodiment, each D 4 is also C3H6. x' and z' are 0 respectively, and each D 4 If α is C3H6, the polyether of the polyether moiety has the chemical formula -C3H 6- O-(C3H6O) y'- C3H 6- It has, where y' is defined above.

[0138] In a given embodiment, the polyether moiety comprises a polyether having the following general chemical formula:

[0139] -CH 2- CH(R 12 )-[D 4 ] m'- O-[C2H4O] x' [C3H6O] y' [C4H8O] z'- [D 4 ] m'- CH(R 12 )-CH 2- ,

[0140] In the above equation, each R 12 is independently a hydrocarbyl group, alkoxy group, silyl group, or H having 1 to 6 carbon atoms; and each D 4 is an independently selected divalent group having 1 to 6 carbon atoms, the subscript m' is 0 or 1, the subscript x' is 0 to 999, the subscript y' is 1 to 1000, the subscript z' is 0 to 999, and the unit represented by subscripts x', y' and z' may be in a randomized form or block form within the polyether.

[0141] Each R 12 is independently selected and may be any of the C1-C6 hydrocarbyl groups described herein. For example, R 12may be methyl, propyl, etc. In a given embodiment, each R 12 is methyl. Alternatively, or additionally, R 12 It can be H, an alkoxy group, or a silyl group.

[0142] Each subscript m' is independently 0 or 1, and thus the polyether of the polyether moiety has 0, 1, or 2 divalent hydrocarbon groups D 4 It may include. Typically, each subscript m' is 1. However, in a given embodiment, at least one subscript m is 0.

[0143] In some embodiments, the polyether moiety may be branched. In such embodiments, the polyether is of the general formula [D 4 ] m'' [P] can have, where D 4 is defined above, where the subscript m'' is ≥ 3 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, etc.), and P is a polyether comprising at least one of the polyethers described above. For example, in some such embodiments, P is a polyether formed from a polyol (e.g., butanediol, glycerol, sorbitol, etc.) and a polyoxyalkylene (e.g., polyoxypropylene), which is m'' D 4 The moiety is terminally capped. In such a case, the number of alcohol functional groups constituting the polyol will correspond to the maximum number of m". However, if not all polyoxyalkylene chains extending from the polyol are terminally capped, m" will be less than the number of alcohol functional groups constituting the polyol.

[0144] Where present, each polyether moiety, or alternatively each polyether of the polyether moiety, typically has a number average molecular weight (M n) is at least 100. In a given embodiment, at least one polyether moiety, alternatively one polyether of the polyether moiety is M n This is at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700. In these or other embodiments, each polyether moiety, alternatively each polyether of the polyether moiety is M n This is at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700, alternatively at least 1,000, alternatively at least 2,000, alternatively at least 4,000, alternatively at least 8,000, alternatively at least 12,000, alternatively at least 16,000, alternatively at least 25,000, alternatively at least 50,000. In a specific embodiment, at least one, alternatively each polyether moiety, alternatively the polyether of the polyether moiety is M n This is 700 to 900. The number average molecular weight can be easily measured using gel permeation chromatography (GPC) technology based on polystyrene standards, or by end-group analysis using nuclear magnetic resonance spectroscopy.

[0145] Polyester

[0146] In some embodiments, the polymer moiety comprises a polyester moiety, or alternatively, a polyester moiety. As used herein, the term “polyester moiety” means a moiety comprising at least one or two ester bonds within the polymer. For example, the polyester moiety itself may be a monomer, oligomer, polymer, aliphatic, aromatic, aromatic aliphatic, etc. Furthermore, the copolymer may comprise a number of different polyester moietys selected independently.

[0147] Methods for manufacturing polyesters (and polyester moiety) are known in the art. For example, polyesters can be manufactured through a conventional esterification process using an acid and a hydroxyl compound (e.g., an aromatic and / or aliphatic alcohol or glycol). The hydroxyl compound is typically a polyhydric alcohol.

[0148] Specific examples of hydroxyl compounds suitable for manufacturing polyesters (and polyester moiety) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,6-hexanedriol, decanediol, dodecanediol α-methyl glucoside, pentaerythritol, and sorbitol. The term “polyhydric alcohol” also includes compounds derived from phenol, such as 2,2-bis(4-hydroxylphenyl)propane, commonly known as bisphenol A.

[0149] Specific examples of acids suitable for manufacturing polyesters (and polyester moiety) include polycarboxylic acids, which include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyl-1,6-hexanoic acid, pimelosanic acid, souveric acid, azelaic acid, sebacic acid, brasylic acid, maleic acid, fumaric acid, glutaconic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethyl-glutaric acid, α,β-diethylsuccinic acid, isophthalic acid, terephthalic acid, hemimellitic acid, phthalic acid, isophthalic acid, and 1,4-cyclohexanedicarboxylic acid.

[0150] Other methods for manufacturing polyesters (and polyester moiety) are also known. For example, polyesters (and polyester moiety) may include ring-opening polymers of cyclic lactones, polycondensation products of hydroxycarboxylic acids, and polycondensation products of dibasic acids and polyols.

[0151] Each specific polyester moiety present in a copolymer depends on the copolymer's end-use application. For example, aliphatic polyester moiety generally has greater flexibility and a smaller glass transition temperature (T) than aromatic polyester moiety. g It provides ), and aromatic polyester moiety typically has a larger glass transition temperature (T g It is more rigid while having ). Similarly, molecular weight and viscosity can be selected and controlled based on the desired properties of the copolymer.

[0152] Where present, each polyester moiety typically has a number average molecular weight (M n ) is at least 100. In a given embodiment, at least one polyester moiety is M n This is at least 100, alternatively at least 125, alternatively at least 150, alternatively at least 200, alternatively at least 250, alternatively at least 300. In these or other embodiments, each polyester moiety is M nThis is at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700, alternatively at least 1,000, alternatively at least 2,000, alternatively at least 4,000, alternatively at least 8,000. In a given embodiment, each polyester moiety is at most M n This is 20,000, alternatively less than 19,000, alternatively less than 18,000, alternatively less than 17,000, alternatively less than 16,000, and alternatively less than 15,000. The number average molecular weight can be easily measured using gel permeation chromatography (GPC) technology based on polystyrene standards.

[0153] polycarbonate

[0154] In some embodiments, the polymer moiety comprises a polycarbonate moiety, or alternatively, a polycarbonate moiety. As used herein, the term "polycarbonate moiety" means a moiety comprising at least one or two carbonate bonds within the polymer. For example, the polycarbonate moiety itself may be a monomer, oligomer, polymer, aliphatic, aromatic, aromatic aliphatic, etc. Furthermore, the copolymer may comprise a number of different polycarbonate moietys selected independently. Examples of suitable polycarbonate moietys are not limited and include polycarbonates (and polycarbonate moietys) formed from any polycarbonate compound, as described in more detail below.

[0155] Methods for manufacturing polycarbonates (and polycarbonate moiety) are known in the art. For example, polycarbonates can be manufactured through conventional processes such as the alkoxylation of phosgene (i.e., COCl2), the transalkoxylation of carbonate monomers, the alkoxylation and / or transalkoxylation of alkyl chloroformates (e.g., methyl chloroformate), or combinations thereof using hydroxyl compounds (e.g., aromatic and / or aliphatic alcohols or glycols). Hydroxyl compounds are typically polyhydric alcohols.

[0156] Specific examples of hydroxyl compounds suitable for manufacturing polycarbonates (and polycarbonate moiety) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,6-hexanedriol, decanediol, dodecanediol α-methyl glucoside, pentaerythritol, and sorbitol. The term “polyhydric alcohol” also includes compounds derived from phenol, such as 2,2-bis(4-hydroxylphenyl)propane, commonly known as bisphenol A.

[0157] Examples of carbonate monomers suitable for manufacturing polycarbonates (and polycarbonate moiety) include acyclic carbonate esters, such as dialkyl carbonates (e.g., dimethyl carbonate), diaryl carbonates (e.g., diphenyl carbonate), and cyclic carbonate esters, such as ethylene carbonate, trimethylene carbonate, etc. Other carbonate monomers may also be used, such as those produced through conventional processes including those using a hydroxyl compound (e.g., those described herein) in oxidative carbonylation (e.g., reaction with carbon monoxide and an oxidizing agent) or in the bisalkoxylation of phosgene. In such processes, the hydroxyl compound may be a monohydric alcohol, such as an alkyl alcohol (e.g., methanol, ethanol, propanol, etc.), phenol, etc.

[0158] Other methods for manufacturing polycarbonates (and polycarbonate moiety) are also known. For example, polycarbonates (and polycarbonate moiety) may comprise ring-opening polymers of oxirane (e.g., epoxide compounds, e.g., propylene oxide) and CO2.

[0159] It will be understood that the polycarbonate (and polycarbonate moiety) prepared as described above may be monofunctional or polyfunctional with respect to the functional groups present therein (e.g., at terminal position(s), and such functional groups are typically selected by those skilled in the art, for example, through a specific manufacturing method used, the order of addition and / or relative amounts of compounds used to form the polycarbonate (and polycarbonate moiety). For example, such a method may be used to prepare polycarbonate diols and / or polycarbonate polyols by utilizing methods of alkoxylation and / or transalkoxylation and / or oxidative oxirane carbonylation of carbonate monomers and / or carbonyl chloride monomers with one or more of the polyhydric alcohols described above. It should also be understood that combinations of hydroxyl compounds can also be used in any one specific manufacturing method, and thus polycarbonates (and polycarbonate moiety) can be homopolymers or copolymers for any repeating segments therein.

[0160] Each specific polycarbonate moiety present in the copolymer depends on the copolymer's end-use application. For example, aliphatic polycarbonate moietyes generally have greater flexibility and a smaller glass transition temperature (T) than aromatic polycarbonate moietyes. g It provides ), and aromatic polycarbonate moiety typically has a larger glass transition temperature (T g It is more rigid while having ). Similarly, the molecular weight and viscosity of any specific polycarbonate moiety can be selected and controlled based on the desired properties of the copolymer.

[0161] Where present, each polycarbonate moiety typically has a number average molecular weight (M n ) is at least 100. In a given embodiment, at least one polycarbonate moiety is M nThis is at least 100, alternatively at least 125, alternatively at least 150, alternatively at least 200, alternatively at least 250, alternatively at least 300. In these or other embodiments, each polycarbonate moiety is M n This is at least 200, alternatively at least 300, alternatively at least 400, alternatively at least 500, alternatively at least 600, alternatively at least 700, alternatively at least 1,000, alternatively at least 2,000, alternatively at least 4,000, alternatively at least 8,000. In a given embodiment, each polycarbonate moiety is at most M n This is 20,000, alternatively less than 19,000, alternatively less than 18,000, alternatively less than 17,000, alternatively less than 16,000, and alternatively less than 15,000. The number average molecular weight can be easily measured using gel permeation chromatography (GPC) technology based on polystyrene standards.

[0162] Structure of copolymer

[0163] In some embodiments, the copolymer has the following general chemical formula:

[0164] ;

[0165] In the above formula, sub-chemical formula R 1 The organosilicon moiety denoted by 3Si- is as defined above with respect to acrylate-functional branched organosilicon compounds; -D- represents the divalent linker defined above with respect to acrylate-functional branched organosilicon compounds and methods of their formation; and -Y 2- is a moiety formed from an acryloxy moiety of an acrylate-functional branched organosilicon compound (i.e., during the reaction between an acrylate-functional branched organosilicon compound and a reactive compound); and Z is a polymer moiety.

[0166] Moiety Y2 is formed from the acryloxy moiety of an acrylate-functional branched organosilicon compound. As such, Y 2 Specific properties of (e.g., structure, chemical formula, etc.) will be controlled by the selection of specific reactive compounds used to produce the copolymer, the type of reaction used in connection therewith, etc., as understood by those skilled in the art in light of the description in this specification.

[0167] In a given embodiment, the copolymer has the following general chemical formula:

[0168] ;

[0169] In the above equation, moiety R 1 3Si-, -D-, -Y 2- , and Z are as defined above, and the subscript x" is ≥ 2. In such an embodiment, the copolymer may comprise a linear structure, for example, when the subscript x" is 2 and the polymer moiety Z is linear, and thus the copolymer has a general structure R 1 3Si-DY 2- ZY 2- D-Si-R 1 It has 3. Alternatively, the copolymer may include a branched structure, which is, for example, where D is at least trivalent and the subscript x" is ≥ 2, alternatively ≥ 3.

[0170] Method for manufacturing a copolymer

[0171] As described above, the copolymer comprises a reaction product of a branched organosilicon compound and a reactive compound. Accordingly, a method for preparing the copolymer is further provided ("polymerization method"). The polymerization method comprises the step of reacting a branched organosilicon compound with a reactive compound to provide the copolymer.

[0172] A second compound that is reactive with branched organosilicon compounds

[0173] The reactive compound is reactive with the branched organosilicon compound. Since the branched organosilicon compound can vary in terms of reactivity, the reactive compound can likewise vary, and the reactive compound will be selected based on the specific branched organosilicon compound used in the polymerization method, the copolymer to be formed, the desired end use of the copolymer, etc.

[0174] Generally, reactive compounds have the chemical formula (R 11 ) a" It has -Z, where Z is the polymer moiety described above with respect to the copolymer, and R 11 Z comprises a functional group reactive to a branched organosilicon compound, and the subscript a" is ≥ 1. Alternatively, Z may be a monomer, for example, a copolymer may be formed by polymerizing monomers in the presence of a branched organosilicon compound, and thus the polymer moiety is formed within the same system. The polymer moiety Z is not limited and may include any of the polymer moiety described above, or alternatively, may be such. Furthermore, the polymer moiety Z comprises a polymer group and a reactive group R 11 Other groups, such as linkers (e.g., divalent organic and / or silicon linkers, such as hydrocarbon linkers, silyl and / or organosilyl linkers, siloxane and / or organosiloxane linkers, etc., or combinations thereof) may be included. Such linkers are included in the reactive mixture between the polymers of moiety Z, and between the polymer of moiety Z and the reactive group R 11 It may exist between, or in both. The subscript a" denotes the group R of the reactive compound capable of reacting with the branched organosilicon compound. 11Indicates the number of. For example, if the subscript a" is 1, the reactive compound may be monoreactive, whereas if the subscript a" is 2, 3, or more, the reactive compound may react with 2, 3, or more equivalents of a branched organosilicon compound (for example, as a result, may form a copolymer having one of the branched structures described above).

[0175] Each R 11 is independently selected and may include any functional group reactive with branched organosilicon compounds, or alternatively, may be such a functional group. For example, R 11 may include a reactive group through substitution reactions, addition reactions, radical reactions, coupling reactions, or combinations thereof, or alternatively, may be such a group. Specific examples of such reactions include nucleophilic substitution, ring-opening addition, transalkoxylation, hydrosilylation, olefin metathesis, condensation, radical coupling and / or polymerization, as well as combinations thereof. Accordingly, each R 11 It may include a nucleophilic group (e.g., hydroxyl group, amine group, thiol group, silanol group, etc.), an ethylene-based unsaturated group (e.g., alkenyl or alkynyl group, any of those listed above), a silicon-bonded hydrogen atom, a condensation group (e.g., carboxylic acid group, silanol group, amide group, etc.), or a combination thereof, or alternatively, these may be.

[0176] Branched organosilicon compounds and reactive compounds are typically reacted in molar ratios of 1.5:1 to 1:1.5, alternatively 1.4:1 to 1:1.4, alternatively 1.3:1 to 1:1.3, alternatively 1.2:1 to 1:1.2, alternatively 1.1:1 to 1:1.1, and alternatively 1.1:1 to 1:1. However, those skilled in the art will select a specific ratio to be used, taking into account, for example, the specific copolymer being produced, the specific branched organosilicon compound and / or reactive compound being used, the desired use of the copolymer being produced, the type of reaction used in the polymerization method, etc.

[0177] Composition and Uses of Branched Organosilicon Compounds and Copolymers

[0178] A composition is also provided. The composition comprises at least one of an acrylate-functional branched organosilicon compound (“compound”) and a copolymer. In various embodiments, the composition comprises the compound but does not comprise the copolymer. In a specific embodiment, the composition further comprises the copolymer in addition to the compound. In another embodiment, the composition comprises the copolymer but does not comprise the compound. The composition is generally not limited and may have various forms, functions, uses, end applications, etc.

[0179] When used, the compound may be present in the composition in varying amounts. This also applies to the copolymer when used in the composition. A person skilled in the art can easily determine suitable amounts of the compound and / or copolymer depending, for example, on a specific composition, compound, or copolymer and the desired result.

[0180] In various embodiments, the composition is further limited to at least one of the following: (i) an emulsion; (ii) an aqueous composition; (iii) a surfactant composition; (iv) a wetting composition; (v) an aqueous film-forming foam; (vi) a surface tension modifier; (vii) an anti-blocking additive; (viii) an agricultural composition; (ix) a coating composition; (x) a paint composition; (xi) a surface treatment composition; (xii) a film-forming composition; and (xiii) a cosmetic composition. Those skilled in the art understand that certain compositions may overlap in form and / or function. References to compositions and any of these specific compositions, e.g., emulsions, may be interchangeable in the following description.

[0181] The compound may be used in a number of applications. In various embodiments, the compound is used as at least one of a surfactant, a dispersant, a wetting agent, an anti-blocking additive, a surface tension modifier, a surface treatment agent, an additive for agricultural compositions, an additive for coatings, an additive for paints, a cosmetic ingredient, a siloxane modifier, and an aqueous film-forming foam component. Those skilled in the art understand that certain uses or applications may overlap in terms of function and / or desired results.

[0182] The copolymer may also be used in a number of applications, such applications being the same or different from the uses described above for the compound. In a given embodiment, the copolymer is used as at least one of a surface treatment agent, a paint additive, a coating additive, and a cosmetic ingredient.

[0183] In this composition, the compound or copolymer may be used alone or together, supplemented by at least one auxiliary component, or optionally act as an auxiliary to at least one other component in the presence of one or more additives. In various embodiments, the compound or copolymer may be referred to as an agent, additive, auxiliary, component, or modifier.

[0184] Each of the compounds or copolymers may react with other components present in the composition or may be inert to them. In a composition or application in which the composition, compound, or copolymer comes into contact with a surface or substrate, there may be bonding to the surface or substrate, wherein such bonding is mechanical / physical, chemical, or a combination thereof. For example, the surface may have functional groups that are reactive with the compound. Such functional groups may be inherent to the surface or may be imparted by one or more conventional surface treatments. Specific exemplary compositions and their components are described below.

[0185] It should be understood that certain components or additives may be classified under different technical terms, and that the mere fact that a component or additive is classified under such terms does not imply that it is limited to such functions. One or more of the additives may be present in any suitable weight percentage (weight%) of the composition, for example, 0.01 wt% to 65 wt%, 0.05 wt% to 35 wt%, 0.1 wt% to 15 wt%, 0.5 wt% to 5 wt%, or 0.1 wt% or less, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 wt%, or 15 wt% or more of the composition. A person skilled in the art can readily determine a suitable amount of the additive, for example, depending on the type of additive and the desired result. Certain optional additives are described in more detail below.

[0186] In various embodiments, the composition comprises or is an emulsion. The emulsion is not limited and is generally selected from the group of silicone / oil-in-water (O / W) and water-in-oil / silicone (W / O) emulsions. The emulsion comprises a non-aqueous phase and an aqueous phase. Typically, the non-aqueous phase is a discontinuous phase in the emulsion, and the aqueous phase is a continuous phase. However, as described below, based on the relative amounts of components in the emulsion, the non-aqueous phase may be a continuous phase, wherein the aqueous phase is a discontinuous phase.

[0187] The discontinuous phase generally forms particles within the continuous phase of the emulsion. The particles are liquid and may alternatively be referred to as droplets. The size of the particles typically depends, for example, on the selection and amount of the components within them.

[0188] In various embodiments, the non-aqueous phase of the emulsion comprises the compound and / or copolymer of the present invention. In a given embodiment, the non-aqueous phase further comprises a carrier vehicle for the compound and / or copolymer. The carrier vehicle may be selected from vehicles understood in the art, such as siloxane carrier vehicles, inorganic and organic solvents, etc. In other or additional embodiments, the non-aqueous phase further comprises a surfactant as further described below. An exemplary emulsion, a composition comprising the emulsion, and a film formed thereby are described in International Patent Publication WO2018145069A1.

[0189] Representative, non-limiting examples of organic solvents include toluene, xylene, and similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons; cyclohexane and similar aliphatic hydrocarbons; low molecular weight alcohols, e.g., methanol, ethanol, propanol, isopropanol, etc.; Low molecular weight ethers include, for example, di(propylene glycol) monomethyl ether, di(ethylene glycol) butyl ether, di(ethylene glycol) methyl ether, di(propylene glycol) butyl ether, di(propylene glycol) methyl ether acetate, di(propylene glycol) propyl ether, ethylene glycol phenyl ether, propylene glycol butyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, propylene glycol propyl ether, 1-phenoxy-2-propanol, tri(propylene glycol) methyl ether and tri(propylene glycol) butyl ether, and other similar glycols.

[0190] The aqueous phase contains water. The water can originate from any source and can be optionally purified, for example, through filtration, distillation, reverse osmosis technology, etc.

[0191] In many embodiments, the emulsion further comprises a surfactant. The surfactant may alternatively be referred to as an emulsifier and generally serves to emulsify the non-aqueous phase in the aqueous phase of the emulsion. The surfactant may be any surfactant suitable for preparing an emulsion having a non-aqueous phase and an aqueous phase.

[0192] For example, surfactants include one or more anionic, cationic, nonionic and / or amphoteric surfactants, organically modified silicones such as dimethicone copolyol, oxyethyleneated and / or oxypropylened ethers of glycerol, oxyethyleneated and / or oxypropylened ethers of fatty alcohols such as ceteareth-30, C12-15 pareth-7, fatty acid esters of polyethylene glycol such as PEG-50 stearate, PEG-40 monostearate, saccharide esters and ethers such as sucrose stearate, sucrose cocoate, and sorbitan stearate, and mixtures thereof, phosphate esters and salts thereof such as DEA oleth-10 phosphate, sulfosuccinates such as disodium PEG-5 citrate lauryl sulfosuccinate and disodium ricinoleamido It may include MEA sulfosuccinate, alkyl ether sulfates, such as sodium lauryl ether sulfate, isethionate, betaine derivatives, and mixtures thereof.

[0193] In a given embodiment, the surfactant includes an anionic surfactant. Anionic surfactants include, for example, carboxylates (sodium 2-(2-hydroxyalkyloxy)acetate), amino acid derivatives (N-acylglutamate, N-acylglycinate, or acylsarcosinate), alkyl sulfates, alkyl ether sulfates and their oxyethyleneated derivatives, sulfons, isethionates and N-acyl isethionates, taurates and N-acyl N-methyltaurate, sulfosuccinates, alkylsulfoacetates, phosphates and alkyl phosphates, polypeptides, anionic derivatives of alkyl polyglycosides (acyl-D-galactoside uronate), and fatty acid soaps, alkali metal sulfoglycinsates, sulfonated glyceryl esters of fatty acids, such as sulfonated monoglycerides of coconut lactic acid, salts of sulfonated monohydric alcohol esters, such as sodium oleyl isethianate, amides of aminosulfonic acids, such as oleyl Sodium salt of methyl tauride, sulfonation product of fatty acid nitriles, e.g., palmitonitrile sulfonate, sulfonated aromatic hydrocarbon, e.g., sodium alpha-naphthalene monosulfonate, condensation product of naphthalene sulfonic acid and formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulfates, e.g., sodium lauryl sulfate, ammonium lauryl sulfate and triethanolamine lauryl sulfate, ether sulfates having an alkyl group of eight or more carbon atoms, e.g., sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium alkyl aryl ether sulfate, and ammonium alkyl aryl ether sulfate, alkylaryl sulfonates having one or more alkyl groups of eight or more carbon atoms, alkali metal alkylbenzenesulfonic acid salts exemplified by sodium salt of hexylbenzenesulfonic acid, Sodium octylbenzenesulfonate, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium cetylbenzenesulfonate, and sodium myristylbenzenesulfonate, CH3(CH2)6CH2O(C2H4O)2SO3H, CH3(CH2)7CH2O(C2H4O) 3.5SO3H, CH3(CH2)8CH2O(C2H4O)8SO3H, CH3(CH2) 19 CH2O(C2H4O)4SO3H, and CH3(CH2) 10 Sulfuric acid esters of polyoxyethylene alkyl ethers containing CH2O(C2H4O)6SO3H, sodium salts, potassium salts and amine salts of alkylnaphthylsulfonic acid, and mixtures thereof are included.

[0194] In these or other embodiments, the surfactant comprises a cationic surfactant. Cationic surfactants include, for example, various fatty acid amines and amides and derivatives thereof, and salts of fatty acid amines and amides. Examples of aliphatic fatty acid amines include dodecylamine acetate, octadecylamine acetate, and acetates of amines of tallow fatty acids; homologues of aromatic amines having fatty acids, e.g., dodecylaniline; fatty amides derived from aliphatic diamines, e.g., undecylimidazoline; fatty amides derived from aliphatic diamines, e.g., ashendecylimidazoline; fatty amides derived from disubstituted amines, e.g., oleylaminodiethylamine; derivatives of ethylenediamine; tallow trimethylammonium chloride, dioctadecyldimethylammonium chloride, didodecyldimethylammonium chloride, dihexadecylammonium chloride; alkyltrimethylammonium hydroxides, e.g., octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide; and hexadecyltrimethylammonium hydroxide, dialkyldimethylammonium Hydroxides, such as octyl dimethylammonium hydroxide, decyl dimethylammonium hydroxide, didodecyl dimethylammonium hydroxide, dioctadecyl dimethylammonium hydroxide, tallow trimethylammonium hydroxide, coconut oil, trimethylammonium hydroxide, methylpolyoxyethylene cocoammonium chloride, and quaternary ammonium compounds and their salts, amide derivatives of amino alcohols, such as beta-hydroxyethylstearylamide, amine salts of long-chain fatty acids, and mixtures thereof are included.

[0195] In these or other embodiments, the surfactant comprises a nonionic surfactant. Nonionic surfactants include, for example, polyoxyethylene alkyl ethers (e.g., lauryl, cetyl, stearyl, or octyl), polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanol, polyoxyalkylene glycol-modified polysiloxane surfactants, polyoxyalkylene-substituted silicones (rake type or ABn type), silicone alkanolamides, silicone esters, silicone glycosides, dimethicone copolyols, fatty acid esters of polyols, for example, sorbitol and glyceryl mono-, di-, tri-, and sesqui-oleates and stearates, glyceryl and polyethylene glycol laurates; Fatty acid esters of polyethylene glycol (e.g., polyethylene glycol monostearate and monolaurate), polyoxyethyleneated fatty acid esters of sorbitol (e.g., stearate and oleate), and mixtures thereof are included.

[0196] In these or other embodiments, the surfactant comprises an amphoteric surfactant. Amphoteric surfactants include, for example, amino acid surfactants, betaine acid surfactants, trimethylnonyl polyethylene glycol ethers, and polyethylene glycol ether alcohols containing a linear alkyl group having 11 to 15 carbon atoms, such as 2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (6 EO) (sold as Tergitol (registered trademark) TMN-6 by OSi Specialties, A Witco Company, Endicott, New York, USA), 2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol (10 EO) (sold as Tergitol (registered trademark) TMN-10 by OSi Specialties, A Witco Company, Endicott, New York, USA), and alkylene-oxypolyethylene oxyethanol (C 11-15 Secondary alkyl, 9 EO) (marketed as Tergitol (registered trademark) 15-S-9 by OSI Specialty, Witco Company, Endicott, New York), Alkylene-oxypolyethylene oxyethanol (C 11-15Secondary alkyl, 15 EO) (sold as Tergitol (registered trademark) 15-S-15 by OSI Specialty, Witco Company, Endicott, New York, USA), octylphenoxypolyethoxyethanol having varying amounts of ethylene oxide units, e.g., octylphenoxypolyethoxyethanol (40 EO) (sold as Triton (registered trademark) X405 by Rohm and Haas Company, Philadelphia, Pennsylvania, USA), nonionic ethoxylated tridecyl ether available under the generic name Trycol from Emery Industries, Moldeen, South Carolina, USA, alkali metal of dialkyl sulfosuccinate available under the generic name Aerosol from American Cyanamid Company, Wayne, New Jersey, USA These include salts, polyethoxylated quaternary ammonium salts of primary fatty amines and ethylene oxide condensation products (available from Armak Company, Chicago, Illinois, USA under the trade names Ethoquad, Ethomeen, or Arquad), polyoxyalkylene glycol-modified polysiloxanes, N-alkylamidobetaines and derivatives thereof, proteins and derivatives thereof, glycine derivatives, sultanes, alkyl polyaminocarboxylates and alkylamphoacetates, and mixtures thereof. These surfactants may also be available from other suppliers under different trade names.

[0197] A surfactant may be included in the emulsion at a concentration effective for emulsifying the non-aqueous phase (or vice versa) in the aqueous phase. Such a concentration is in the range of greater than 0 to 10 weight percent, alternatively 0.3 to 5 weight percent, based on the total weight of the emulsion. The surfactant or a combination of surfactants may be present in the aqueous phase of the emulsion, the non-aqueous phase of the emulsion, the interface between the aqueous phase and the non-aqueous phase, or a combination thereof.

[0198] The emulsion may further comprise one or more various optional additives, such as coupling agents, antistatic agents, ultraviolet (UV) absorbers, plasticizers, leveling agents, preservatives, surface active substances (surfactants or detergents or emulsifiers), foam boosters, depositing agents, thickeners, water stabilizers, fillers, suspending agents, biocides, freeze / thaw additives, antifreeze agents, viscosity modifiers, foam control agents, dyes (e.g., pigments), binders, and combinations thereof.

[0199] In addition to or alternatively to the above, the emulsion may further include various additive compounds to improve the properties of the film formed therefrom. Examples of additive compounds are silanes, such as tetrakis(dimethylamine)silane, tetraethyl orthosilicate, glycidoxypropyl trimethoxysilane, triethylsilane, isobutyl trimethoxysilane; and siloxanes, such as heptamethyltrisiloxane, tetramethyldisiloxane, etc.

[0200] In some embodiments, the emulsion is a coating composition or may be formulated into a coating composition. Such a coating composition is typically used to provide a continuous protective coating on a substrate by applying the coating composition to the surface of the substrate. Examples of such substrates include organic or inorganic components and may include household materials such as leather, paper, wood, metal, plastic, fabric, paint, etc. The coating composition may also be suitable for use in other applications, such as as a component in paint, for example, as a protective and / or decorative coating.

[0201] In various embodiments, compounds and / or copolymers may be used as additives for epoxy coatings. A number of epoxy coatings are understood in the art, including those described in U.S. Patent No. 8722148 and U.S. Patent Application Publication No. 20060205861.

[0202] In various embodiments, the composition comprises an emulsion and an organic binder. The emulsion may be formed in situ within the composition, or the composition may be provided by first preparing the emulsion and then combining it with an organic binder along with any other optional component. In a specific embodiment, the composition is formed by combining the emulsion and the organic binder with any optional component. The emulsion is typically present in the composition, that is, forming a composition having the emulsion does not destroy the emulsion.

[0203] Organic binders are not limited and are generally selected based on the end-use application of the composition. While exemplary examples are described below, any organic binder may be used in the composition. Organic binders may be reactive or non-reactive and may be thermoplastic and / or thermosetting. Typically, organic binders are organic polymers and / or resins.

[0204] In a given embodiment, the organic binder comprises natural latex. In these or other embodiments, the organic binder comprises synthetic latex. The organic binder may also be a combination of natural latex and synthetic latex. For example, when the composition is used to manufacture a film or paint, the organic binder is typically natural latex and / or synthetic latex. Natural latex and synthetic latex are known in the art. For example, depending on the choice of organic binder, the composition may be used as a solvent-free paint, such as a heat-resistant paint. The paint may be used for thermal insulation applications, anti-fouling applications, construction applications, commercial / industrial or residential applications, protection applications, leather applications, textile applications, etc.

[0205] Specific examples of organic binders include, but are not limited to, polyolefins, acrylic polymers, polyvinyl acetate, polyvinyl chloride, styrene (e.g., styrene-butadiene rubber), acrylonitrile-butadiene, epoxy resins, phenols, polyesters, polyvinyl butyral, phenoxy, polyurea, cellulose resins, polyurethanes, polyamides, polyethers, alkyds, silicones, acrylonitrile, etc. Organic binders may include combinations of such organic binders, or copolymers or terpolymers comprising one or more such organic binders.

[0206] The content of the organic binder in the composition may vary depending on a number of factors, such as the selection thereof, the type and amount of emulsion present in the composition, and the end-use application of the composition. An increased loading of the organic binder generally causes the film to have greater hardness and other increased physical properties. In a given embodiment, the composition comprises the binder in an amount greater than 0 to less than 100 weight%, alternatively greater than 0 to 50 weight%, alternatively 0.1 to 40 weight%, and alternatively 5 to 15 weight% based on the total weight of the composition.

[0207] The organic binder may be dispersed or disposed in a carrier vehicle. The carrier vehicle may be any suitable carrier vehicle that typically solubilizes the organic binder. Typically, the carrier vehicle depends on the organic binder used. The carrier vehicle may be water so that the composition as a whole is water-based, or it may be a solvent other than water, e.g., an organic solvent. In a given embodiment, as with an emulsion, water is substantially absent from the composition. Substantially absent from water is defined in relation to an emulsion.

[0208] In some embodiments, the composition further comprises one or more optional components. The composition may comprise any of the optional components described above with respect to the emulsion. These optional components may be included in the composition from what is present in the emulsion, may be included in the composition independently of the emulsion, or may be both. Specific examples of optional components include, but are not limited to, coloring agents, adhesion aids, surfactants, thickeners, defoaming agents, compatibilizers, UV stabilizers, antioxidants, biocides, flame retardants, etc. Some of these optional components may be present in the emulsion as described above and thus included in the composition, or one or more of these optional components may be incorporated when forming the composition. Any of the optional components described above with respect to the emulsion may also be present in the composition through introduction from the emulsion or through the inclusion of additional amounts of specific components. For example, the composition may comprise a catalyst, which may be the same as or different from any catalyst that may be present in the emulsion.

[0209] In a given embodiment, the composition further comprises one or more coloring agents, such as pigments, dyes, etc. Such coloring agents may be organic or inorganic, synthetic or natural coloring agents. Examples of coloring agents are described above in relation to the emulsion. The emulsion and the composition itself may comprise different coloring agents selected independently.Examples of additional suitable colorants include cadmium yellow, cadmium red, cadmium green, cadmium orange, carbon black (including vine black and lamp black), ivory black (bone char), chrome yellow, chrome green, cobalt violet, cobalt blue, cerulean blue, aureolin (cobalt yellow), azurite, Han purple, Han blue, Egyptian blue, malachite, Paris green, phthalocyanine blue BN, phthalocyanine green G, verdigris, viridian, sanguine, caput mortuum, oxide red, red ochre, Venetian red, Prussian blue, yellow ochre, and raw sienna. Sienna), Burnt Sienna, Raw Umber, Burnt Umber, Cremnitz White, Naples Yellow, Vermilion Titanium Yellow, Titanium Beige, Titanium White (TiO2), Titanium Black, Ultramarine, Ultramarine Green Shade, Zinc White, Zinc Ferrite, Alizarin (Synthetic or Natural), Alizarin Crimson (Synthetic or Natural), Gamboge, Cochineal Red, Rose Madder, Indigo, Indian Yellow, Tyrian Purple, Quinacridone, Magenta, Phthalo Green, Phthalo Blue, Pigment Red 170, or any combination thereof are included.

[0210] In certain embodiments, the composition further comprises an adhesion aid. A suitable adhesion aid comprises any compound that reduces the minimum film-forming temperature of the organic binder when the organic binder actually forms a film and / or increases the rate of solid film formation from the organic binder when any carrier vehicle or water is removed from the composition. Examples of suitable adhesion aids include glycol ethers, 2,2,4-trimethyl-1,3-pentanediol isobutyrate, and combinations thereof.

[0211] In a given embodiment, the composition comprises a surfactant. The surfactant may be the same as or different from any surfactant used in the emulsion, and examples thereof are described above.

[0212] To achieve desired viscosity and flow characteristics, a thickener (or rheology modifier) ​​may also be included in the composition. Depending on the selection of the thickener, such as the selection of the organic binder, this thickener may function, for example, by forming a number of hydrogen bonds with the organic binder, thereby causing chain entanglement, looping, and / or swelling, which results in volume limitation. In a given embodiment, a cellulose derivative, such as hydroxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose, may be used as a thickener.

[0213] In some embodiments, the composition comprises an antifoaming agent. The antifoaming agent may be any suitable chemical additive that reduces and interferes with foam formation in the composition. Antifoaming agents are known in the art and are typically selected based on other components present in the composition.

[0214] Where the composition includes a compatibilizer, the compatibilizer may be any compound or component that modifies, or alternatively improves, the wetting of the components in the composition. Examples of such compatibilizers include titanium alkalate, esters of phosphoric acid, phosphonic acid, and silicic acid, metallic salts and esters of aliphatic, aromatic, and alicyclic acids, ethylene / acrylic acid or methacrylic acid, ethylene / esters of acrylic acid or methacrylic acid, ethylene / vinyl acetate resin, styrene / maleic anhydride resin or esters thereof, acrylonitrile butadiene styrene resin, methacrylate / butadiene styrene resin (MBS), styrene acrylonitrile resin (SAN), and butadiene acrylonitrile copolymer. Alternatively or additionally, the compatibilizer may comprise a silane, e.g., a hydrocarbonoxysilane, e.g., alkoxysilane, a combination of alkoxysilane and hydroxy-functional polyorganosiloxane, an amino-functional silane, or a combination thereof. The silane may comprise any functional group, which may be an adhesion-promoting group such as an amino, epoxy, mercapto, and / or acrylate group. A combination of functional groups may be used, for example, (D) the compatibilizer may comprise an epoxy-functional alkoxysilane. Suitable epoxy-functional organic groups are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups, e.g., vinyl, allyl, hexenyl, undecylenyl. Examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof.Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and combinations thereof. Aminofunctional silanes, such as aminofunctional alkoxysilanes, may have various amino groups as understood in the art. Other examples of compatibilizers include modified polyethylene and modified polypropylene obtained by modifying polyethylene and polypropylene, respectively, using reactive groups comprising polar monomers such as maleic anhydride or ester, acrylic acid or methacrylic acid or ester, vinyl acetate, acrylonitrile, and styrene.

[0215] Specific examples of UV stabilizers include branched and linear 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methyl-phenol (TINUVIN (Trademark) 571). Additional examples of suitable UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; methyl 1,2,2,6,6-pentamethyl-4-piperidyl / sebacate; and combinations thereof (TINUVIN (Trademark) 272). These and other TINUVIN (Trademark) additives, such as TINUVIN (Trademark) 765, are available for purchase from Ciba Specialty Chemicals, Tarrytown, New York. Other UV and light stabilizers are available for purchase, exemplified by LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from EI du Pont de Nemours and Company, Delaware, USA. An example of an oligomeric antioxidant stabilizer (particularly a hindered amine light stabilizer (HALS)) is Ciba Tinubin (trademark) 622, which is a dimethyl ester of butaneic acid copolymerized with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol.

[0216] When used, the antioxidant may be any antioxidant known in the art. Specific examples thereof include phenolic antioxidants and combinations of phenolic antioxidants and stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially hindered phenols; and sterically hindered amines, such as tetramethylpiperidine derivatives. Suitable phenolic antioxidants include Vitamin E and Irganox (Trademark) 1010 from Ciba Specialty Chemicals, USA. Irganox (Trademark) 1010 comprises pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). Additional examples of antioxidants include acetyl cysteine, arbutin, ascorbic acid, ascorbic acid polypeptide, ascorbyl dipalmitate, ascorbyl methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, BHA, p-hydroxyanisole, BHT, t-butyl hydroquinone, caffeic acid, Camellia sinensis oil, chitosan ascorbate, chitosan glycolate, chitosan salicylate, chlorogenic acid, cysteine, cysteine ​​HCl, decyl mercaptomethylimidazole, erythorbic acid, diamyl hydroquinone, di-t-butyl hydroquinone, disecetyl thiodipropionate, dicyclopentadiene / t-butyl cresol copolymer, digalloyl trioleate, and dilauryl. Thiodipropionate, Dimyristyl thiodipropionate, Dioleyl tocopheryl methylsilanol, Isoquercitrin, Diosmin, Disodium ascorbyl sulfate, Disodium rutinyl disulfate, Distearyl thiodipropionate, Ditridecyl thiodipropionate, Dodecyl gallate, Ethyl ferulate, Ferulic acid, Hydroquinone, Hydroxylamine HCl, Hydroxylamine sulfate, Iso-octyl thioglycolate, Kojic acid, Madecassicoside, Magnesium ascorbate, Magnesium ascorbyl phosphate, Melatonin, Methoxy-PEG-7 rutinyl succinate,Methylene di-t-butylcresol, methylsilanol ascorbate, nordihydroguaiaretic acid, octyl gallate, phenylthioglycolic acid, phloroglucinol, potassium ascorbyl tocopheryl phosphate, thiodiglycolamide, potassium sulfite, propyl gallate, rosmarinic acid, rutin, sodium ascorbate, sodium ascorbyl / cholesteryl phosphate, sodium bisulfite, sodium erythorbate, sodium metabisulfide, sodium sulfite, sodium thioglycolate, sorbityl furfural, tea tree (Melaleuca aftemifolia) oil, tocopheryl acetate, tetrahexyldecyl ascorbate, tetrahydrodiferulloylmethane, tocopheryl linoleate / oleate, Thiodiglycol, tocopheryl succinate, thiodiglycolic acid, thioglycolic acid, thiolactic acid, thiosalicylic acid, thiotaurine, retinol, tocopheres-5, tocopheres-10, tocopheres-12, tocopheres-18, tocopheres-50, tocopherol, tocopersolan, tocopheryl linoleate, tocopheryl nicotinate, tocoquinone, o-tolyl biguanide, tris(nonylphenyl) phosphite, ubiquinone, zinc dibutyl dithiocarbamate, and mixtures thereof.

[0217] Biocides may be exemplified by fungicides, herbicides, insecticides, antimicrobial agents, or combinations thereof.

[0218] Specific examples of fungicides include N-substituted benzimidazole carbamates, benzimidazolyl carbamates, such as methyl 2-benzimidazolyl carbamate, ethyl 2-benzimidazolyl carbamate, isopropyl 2-benzimidazolyl carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, methyl N-{2-[1-(N-methylcarbamoyl)benzimidazolyl]}carbamate, and methyl N-{2-[1-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, methyl N-{2-[1-(N-methylcarbamoyl)-5-methylbenzimidazolyl]}carbamate, ethyl N-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[2-(N-methylcarbamoyl)benzimidazolyl]}carbamate, ethyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, ethyl N-{2-[1-(N-methylcarbamoyl)-6-methylbenzimidazolyl]}carbamate, isopropyl N-{2-[1-(N,N-dimethylcarbamoyl)benzimidazolyl]}carbamate, isopropyl N-{2-[1-(N-methylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, methoxyethyl N-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1-(N-butylcarbamoyl)benzimidazolyl]}carbamate, methyl N-{1-(N,N-dimethylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[N-methylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[1-(N-butylcarbamoyloxy)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1-(N-propylcarbamoyl)benzimidazolyl]}carbamate, ethoxyethyl N-{2-[1-(N-butylcarbamoyloxy)benzimidazolyl]}carbamate, methyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-chlorobenzimidazolyl]}carbamate, and methyl N-{2-[1-(N,N-dimethylcarbamoyl)-6-nitrobenzimidazolyl]}carbamate;10,10'-Oxybisphenoxarsine (trademark Vinyzene, having OBPA), di-iodomethyl-para-tolylsulfone, benzothiophen-2-cyclohexylcarboxamide-S,S-dioxide, N-(fluorodichloride methylthio)phthalimide (trademark Fluor-Folper, and having Preventol A3); Includes methyl-benzimidiazole-2-ylcarbamate (trademark Carbendazim, and having Preventol BCM), zinc-bis(2-pyridylthio-1-oxide) (zinc pyrithione) 2-(4-thiazolyl)-benzimidazole, N-phenyl-iodopropargylcarbamate, N-octyl-4-isothiazolin-3-one, 4,5-dichloride-2-n-octyl-4-isothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one and / or triazolyl compounds, e.g., tebuconazole combined with silver-containing zeolite;

[0219] Alternatively, the biocide may comprise a boron-containing material, e.g., boric anhydride, borax, or disodium octaborate tetrahydrate; which may function as an insecticide, fungicide, and / or flame retardant.

[0220] Specific examples of suitable flame retardants include carbon black, hydrated aluminum hydroxide, and silicates, such as wollastonite, platinum, and platinum compounds. Alternatively, if used, flame retardants may be halogenated flame retardants, e.g., decabromodiphenyl oxide, octabromodiphenyl oxide, hexabromocyclododecane, decabromobiphenyl oxide, diphenoxybenzene, ethylene bis-tetrabromophthalmide, pentabromoethylbenzene, pentabromobenzyl acrylate, tribromophenyl maleate imide, tetrabromobisphenyl A, bis-(tribromophenoxy)ethane, bis-(pentabromophenophenoxy)ethane, polydivomophenylene oxide, tribromophenylallyl ether, bis-dibromopropyl ether, tetrabromophthalic anhydride, dibromoneopentyl glycol, dibromoethyl dibromocyclohexane, pentabromodiphenyl oxide, tribromostyrene, It can be selected from pentabromochlorocyclohexane, tetrabromoxylene, hexabromocyclododecane, brominated polystyrene, tetradecabromodiphenoxybenzene, trifluoropropene, and PVC. Alternatively, if used, the flame retardant may be selected from phosphorus-based flame retardants, e.g., (2,3-dibromopropyl)-phosphate, phosphorus, cyclic phosphate, triaryl phosphate, bis-melamine pentate, pentaerythritol bicyclic phosphate, dimethyl methyl phosphate, phosphine oxide diol, triphenyl phosphate, tris-(2-chloroethyl) phosphate, phosphate esters, e.g., tricreyl, trixylenyl, isodecyl diphenyl, ethylhexyl diphenyl of various amines, phosphate salts, e.g., ammonium phosphate, trioctyl, tributyl, or tris-butoxyethyl phosphate esters.Other suitable flame retardants may include tetraalkyl lead compounds, e.g., tetraethyl lead, iron pentacarbonyl, manganese methyl cyclopentadienyl tricarbonyl, melamine and derivatives, e.g., melamine salts, guanidine, dicyandiamide, ammonium sulfamate, alumina trihydrate, and magnesium hydroxide alumina trihydrate.

[0221] The aqueous composition comprises, as a component, any composition comprising water as a primary or multiple component (e.g., as a solvent, carrier, or medium). In these embodiments, the aqueous composition further comprises compounds and / or copolymers of the present invention.

[0222] As understood in the art, surfactants are compounds that lower surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid. Surfactants can act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants. Surfactants can serve as cleaning agents, wetting agents, dispersants, emulsifiers, foaming agents, and defoaming agents in many practical applications and products, including but not limited to detergents, fabric softeners, emulsions, soaps, paints, adhesives, inks, anti-fog, ski wax, snowboard wax, deinking of recycled paper, flotation, washing and enzymatic processes, and laxatives. Agrochemical formulations, such as some herbicides, insecticides, biocides (fungicides), and spermicides, may also contain one or more surfactants. Personal care products, such as cosmetics, shampoo, shower gel, hair conditioner (after shampooing), and toothpaste, often contain one or more surfactants.

[0223] In various embodiments, the surfactant composition comprises compounds and / or copolymers of the present invention. In certain embodiments, the surfactant composition further comprises one or more additives understood in the art, such as water and / or other vehicles, one or more conventional surfactants, etc. Those skilled in the art understand that the surfactant composition may also be referred to as a wetting composition, a surface tension modifier, or a dispersant composition. In some applications, there may be some nuance regarding differences in the form, function, and / or end application of such compositions.

[0224] In other embodiments, the compound itself—and / or the copolymer itself—is a surfactant. In these embodiments, the compound and / or copolymer may be referred to as a dispersant, a wetting agent, or a surface tension modifier.

[0225] In various embodiments, the composition is selected from the group consisting of foamed and substantially non-foamed compositions, aqueous and non-aqueous compositions, and combinations thereof. A specified film is described below. The composition may be curable, partially curable, or uncurable. In embodiments where the composition is at least partially curable or curable, the composition may change its form, such as from a liquid to a more viscous liquid, gel, semi-solid, or solid.

[0226] In various embodiments, the composition is useful as an anti-blocking (or anti-blocking) additive (or agent). In these embodiments, the composition may also provide scratch resistance and a low coefficient of friction (COF). In certain embodiments, the compound itself—and / or the copolymer itself—is the anti-blocking additive.

[0227] Anti-blocking agents are often used in or for films, such as polyolefin films, to improve the slippage between individual molecules of the anti-blocking agent, and are an important component for the post-processing transformation (cutting, folding, welding, etc.) of such films. Blocking is a common problem faced by manufacturers of films and coatings. Blocking is the adhesion between two adjacent layers of a film. This is a problem most associated with polyethylene and polypropylene films (either blown or cast), and to a lesser extent with extrusion-coated or laminated products. Blocking of adjacent film layers occurs due to the presence of van der Waals forces between the amorphous regions of the polymer. These forces increase as the distance between the two layers decreases, and consequently, blocking increases when the two layers are pressed together (e.g., during lamination of the transformed finished film or bonding onto a take-up roll). Another possible reason for blocking is the presence of low molecular weight chemical species (e.g., oligomers) that tend to migrate to the surface of the film.

[0228] An effective method to address these handling problems is to add anti-blocking additives. Anti-blocking additives present in the resin protrude microscopically from the film surface. This creates protrusions ("little bumps"), which help minimize surface contact between films and increase the distance between the two layers, thereby minimizing blocking.

[0229] Blocking between adjacent layers increases friction, and the addition of anti-blocking agents generally contributes to a reduction in the COF between films. COF is a measure of the relative difficulty one surface experiences when sliding over an adjacent surface. The greater the resistance to sliding, the higher the COF value (for example, "low-slip" or "no-slip" films are sometimes referred to as "high COF" films).

[0230] In various embodiments, the composition is an agricultural composition. At least one of the compounds and copolymers may be used as an additive for the agricultural composition. Numerous types of compositions for promoting agriculture are understood in the art, including those that promote plant growth, suppress or prevent weeds, suppress or prevent harmful animals and insects, etc. Many agronomically suitable additives, adjuvants, and / or phytocatalysts, including fertilizers containing elements such as nitrogen, phosphorus, potassium, elevated carbon dioxide, hydrogen peroxide, iron, and manganese; secondary nutrients such as sources of sulfur, calcium, and magnesium; micronutrients such as boron, cobalt, copper, molybdenum, zinc, and nickel; water-soluble carbohydrates such as sucrose, fructose, and glucose; and various alkyl glucosides, are applied to plants to support or enhance plant growth, regardless of whether plant growth regulators or genetically modified plants are used.

[0231] In various embodiments, the composition comprises at least one insecticide. The term insecticide is understood to include herbicides, insecticides, acaricides, nematicides, ectoparasites, fungicides, and plant growth regulators. The composition is not limited in this regard.

[0232] Examples of a class of compounds having herbicidal activity include imidazolinone, e.g. imazaquin; sulfonylurea, e.g. chlorimurone-ethyl; triazolopyrimidine sulfonamide, e.g. flumethulam; aryloxyphenoxypropionate, e.g. quizalopov-ethyl; aryl urea, e.g. isoproturone and chlorotolurone; triazine, e.g. atrazine and simazine; aryl carboxylic acid, e.g. picloram; aryloxyalkanic acid, e.g. MCPA; chloroacetanilide, e.g. metazachlor; ditroaniline, e.g. oryzalin; pyrazol, e.g. pyrazolinate; and diphenyl ether, e.g. bifenox. Examples of a class of compounds having insecticidal activity include benzoyl urea, e.g., hexaflumurone; diacylhydrazine, e.g., tebufenozide; carbamate, e.g., carbofuran; pyrethroid, e.g., cypermethrin; organic phosphate, e.g., phosmet; triazole; and natural products, e.g., spinosins.

[0233] Examples of a class of compounds having fungicide activity include morpholine, e.g., dimethomorph, phenylamide, e.g., benzalaxyl, azole, e.g., hexaconazole, strobilurin, e.g., azoxystrobin, phthalonitrile, e.g., chlorothalonil, and phenoxyquinoline, e.g., quinoxifene.

[0234] Examples of insecticides / caricides are ventiocarb, diflubenzuron, teflubenzuron, lufenuron, diapentiuron or pyrethroids, such as bifenthrin, bioallethrin, tau-fluvalinate, resmethrin, permethrin, cypermethrin, cyfluthrin, cyhalothrin, deltamethrin, tefluthrin or tetramethrin; furteron pymetrozine, thiocyclam, phenoxycarb, metoprene, abamectin and emamectin.

[0235] In various embodiments, compounds and / or copolymers may be used as intermediates for the treatment of particles, for example, for treating the surface of metal oxide particles. The particles may have various sizes and particle size distributions, including nano-size and micro-size.

[0236] The metal oxide particles may be any suitable metal oxide particles. Suitable metal oxide particles include, for example, aluminum oxide, titanium oxide, silica, tin oxide, magnesium oxide, zinc oxide, strontium oxide particles, mixtures thereof, and co-oxides thereof.

[0237] The particles may be electrically and / or thermally conductive or non-conductive. In a given embodiment, the particles are classified as electrically conductive fillers, which are metals or conductive non-metals; or may be metals or non-metal particles having an outer surface of metal, wherein the outer surface metal is a precious metal such as silver, gold, platinum, palladium and alloys thereof, or a base metal such as nickel, aluminum, copper or steel. The particles may also have an outer surface of metal together with a core of particles made of copper, solid glass, hollow glass, mica, nickel, ceramic fibers or polymers, such as polystyrene and polymethyl methacrylate.

[0238] In a given embodiment, the particles are classified as a thermally conductive filler, which may be metal particles, metal oxide particles, thermally conductive non-metal powder, or a combination thereof. The thermally conductive filler may be aluminum, copper, gold, nickel, silver, alumina, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, zinc oxide, barium titanate, diamond, graphite, carbon or silicon nano-sized particles, boron nitride, aluminum nitride, boron carbide, titanium carbide, silicon carbide, and tungsten carbide.

[0239] Examples of mineral fillers or pigments that may be treated include titanium dioxide, aluminum trihydroxide (also called ATH), magnesium dihydroxide, mica, kaolin, calcium carbonate, unhydrated, partially hydrated or hydrated fluorides, chlorides, bromides, iodides, chromates, carbonates, hydroxides, phosphates, hydrogen phosphates, nitrates, oxides, and sulfates of sodium, potassium, magnesium, calcium, and barium; zinc oxide, aluminum oxide, antimony pentoxide, antimony trioxide, beryllium oxide, chromium oxide, iron oxide, lithopone, boric acid, or borate salts, e.g., zinc borate, barium metaborate, or aluminum borate; mixed metal oxides, e.g., silica including aluminosilicate, vermiculite, dry silica, fused silica, and precipitated silica, quartz, sand, and silica gel; Rice hull ash, ceramic and glass beads, zeolite, metals, e.g., aluminum flakes or powder, bronze powder, copper, gold, molybdenum, nickel, silver powder or flakes, stainless steel powder, tungsten, hydrated calcium silicate, barium titanate, silica-carbon black composites, functionalized carbon nanotubes, cement, fly ash, slate flour, ceramic or glass beads, bentonite, clay, talc, anthracite, apatite, attapulgite, boron nitride, crristobalite, diatomite, dolomite, ferrite, feldspar, graphite, calcined kaolin, molybdenum disulfide, perlite, pumice, pyrophyllite, sepiolite, zinc tartrate, zinc sulfide, or It includes wollastonite.

[0240] Other fillers that may be treated include natural fibers, such as wood flour, wood fibers, cotton fibers, or agricultural fibers, such as straw, hemp, flax, kenaf, kapok, jute, ramie, sisal, heneken, corn fibers, or coir, nut shells or rice bran, lignin, starch, or cellulose and cellulose-containing products, or certain synthetic fibers, such as aramid fibers, nylon fibers, cotton fibers, or glass fibers, or plastic microspheres of polytetrafluoroethylene or polyethylene, and the present invention comprises the treatment of such fillers. The fillers may be solid organic pigments, such as azo, indigoid, triphenylmethane, anthraquinone, hydroquinone, or xanthine dyes, or solid organic flame retardants, such as polychlorobiphenyl or decabromodiphenyl oxide or phosphorus-containing flame retardants.

[0241] In various embodiments, the compound and / or copolymer may be used to modify a composition comprising a siloxane or at least one siloxane. The modification may be direct or indirect, such as when the compound can react with the siloxane. Further embodiments of the composition are described below.

[0242] The composition may include one or more fillers. The fillers may be one or more reinforcing fillers, non-reinforcing fillers, or mixtures thereof. Examples of finely divided reinforcing fillers include dry and precipitated silica with a high surface area containing rice hull ash and trace amounts of calcium carbonate. Examples of finely divided non-reinforcing fillers include crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, carbon black, talc, and wollastonite. Other fillers that may be used alone or in addition to the above include carbon nanotubes, e.g., multi-walled carbon nanotubes, aluminite, hollow glass spheres, calcium sulfate (hardyx gypsum), gypsum, calcium sulfate, magnesium carbonate, clay, e.g., kaolin, aluminum trihydroxide, magnesium hydroxide (hydrotalc), graphite, copper carbonate, e.g., malachite, nickel carbonate, e.g., zarachite, barium carbonate, e.g., toxicite and / or strontium carbonate, e.g., strontianite. Additional alternative fillers include aluminum oxide and silicates from the group consisting of olivine; garnet; aluminosilicate; cyclic silicates; chain silicates; and sheet silicates. In a given embodiment, the composition comprises at least one filler comprising hollow particles, e.g., hollow spheres. Such a filler may be useful for contributing to the porosity and / or overall pore fraction of the foam. In a given embodiment, some fillers may be used to adjust the thixotropic properties of the composition.

[0243] The filler may optionally be surface-treated with a treatment agent, if present. Treatment agents and treatment methods are known in the art. Surface treatment of the filler(s) is typically performed, for example, using a fatty acid or fatty acid ester, for example, a stearate, or using an organosilane, organosiloxane, or organosilazane, for example, a hexaalkyl disilazane or a short-chain siloxane diol. Generally, surface treatment makes the filler(s) hydrophobic, thereby making them easier to handle and easier to obtain a homogeneous mixture with other components in the composition. Silanes, for example, R 5 e Si(OR 6 ) 4-e (Here, R 5 is a substituted or unsubstituted monovalent hydrocarbon group having 6 to 20 carbon atoms, for example, an alkyl group, e.g., hexyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl, and an aralkyl group, e.g., benzyl and phenylethyl, and R 6 (which is an alkyl group having 1 to 6 carbon atoms, and the subscript "e" is 1, 2, or 3) may also be used as a filler treatment agent. In a given embodiment, at least one compound and copolymer may be used as a treatment agent as described above, optionally in combination with one or more conventional treatment agents.

[0244] In various embodiments, the composition further comprises a reaction inhibitor. For example, alkyne alcohols, such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexin-3-ol or 2-phenyl-3-butyn-2-ol; ene-yne ​​compounds, such as 3-methyl-3-pentene-1-phosphorus or 3,5-dimethyl-3-hexene-1-phosphorus; or 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane or benzotriazole may be included in the composition as optional components.

[0245] In various embodiments, the composition further comprises a thixotropic agent. Suitable thixotropic agents include rheological agents, specific examples of such rheological agents can be found in U.S. Patent Application Publications No. 2018 / 0066115 A1 and No. 2018 / 0208797 A1.

[0246] In various embodiments, the composition further comprises an adhesion promoter. The adhesion promoter can improve the adhesion of the foam to a base material, e.g., a second surface (36), that is in contact during curing. In a given embodiment, the adhesion promoter is selected from an organosilicon compound in which at least one alkoxy group within a molecule is bonded to a silicon atom. Such alkoxy groups are exemplified by methoxy groups, ethoxy groups, propoxy groups, butoxy groups, and methoxyethoxy groups. Furthermore, the non-alkoxy groups bonded to the silicon atom of such organosilicon compounds are substituted or unsubstituted monovalent hydrocarbon groups, e.g., alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl halides, etc.; epoxy group-containing monovalent organic groups, e.g., 3-glycidoxypropyl groups, 4-glycidoxybutyl groups, or similar glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl group, 3-(3,4-epoxycyclohexyl)propyl group, or similar epoxycyclohexylalkyl group; and 4-oxyranylbutyl group, 8-oxyranyloctyl group, or similar oxyranylalkyl group; acrylic group-containing monovalent organic group, e.g. 3-methacryloxypropyl group, etc.; and hydrogen atoms are exemplified.

[0247] These organosilicon compounds generally possess silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms. Furthermore, due to their ability to impart good adhesion to various types of base materials, these organosilicon compounds generally possess at least one epoxy-containing monovalent organic group within a single molecule. Examples of this type of organosilicon compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. The molecular structures of organosiloxane oligomers or alkyl silicates are exemplified by linear chain structures, partially branched linear chain structures, branched chain structures, cyclic structures, and network structures. Linear chain structures, branched chain structures, and network structures are typical. These types of organosilicon compounds include silane compounds, such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc.; Siloxane compounds having at least one silicon-bonded alkenyl group or silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group within one molecule; a mixture of a silane compound or siloxane compound having at least one silicon-bonded alkoxy group and a siloxane compound having at least one silicon-bonded hydroxyl group and at least one silicon-bonded alkenyl group within one molecule; and exemplified by methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate.

[0248] In various embodiments, the composition comprises at least one blowing agent. When used, the blowing agent may be selected from the group consisting of chemical blowing agents, physical blowing agents, and combinations thereof. The amount of blowing agent used may vary depending on the desired result. For example, the amount of blowing agent may vary to match the final foam density and foam rise profile.

[0249] The composition may comprise a carrier vehicle (or diluent) comprising silicones of both linear and cyclic forms, organic oils, organic solvents, and mixtures thereof. Specific examples of solvents can be found in U.S. Patent No. 6,200,581. The carrier vehicle is also a low-viscosity organic polysiloxane or volatile methylsiloxane or volatile ethylsiloxane or volatile methyl ethylsiloxane having a viscosity at 25°C in the range of 1 to 1,000 mm² / sec, for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane. It may be polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof.

[0250] In some embodiments, the composition comprises one or more additional components, such as a rheology modifier, a polar organic solvent, a thickener, an inorganic salt (e.g., calcium chloride), a personal care activator / component, a fragrance, or a combination thereof. Typically, one or more additional components are selected based on the desired use of the composition. For example, in some embodiments, the composition is formulated for use as a personal care composition and further comprises a personal care component. A specific personal care component, or a mixture of specific personal care components, may be selected based on the type of personal care composition, and the composition is formulated as is. In these embodiments, the personal care component may be a liquid, a solid, an encapsulated liquid, etc. Various examples of personal care components are described below. Any of these personal care components, or a combination of two or more different personal care components, may be used as a personal care component. For clarity and consistency, "personal care component" includes embodiments in which the composition comprises only one or more personal care components.

[0251] In certain embodiments, the personal care ingredient is an antiperspirant and / or deodorant (AP / DEO). In these embodiments, the composition may be referred to as an antiperspirant and / or deodorant (AP / DEO) composition. Examples of antiperspirants and deodorants include aluminum chloride, aluminum zirconium tetrachlorohydrex GLY, aluminum zirconium tetrachlorohydrex PEG, aluminum chlorohydrex, aluminum zirconium tetrachlorohydrex PG, aluminum chlorohydrex PEG, aluminum zirconium trichlorohydrate, aluminum chlorohydrex PG, aluminum zirconium trichlorohydrex GLY, hexachlorophene, benzalkonium chloride, aluminum sesquichlorohydrate, sodium bicarbonate, aluminum sesquichlorohydrex PEG, chlorophyllin copper complex, triclosan, aluminum zirconium octachlorohydrate, zinc ricinoleate, and mixtures thereof.

[0252] In a given embodiment, the personal care ingredient includes a skin care ingredient. When used to prepare a composition, the skin care ingredient is typically selected from water phase stabilizers, cosmetic biocides, conditioning agents (which may be silicone, cationic, hydrophobic, etc.), emollients, moisturizers, colorants, dyes, ultraviolet (UV) absorbers, sunscreens, antioxidants, fragrances, antimicrobial agents, antibacterial agents, antifungal agents, anti-aging active agents, anti-acne agents, skin lightening agents, pigments, preservatives, pH adjusters, electrolytes, chelating agents, plant extracts, sebum absorbents, sebum regulators, vitamins, waxes, surfactants, cleansing agents, emulsifiers, thickeners, propellant gases, skin protectants, film-forming polymers, light scattering agents, and combinations thereof. In some of these embodiments, the composition may be referred to as a skin care composition, cosmetic composition, sunscreen, shower gel, soap, hydrogel, cream, lotion, balm, foundation, lipstick, eyeliner, cuticle coat, blush, etc., based on the specific personal care ingredient used. Various chemical species of such skin care ingredients are described below, where similar chemical species and alternative chemical species are known to those skilled in the art.

[0253] Examples of softeners include volatile or non-volatile silicone oils; silicone resins, such as polypropylsilsesquioxane and phenyl trimethicone; silicone elastomers, such as dimethicone crosslinked polymers; alkylmethylsiloxanes, such as C 30-45 Alkyl methicones; volatile or non-volatile hydrocarbon compounds, e.g., squalene, paraffin oil, petroleum jelly oil, and naphthalene oil; hydrogenated or partially hydrogenated polyisobutene; isoeicosane; squalane; isoparaffin; isododecane; isodecane or isohexa-decane; branched C8-C 16Esters; isohexyl neopentanoate; ester oils, e.g., isononyl isononanoate, cetostearyl octanoate, isopropyl myristate, palmitate derivatives (e.g., dextrin palmitate), stearate derivatives, diisostearyl malate, isostearyl isostearate, and heptanoates, octanoates, decanoates, or ricinoleates of alcohols or polyalcohols, or mixtures thereof; hydrocarbon oils of plant origin, e.g., malt, sunflower, grapeseed, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, blackcurrant, evening primrose; or triglycerides of caprylic acid / capric acid; higher fatty acids, e.g., oleic acid, linoleic acid, or linolenic acid; and a mixture of these is included.

[0254] Examples of waxes include hydrocarbon waxes, e.g., beeswax, lanolin wax, rice wax, carnauba wax, candelilla wax, microcrystalline wax, paraffin, ozokerite, polyethylene wax, synthetic waxes, ceresin, lanolin, lanolin derivatives, cocoa butter, shellac wax, bran wax, capok wax, sugarcane wax, montan wax, whale wax, bayberry wax, silicone wax (e.g., polymethylsiloxane alkyl, alkoxy and / or ester, C 30-45 Alkyl dimethylsilyl polypropylsilsesquioxane), stearyl dimethicone, alkylmethylsiloxane containing long-chain alkyl groups within alkylmethylsiloxy units, and mixtures thereof are included.

[0255] Examples of moisturizers include low molecular weight aliphatic diols, such as propylene glycol and butylene glycol; polyols, such as glycerin and sorbitol; and polyoxyethylene polymers, such as polyethylene glycol 200; hyaluronic acid and derivatives thereof; and mixtures thereof.

[0256] Examples of thickeners include acrylamide copolymers, acrylate copolymers and their salts (e.g., sodium polyacrylate), xanthan gum and derivatives, cellulose gum and cellulose derivatives (e.g., methylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polypropylhydroxyethylcellulose), starch and starch derivatives (e.g., hydroxyethylamylose and starch amylase), polyoxyethylene, carbomer, alginate (e.g., sodium alginate), gum arabic, cassia gum, carob gum, scleroglucan gum, gellan gum, ramicane gum, karaya gum, carrageenan gum, guar gum and guar gum derivatives, cocamide derivatives (including cocamidopropyl betaine and cocamide MIPA), alkyl alcohols (e.g., cetearyl alcohol, stearyl alcohol, and other fatty alcohols). Gelatin, PEG derivatives, saccharides (e.g., fructose, glucose) and saccharide derivatives (e.g., PEG-120 methyl glucose dioleate) and mixtures thereof are included.

[0257] Examples of aqueous stabilizers include electrolytes (e.g., alkali metal salts and alkaline earth metal salts, particularly chlorides, borates, citrates, and sulfate salts of sodium, potassium, calcium, and magnesium, as well as aluminum chlorohydrate, and polyelectrolytes, particularly hyaluronic acid and sodium hyaluronate), polyols (glycerin, propylene glycol, butylene glycol, and sorbitol), alcohols, such as ethyl alcohol, and hydrocolloids, and mixtures thereof.

[0258] Examples of pH adjusters include any water-soluble acid, such as a carboxylic acid or an inorganic acid, such as hydrochloric acid, sulfuric acid, and phosphoric acid; monocarboxylic acids, such as acetic acid and lactic acid; and polycarboxylic acids, such as succinic acid, adipic acid, citric acid, and mixtures thereof.

[0259] Examples of preservatives and cosmetic biocides include paraben derivatives (e.g., methylparaben, propylparaben), hydantoin derivatives, chlorhexidine and its derivatives, imidazolidinyl urea, diazolidinyl urea, phenoxyethanol, silver derivatives, salicylate derivatives, triclosan, cyclopyroxolamine, hexamidine, oxyquinoline and its derivatives, PVP-iodine, zinc salts and derivatives, e.g., zinc pyrithione, methylchloroisothiazolinone, methylisothiazolinone, and mixtures thereof.

[0260] Examples of sebum absorbents or sebum regulators include silica silylate, silica dimethyl silylate, dimethicone / vinyl dimethicone crosslinked polymers, polymethyl methacrylate, crosslinked methyl methacrylate and aluminum starch octenylsuccinate, and mixtures thereof.

[0261] Examples of pigments and colorants include surface-treated or untreated iron oxide, surface-treated or untreated titanium dioxide, surface-treated or untreated mica, silver oxide, silicates, chromium oxide, carotenoids, carbon black, ultramarines, chlorophyllin derivatives, and yellow ochre. Examples of organic pigments include aromatic types including azos, indigoids, triphenylmethane, anthraquinones, and xanthine dyes (these are designated as D&C and FD&C blue, brown, green, orange, red, yellow, etc.), and mixtures thereof. Surface treatment agents include these treatment agents based on lecithin, silicones, silanes, fluoro compounds, and mixtures thereof.

[0262] Examples of silicone conditioning agents include silicone oils, e.g., dimethicone; silicone gums, e.g., dimethiconol; silicone resins, e.g., trimethylsiloxysilicate, polypropylsilsesquioxane; silicone elastomers; alkylmethylsiloxanes; organically modified silicone oils, e.g., amodimethicone, aminopropylphenyltrimethicone, phenyltrimethicone, trimethylpentaphenyltrisiloxane, silicone quaternium-16 / glycidoxydimethicone crosslinked polymer, silicone quaternium-16; saccharide-functional siloxanes; carbinol-functional siloxanes; silicone polyethers; siloxane copolymers (divinyldimethicone / dimethicone copolymers); acrylate or acrylic-functional siloxanes; and mixtures or emulsions thereof.

[0263] Examples of cationic conditioning agents include guar derivatives, e.g., hydroxypropyltrimethylammonium derivatives of guar gum; cationic cellulose derivatives, cationic starch derivatives; quaternary nitrogen derivatives of cellulose ethers; homopolymers of dimethyldiallylammonium chloride; copolymers of acrylamide and dimethyldiallylammonium chloride; homopolymers or copolymers derived from acrylic acid or methacrylic acid containing cationic nitrogen functional groups attached to the polymer by ester or amide bonds; polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with fatty alkyl dimethylammonium-substituted epoxides; polycondensation products of N,N'-bis-(2,3-epoxypropyl)-piperazine or piperazine-bis-acrylamide and piperazine; and copolymers of acrylic acid esters and vinylpyrrolidone having quaternary nitrogen functional groups. Specific materials include various polyquats, e.g., polyquaternium-7, polyquaternium-8, polyquaternium-10, polyquaternium-11, and polyquaternium-23. Other categories of conditioners include cationic surfactants, e.g., cetyl trimethylammonium chloride, cetyl trimethylammonium bromide, stearyl trimethylammonium chloride, and mixtures thereof. In some cases, cationic conditioning agents are also hydrophobically modified, e.g., hydrophobically modified quaternized hydroxyethylcellulose polymers; cationicly hydrophobically modified galactomannan ethers; and mixtures thereof.

[0264] Examples of hydrophobic conditioning agents include guar derivatives; galactomannan gum derivatives; cellulose derivatives; and mixtures thereof.

[0265] UV absorbers and sunscreens include those that absorb ultraviolet rays in the range of 290 to 320 nanometers (UV-B region) and those that absorb ultraviolet rays in the range of 320 to 400 nanometers (UV-A region).

[0266] Some examples of sunscreen agents are aminobenzoic acid, cinoxate, diethanolamine methoxycinnamate, digalloyl trioleate, dioxybenzone, ethyl 4-[bis(hydroxypropyl)]aminobenzoate, glyceryl aminobenzoate, homosalate, lawsone containing dihydroxyacetone, menthyl anthranilate, octocrylene, ethylhexyl methoxycinnamate (or octyl methoxycinnamate), octyl salicylate (or ethylhexyl salicylate), oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, red petroleum jelly, sulisobenzone, titanium dioxide, trolamine salicylate, and mixtures thereof.

[0267] Some examples of UV absorbers include acetaminosalol, allantoin, PABA, benzalphthalide, benzophenone, benzophenone 1-12,3-benzylidene camphor, benzylidene camphor hydrolyzed collagen sulfonamide, benzylidene camphor sulfonic acid, benzyl salicylate, bornellone, bumetriozole, butyl methoxydibenzoylmethane, butyl PABA, ceria / silica, ceria / silica talc, cinoxate, DEA-methoxycinnamate, dibenzoxazole naphthalene, di-t-butyl hydroxybenzylidene camphor, digalloyl trioleate, diisopropyl methyl cinnamate, dimethyl PABA ethyl cetearyldimonium tosylate, dioctyl butamidotriazone, diphenyl carbomethoxyacetoxynaphtopyran, disodium bisethylphenyl Thiaminotriazine stilbendisulfonate, disodium distyrylbiphenyl triaminotriazine stilbendisulfonate, disodium distyrylbiphenyl disulfonate, drometrizole, drometrizole trisiloxane, ethyl dihydroxypropyl PABA, ethyl diisopropylcinnamate, ethyl methoxycinnamate, ethyl PABA, ethyl urocanate, ethrocrylene ferulic acid, glyceryl octanoate dimethoxycinnamate, glyceryl PABA, glycol salicylate, homosalate, isoamyl p-methoxycinnamate, isopropylbenzyl salicylate, isopropyl dibenzolilmethane, isopropyl methoxycinnamate, octyl methoxycinnamate, menthyl anthranilate, menthyl salicylate, 4-methylbenzylidene, camphor, octocrylene, octrizol, octyl dimethyl PABA, Ethylhexyl methoxycinnamate, Octyl salicylate, Octyl triazone, PABA, PEG-25 PABA, Pentyl dimethyl PABA, Phenylbenzimidazole sulfonic acid, Polyacrylamidomethyl benzylidene camphor, Potassium methoxycinnamate, Potassium phenylbenzimidazole sulfonate, Red Vaseline, Sodium phenylbenzimidazole sulfonate, Sodium urocanate, TEA-phenylbenzimidazole sulfonate, TEA-salicylate, Terephthalylidene dicamphor sulfonic acid, Titanium dioxide, TriPABA panthenol, Urocanic acid,VA / crotonate / methacryloxybenzophenone-1 copolymer and mixtures thereof.

[0268] Examples of skin protectants include allantoin, aluminum acetate, aluminum hydroxide, aluminum sulfate, calamine, cocoa butter, cod liver oil, colloidal oatmeal, dimethicone, glycerin, kaolin, lanolin, mineral oil, petroleum jelly, shark liver oil, sodium bicarbonate, talc, witch hazel, zinc acetate, zinc carbonate, zinc oxide, and mixtures thereof.

[0269] Examples of dyes include 1-acetoxy-2-methylnaphthalene; acid dyes; 5-amino-4-chloro-o-cresol; 5-amino-2,6-dimethoxy-3-hydroxypyridine; 3-amino-2,6-dimethylphenol; 2-amino-5-ethylphenol HCl; 5-amino-4-fluoro-2-methylphenol sulfate; 2-amino-4-hydroxyethylaminoanisole; 2-amino-4-hydroxyethylaminoanisole sulfate; 2-amino-5-nitrophenol; 4-amino-2-nitrophenol; 4-amino-3-nitrophenol; 2-amino-4-nitrophenol sulfate; m-aminophenol HCl; p-aminophenol HCl; m-aminophenol; o-aminophenol; 4,6-bis(2-hydroxyethoxy)-m-phenylenediamine HCl; 2,6-Bis(2-hydroxyethoxy)-3,5-pyridinediamine HCl; 2-chloro-6-ethylamino-4-nitrophenol; 2-chloro-5-nitro-N-hydroxyethyl p-phenylenediamine; 2-chloro-p-phenylenediamine; 3,4-diaminobenzoic acid; 4,5-diamino-1-((4-chlorophenyl)methyl)-1H-pyrazole-sulfate; 2,3-diaminodihydropyrazolelopyrazolone dimethosulfonate; 2,6-diaminopyridine; 2,6-diamino-3-((pyridine-3-yl)azo)pyridine; dihydroxyindole; dihydroxyindolin; N,N-dimethyl-p-phenylenediamine; 2,6-dimethyl-p-phenylenediamine; N,N-Dimethyl-p-phenylenediamine sulfate; Direct dye; 4-Ethoxy-m-phenylenediamine sulfate; 3-Ethamino-p-Cresol sulfate; N-Ethyl-3-Nitro PABA; Gluconamidopropyl Aminopropyl Dimethicone; Haematoxylon brasiletto wood extract; HC dye; Lawsonia inermis (Henna) extract; Hydroxyethyl-3,4-Methylenedioxyaniline HCl; Hydroxyethyl-2-Nitro-p-Toluidine; Hydroxyethyl-p-phenylenediamine sulfate; 2-Hydroxyethyl Picramic Acid; Hydroxypyridinone; Hydroxysuccinimidyl C 21 -C 22Isoalkyl acidate; Isatin; Isatis tinctoria leaf powder; 2-methoxymethyl-p-phenylenediamine sulfate; 2-methoxy-p-phenylenediamine sulfate; 6-methoxy-2,3-pyridinediamine HCl; 4-methylbenzyl 4,5-diaminopyrazole sulfate; 2,2'-methylenebis-4-aminophenol; 2,2'-methylenebis-4-aminophenol HCl; 3,4-methylenedioxyaniline; 2-methylesorcinol; methylrosanillinium chloride; 1,5-naphthalenediol; 1,7-naphthalenediol; 3-nitro-p-cresol; 2-nitro-5-glyceryl methylaniline; 4-nitroguaiacol; 3-Nitro-p-hydroxyethylaminophenol; 2-Nitro-N-hydroxyethyl-p-anisidine; Nitrophenol; 4-Nitrophenylaminoethylurea; 4-Nitro-o-phenylenediamine dihydrochloride; 2-Nitro-p-phenylenediamine dihydrochloride; 4-Nitro-o-phenylenediamine HCl; 4-Nitro-m-phenylenediamine; 4-Nitro-o-phenylenediamine; 2-Nitro-p-phenylenediamine; 4-Nitro-m-phenylenediamine sulfate; 4-Nitro-o-phenylenediamine sulfate; 2-Nitro-p-phenylenediamine sulfate; 6-Nitro-2,5-pyridinediamine; 6-Nitro-o-toluidine; PEG-3 2,2'-di-p-phenylenediamine; p-phenylenediamine HCl; p-phenylenediamine sulfate; phenylmethylpyrazolone; N-phenyl-p-phenylenediamine HCl; pigment blue 15:1; pigment violet 23; pigment yellow 13; pyrocatechol; pyrogallol; resorcinol; sodium picramate; sodium sulfanilate; solvent yellow 85; solvent yellow 172; tetraaminopyrimidine sulfate; tetrabromophenol blue; 2,5,6-triamino-4-pyrimidinol sulfate; 1,2,4-trihydroxybenzene are included.

[0270] Examples of fragrances include fragrance ketones and fragrance aldehydes. Exemplary fragrance ketones are buccoxime; isojasmon; methyl beta-naphthyl ketone; musk indanone; tonalid / musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-Ionone, Beta-Ionone, Gamma-Methyl Ionone, Fleuramone, Dihydrojasmon, Cis-Jasmon, Iso-E-Super, Methyl-Cedrenyl-Ketone or Methyl-Cedrillon, Acetophenone, Methyl-Acetophenone, Para-Methoxy-Acetophenone, Methyl-Beta-Naphthyl-Ketone, Benzyl-Acetone, Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone, 6-isopropyldecahydro-2-naphtone, dimethyl-octenone, Freskomenthe, 4-(1-ethoxyvinyl)-3,3,5,5,-tetramethyl-cyclohexanone, methyl-heptenone, 2-(2-(4-methyl-3-cyclohexene-1-yl)propyl)-cyclopentanone, 1-(p-menten-6(2)-yl)-1-propanone, 4-(4-hydroxy-3-methoxyphenyl)-2-butanone, 2-acetyl-3,3-dimethyl-norbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 4-damascol, Dulcinyl, or Cassione, Gelsone, hexylone, isocyclemon E, methylcyclocitron, methyl-lavender-ketone, Orivon, para-tert-butyl-cyclohexanone, Verdone, Delphone, Muscone, neobutenone, Plicatone, Veloutone, 2,4,4,7-tetramethyl-oct-6-en-3-one and Tetrameran.Fragrances may be derived from or extracted from flowers, seeds, leaves, and / or roots of plants, seaweed, etc. Fragrances may be extracted from animals, for example, from secretory glands, and may be musk or sperm oil. Fragrances may also be artificially synthesized, for example, menthol, acetate, vanilla, etc.

[0271] In a specific embodiment, the fragrance ketone for the odor characteristic is selected from alpha damaskone, delta damaskone, iso damaskone, carbon, gamma-methyl-ionone, iso-E-super, 2,4,4,7-tetramethyl-oct-6-en-3-one, benzyl acetone, beta damaskone, damaskenone, methyl dihydrozasmonate, methyl cedrillone, and mixtures thereof.

[0272] In certain embodiments, for scent characteristics, the fragrance aldehyde is adoxal; anisate aldehyde; simal; ethyl vanillin; fluorohydral; heional; heliotropin; hydroxycitronellal; coavone; lauric acid aldehyde; linal; methyl nonyl acetaldehyde; PT. businal; phenyl acetaldehyde; undecylenate aldehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecene-1-al, alpha-n-amyl cinnamate aldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tert-butylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal, 2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexene-1-yl)butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadiene-1-al, 3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde, 4-isopropylbenzaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naftaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2-methyl-3-(isopropylphenyl)propanal, 1-decanal;Decylaldehyde, 2,6-dimethyl-5-heptenal, 4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal, octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamatealdehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyl octanal, undesenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4-(3)(4-methyl-3-pentenyl)-3-cyclohexene-carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tert-butyl)propanal, dihydrocinnamaldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or 6-methoxy 10-hexahydro-4,7-methanoindane-1 or 2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclohexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, p-tolylacetaldehyde;4-Methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexene-1-yl)-2-butenal, ortho-methoxycinnamate aldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, phenoxyaldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-methanoindane-1-carboxaldehyde, 2-methyl octanal, alpha-methyl-4-(1-methyl ethyl)benzene acetaldehyde, Selected from 6,6-dimethyl-2-norpinene-2-propionaldehyde, para-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naftaldehyde, 3-propyl-bicyclo[2.2.1]-hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal, trans-2-hexenal, 1-p-menten-q-carboxaldehyde, and mixtures thereof.;

[0273] Examples of antioxidants include acetyl cysteine, arbutin, ascorbic acid, ascorbic acid polypeptide, ascorbyl dipalmitate, ascorbyl methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, BHA, p-hydroxyanisole, BHT, t-butyl hydroquinone, caffeic acid, Camellia sinensis oil, chitosan ascorbate, chitosan glycolate, chitosan salicylate, chlorogenic acid, cysteine, cysteine ​​HCl, decyl mercaptomethylimidazole, erythorbic acid, diamyl hydroquinone, di-t-butyl hydroquinone, disecetyl thiodipropionate, dicyclopentadiene / t-butyl cresol copolymer, digalloyl trioleate, dilauryl thiodipropionate, and dimyristyl. Thiodipropionate, Dioleyl Tocopheryl Methylsilanol, Isoquercitrin, Diosmin, Disodium Ascorbyl Sulfate, Disodium Rutinyl Disulfate, Distearyl Thiodipropionate, Ditridecyl Thiodipropionate, Dodecyl Gallate, Ethyl Ferulate, Ferulic Acid, Hydroquinone, Hydroxylamine HCl, Hydroxylamine Sulfate, Iso-Octyl Thioglycolate, Kojic Acid, Madecassicoside, Magnesium Ascorbate, Magnesium Ascorbyl Phosphate, Melatonin, Methoxy-PEG-7 Rutinyl Succinate, Methylene Di-t-Butylcresol, Methylsilanol Ascorbate, Nordihydroguaiaretic Acid, Octyl Gallate, Phenylthioglycolic Acid, Phloroglucinol, Potassium Ascorbyl Tocopheryl Phosphate, Thiodiglycolamide, Potassium sulfite, Propyl gallate, Rosmarinic acid, Rutin, Sodium ascorbate, Sodium ascorbyl / cholesteryl phosphate, Sodium bisulfite, Sodium erythorbate, Sodium metabisulfide, Sodium sulfite, Sodium thioglycolate, Sorbityl furfural, Tea tree (Melareuca aptemifolia) oil, Tocopheryl acetate, Tetrahexyldecyl ascorbate, Tetrahydrodiferulloylmethane, Tocopheryl linoleate / oleate, Thiodiglycol, Tocopheryl succinate, Thiodiglycolic acid, Thioglycolic acid,Thiolactic acid, thiosalicylic acid, thiotaurine, retinol, tocopheres-5, tocopheres-10, tocopheres-12, tocopheres-18, tocopheres-50, tocopherol, tocopersolan, tocopheryl linoleate, tocopheryl nicotinate, tocoquinone, o-tolyl biguanide, tris(nonylphenyl) phosphite, ubiquinone, zinc dibutyl dithiocarbamate, and mixtures thereof.

[0274] Examples of propellant gases include carbon dioxide, nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane, or propane, and chlorinated or fluorinated hydrocarbons such as dichlorodifluoromethane and dichlorotetrafluoroethane or dimethyl ether; and mixtures thereof.

[0275] In certain embodiments, the composition is a sunscreen. In these embodiments, the personal care ingredient comprises a sunscreen agent. The sunscreen agent may be, for example, a sunscreen additive, an SPF booster, a light stabilizer, a film-forming polymer, etc. The sunscreen may also, or alternatively, be used in sunless tanning applications. Specific examples of sunscreen agents are mentioned above.

[0276] In other embodiments, the personal care ingredient includes a hair care ingredient. In these embodiments, the composition may be referred to as a hair care composition. When used to prepare the composition, the hair care ingredient is typically selected from conditioning agents (which may be silicones, cationic, hydrophobic, etc.), coloring agents, dyes, ultraviolet (UV) absorbers, preservatives, plant extracts, fatty alcohols, vitamins, fragrances, anti-dandruff agents, color protection additives, pearlizing agents, pH adjusters, electrolytes, chelating agents, styling agents, ceramides, amino acid derivatives, suspending agents, surfactants, cleansing agents, emulsifiers, thickeners, oxidizing agents, reducing agents, film-forming polymers, and combinations thereof. For some of these hair care embodiments, the composition may be referred to as a shampoo, rinse-off conditioner, leave-in conditioner, gel, pomade, serum, spray, color product, or mascara. Many examples of these hair care ingredients are mentioned above as suitable personal care ingredients.

[0277] Examples of oxidizing agents are ammonium persulfate, calcium peroxide, hydrogen peroxide, magnesium peroxide, melamine peroxide, potassium bromate, potassium caroate, potassium chlorate, potassium persulfate, sodium bromate, sodium carbonate peroxide, sodium chlorate, sodium iodate, sodium perborate, sodium persulfate, strontium dioxide, strontium peroxide, urea peroxide, zinc peroxide, and mixtures thereof.

[0278] Examples of reducing agents include ammonium bisulfite, ammonium sulfite, ammonium thioglycolate, ammonium thiolactate, cysteamine HCl, cysteine, cysteine ​​HCl, ethanolamine thioglycolate, glutathione, glyceryl thioglycolate, glyceryl thiopropionate, hydroquinone, p-hydroxyanisole, isooctyl thioglycolate, magnesium thioglycolate, mercaptopropionic acid, potassium metabisulfite, potassium sulfite, potassium thioglycolate, sodium bisulfite, sodium hydrosulfite, sodium hydroxymethanesulfonate, sodium metabisulfite, sodium sulfite, sodium thioglycolate, strontium thioglycolate, superoxide dismutase, thioglycerin, thioglycolic acid, thiolactic acid, thiosalicylic acid, zinc formaldehyde sulfoxylate, and their It is a mixture.

[0279] Examples of anti-dandruff agents include pyridinethion salts, selenium compounds such as selenium disulfide, and soluble anti-dandruff agents and mixtures thereof.

[0280] In other embodiments, the personal care ingredient includes a nail care ingredient. In these embodiments, the composition may be referred to as a nail care composition. When used to prepare the composition, the nail care ingredient may be any ingredient used in the nail care composition, e.g., nail polish, nail gel, nail tip, acrylic finish, etc. Examples of such nail care ingredients include pigments, resins, solvents, volatile halogenated compounds (e.g., methoxynonafluorobutane and / or ethoxynonafluorobutane), etc.

[0281] More specifically, examples of nail care ingredients include butyl acetate; ethyl acetate; nitrocellulose; acetyl tributyl citrate; isopropyl alcohol; adipic acid / neopentyl glycol / trimelitic anhydride copolymer; stearalkonium bentonite; acrylate copolymer; calcium pantothenate; Cetraria islandica extract; Chondrus crispus; styrene / acrylate copolymer; trimethylpentanediyl dibenzoate-1; polyvinyl butyral; N-butyl alcohol; propylene glycol; butylene glycol; mica; silica; tin oxide; calcium borosilicate; synthetic fluorophlogopite; polyethylene terephthalate; sorbitan laurate derivative; talc; jojoba extract; diamond powder; isobutylphenoxy epoxy resin; silk powder; and a mixture of these is included.

[0282] In other embodiments, the personal care ingredient includes a dental care ingredient. In these embodiments, the composition may be referred to as a dental care composition. One specific example of such a dental care composition is toothpaste. Another example of a dental care composition is a teeth whitening composition. The dental care ingredient may be any dental care ingredient suitable for a dental care composition, such as an abrasive compound (e.g., aluminum hydroxide, calcium carbonate, silica, zeolite), a fluoride compound, a surfactant, a flavoring agent, a remineralizer, an antibacterial agent, etc.

[0283] In a given embodiment, the personal care ingredient comprises a film-forming polymer, which may be used as a personal care ingredient regardless of whether the composition is used for skin care, hair care, etc. As used herein, "film-forming polymer" means a polymer or oligomer capable of forming a film on a substrate, either by itself or optionally in the presence of a film-forming agent. The film-forming polymer may form a film upon the application of curing conditions, e.g., upon the application of heat, upon exposure to atmospheric conditions, etc. Alternatively, the film-forming polymer may form a film upon the evaporation of any carrier vehicle on which the film-forming polymer may optionally be disposed. The film-forming polymer may undergo a reaction, for example, the film-forming polymer may be crosslinked upon film formation or otherwise may include additional bonding. However, the film-forming polymer may form a film in the absence of such a reaction. The film-forming polymer may be a gelling agent. Film-forming polymers are particularly advantageous when the composition is a sunscreen, but personal care ingredients may likewise include film-forming polymers in other compositions.

[0284] The substrate on which the film is formed may be any substrate, but the substrate is generally a part of a mammal, particularly a human, as described in more detail below in relation to the processing method. Specific examples of suitable substrates include skin, hair, and nails.

[0285] Generally, the film is continuous, but the film may have a varying thickness. Continuity means that the film does not form any openings. The film may be referred to as being macroscopically continuous. The film may be supported by a substrate or bonded to the substrate, for example, physically and / or chemically. In a given embodiment, the film may be optionally removable from the substrate, for example, the film may be peelable from the substrate. The film may remain intact as a free-standing film when separated from the substrate, or may be separated by the application of shearing, which may impair or destroy the continuity of the film.

[0286] Specific examples of suitable film-forming polymers include acrylic polymers, silicone resins (e.g., polypropylsilsesquioxane), polyurethanes, polyurethane-acrylics, polyesters, polyester-polyurethanes, polyether-polyurethanes, polyesteramides, alkyds, polyamides, polyureas, polyureas-polyurethanes, cellulose-based polymers (e.g., nitrocellulose), silicones, acrylic-silicones, polyacrylamides, fluoropolymers, polyisoprenes, and any copolymers or terpolymers comprising these or any one thereof. As used herein in relation to suitable film-forming polymers, the term “silicone” includes linear, branched, and resinous silicones, although resinous silicones are generally referred to as silicone resins rather than polymers. Silicones may be modified, for example, silicones may be silicone-grafted acrylic polymers.

[0287] As described above, the film-forming polymer may be disposed in a carrier vehicle, and the carrier vehicle may partially or completely solubilize the film-forming polymer. Depending on the choice of the film-forming polymer, the carrier vehicle may be, for example, an oil, e.g., an organic oil and / or silicone oil, a solvent, water, etc. The film-forming polymer may be in the form of polymer particles, which are optionally surface-stabilized with at least one stabilizer, and the polymer particles may exist as a dispersion or an emulsion.

[0288] The film-forming polymer may be a block polymer, which may be styrene-free. Typically, the block polymer comprises at least one first block and at least one second block, which may be connected together through an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. Generally, the glass transition temperatures of the first and second blocks are different from each other.

[0289] Monomers that can be used to manufacture block polymers include, for example, methyl methacrylate, isobutyl (meth)acrylate and isobornyl (meth)acrylate, methyl acrylate, isobutyl acrylate, n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate, isodecylacrylamide 2-ethylhexyl acrylate and mixtures thereof.

[0290] In certain embodiments, the film-forming polymer may be obtained or produced through free radical polymerization. For example, the film-forming polymer may be produced through the free radical polymerization of at least one silicon- or hydrocarbon-based macromonomer containing a polymerizable terminal group and at least one acrylic monomer.

[0291] Specific examples of hydrocarbon-based macromonomers include linear or branched C8-C 22Homopolymers and copolymers of alkyl acrylates or methacrylates are included. The polymerizable end groups may be vinyl groups or (meth)acrylate groups, for example, poly(2-ethylhexyl acrylate) macromonomers; poly(dodecyl acrylate) or poly(dodecyl methacrylate) macromonomers; poly(stearyl acrylate) or poly(stearyl methacrylate) macromonomers, etc. Such macromonomers generally contain one (meth)acrylate group as a polymerizable end group.

[0292] Additional examples of hydrocarbon-based macromonomers include polyolefins containing ethylene-based unsaturated terminal groups (as polymerizable terminal groups), e.g., (meth)acrylate terminal groups. Specific examples of such polyolefins include polyethylene macromonomers, polypropylene macromonomers, polyethylene / polypropylene copolymer macromonomers, polyethylene / polybutylene copolymer macromonomers, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; and poly(ethylene / butylene)-polyisoprene macromonomers.

[0293] Examples of silicon-based macromonomers include organopolysiloxanes containing polymerizable end groups, e.g., (meth)acrylate end groups. Organopolysiloxanes can be linear, branched, partially branched, or dendritic. In various embodiments, the organopolysiloxane is linear. In these embodiments, the organopolysiloxane may be polydimethylsiloxane, but hydrocarbon groups other than methyl groups may be present therein with or instead of methyl groups. Typically, the polymerizable end group is located at the end, but the polymerizable end group may optionally be located at the pendant. A specific example of a silicon-based macromonomer is monomethacryloxypropyl polydimethylsiloxane.

[0294] In a given embodiment, the film-forming polymer is an organic film-forming polymer that is soluble in oil as a carrier vehicle. In these embodiments, the film-forming polymer may be referred to as an oil-soluble polymer. The oil-soluble polymer may have any type, and specific examples thereof include olefins, cycloolefins, butadiene, isoprene, styrene, vinyl ethers, vinyl esters, vinyl amides, (meth)acrylic acid esters or amides, etc., or are formed therefrom.

[0295] In one embodiment, the lipid-soluble polymer is formed from a monomer selected from the group consisting of isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and combinations thereof.

[0296] Alternatively, the lipid-soluble polymer may be an acrylic-silicone grafted polymer, which typically comprises a silicone backbone and an acrylic graft, or alternatively, an acrylic backbone and a silicone graft.

[0297] Film-forming polymers can be halogenated, for example, film-forming polymers may contain fluorine atoms.

[0298] Alternatively, as described above, the film-forming polymer may be a cellulose-based polymer, such as nitrocellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, or ethylcellulose. Also, alternatively, the film-forming polymer may comprise a polyurethane, an acrylic polymer, a vinyl polymer, polyvinyl butyral, an alkyd resin, or a resin derived from an aldehyde condensation product, such as an arylsulfonamide-formaldehyde resin.

[0299] Additionally, as described above, the film-forming polymer may comprise silicon, which may be linear, branched, or dendritic. Dendritic silicon comprises at least one T and / or Q unit as generally understood in the art. Examples of dendritic silicon include silsesquioxane. The silicon may comprise any combination of M, D, T, and Q units, insofar as the silicon constitutes the film-forming polymer.

[0300] If the film-forming polymer comprises silicone, the film-forming polymer may comprise an amphiphilic silicone. The amphiphilic silicone typically comprises a silicone portion compatible with the silicone medium and a hydrophilic portion. The hydrophilic portion may be a residue of a compound selected from, for example, alcohols and polyols having 1 to 12 hydroxyl groups, and polyoxyalkylenes (e.g., those containing oxypropylene units and / or oxyethylene units).

[0301] Amphiphilic silicones may be oils that have or do not have gelling activity. Oils of this type may include, for example, dimethicone copolyols, bis-hydroxyethoxypropyl dimethicone, etc.

[0302] In one embodiment, the film-forming polymer comprises a silicone organic elastomer gel. The silicone organic elastomer gel comprises linear organopolysiloxane chains crosslinked via polyoxyalkylenes. The silicone organic elastomer gel may further comprise hydrophilic polyether functional groups suspended from the linear organopolysiloxane chains. Specific examples of suitable silicone organic elastomer gels are disclosed in international patent application PCT / US2010 / 020110.

[0303] In various embodiments, personal care ingredients may include or be referred to as personal care activators, healthcare activators, or combinations thereof (collectively, “activators” or “activators”). As used herein, “personal care activator” means any compound or mixture of compounds known in the art as an additive in personal care formulations, typically to provide cosmetic and / or aesthetic effects. “Healthcare activator” means any compound or mixture of compounds known in the art to provide pharmaceutical or medical effects. Accordingly, “healthcare activator” includes materials generally used and considered as active ingredients or active drug ingredients as defined in the literature [United States Department of Health & Human Services Food and Drug Administration, contained in Title 21, Chapter I, of the Code of Federal Regulations, Parts 200-299 and Parts 300-499]. Specific personal care activators and healthcare activators are described below. These personal care active agents and healthcare active agents may constitute personal care ingredients regardless of whether the personal care ingredients are used to form, for example, AP / DEO compositions, skin care compositions, hair care compositions, nail care compositions, and / or dental care compositions. For example, in various embodiments, the same personal care ingredient may be used to form either a hair care composition or a skin care composition. As is understood in the art, at least some of the personal care active agents described below are chemical species of the specific personal care ingredients introduced above in relation to the skin care composition, hair care composition, nail care composition, and dental care composition, respectively.For example, a number of chemical species of plants or plant extracts are listed below, and these are exemplary examples of the plant extracts listed above as suitable personal care ingredients. The active ingredients or active agents listed below may constitute the personal care ingredients of the composition or may be used in the form of combinations with them.

[0304] Active ingredients useful for use in the composition include vitamins and vitamin derivatives—including "pro-vitamins." Vitamins useful in the present invention include vitamin A1, retinol, and C2-C of retinol. 18 Retinol includes, but is not limited to, esters, vitamin E, tocopherol, esters of vitamin E, and mixtures thereof. Retinol includes trans-retinol, 1,3-cis-retinol, 11-cis-retinol, 9-cis-retinol, and 3,4-didehydro-retinol, vitamin C and its derivatives, vitamin B1, vitamin B2, provitamin B5, panthenol, vitamin B6, vitamin B12, niacin, folic acid, biotin, and pantothenic acid. Other suitable vitamin and INCI names for the vitamin considered to be included in the present invention are ascorbyl dipalmitate, ascorbyl methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate, ascorbyl glucoside, sodium ascorbyl phosphate, sodium ascorbate, disodium ascorbyl sulfate, and potassium (ascorbyl / tocopheryl) phosphate. Generally, retinol, all trans retinoic acid and derivatives, their isomers and analogs are collectively referred to as "retinoids".

[0305] It should be noted that retinol is the International Nomenclature Cosmetic Ingredient Name (INCI) for Vitamin A, as defined by the Cosmetic, Toiletry, and Fragrance Association (CTFA) in Washington, D.C. The INCI names for other suitable vitamins and vitamins considered to be included in this specification are retinyl acetate, retinyl palmitate, retinyl propionate, α-tocopherol, tocopherol, tocopheryl acetate, tocopheryl linoleate, tocopheryl nicotinate, and tocopheryl succinate.

[0306] Some examples of commercially available products suitable for use in the present invention are vitamin A acetate and vitamin C (both of which are products of Fluka Chemie AG, Buchs, Switzerland); COVI-OX T-50, a vitamin E product of Henkel Corporation, La Grange, Illinois, USA; COVI-OX T-70, another vitamin E product of Henkel Corporation, La Grange, Illinois, USA; and vitamin E acetate, a product of Roche Vitamins & Fine Chemicals, Nutley, New Jersey, USA.

[0307] The active agent may be a protein, e.g., an enzyme. Enzymes include, but are not limited to, commercially available types, improved types, recombinant types, wild types, variants not found in nature, and mixtures thereof. For example, suitable enzymes include hydrolases, cutinases, oxidases, transferases, reductases, hemicellulases, esterases, isomerases, pectinases, lactases, peroxidases, laccases, catalases, and mixtures thereof. Hydrolases include, but are not limited to, proteases (bacterial, fungal, acidic, neutral, or alkaline), amylases (alpha or beta), lipases, mannanases, cellulases, collagenases, lysozyme, superoxide dismutase, catalases, and mixtures thereof. Proteases include trypsin, chymotrypsin, pepsin, pancreatin, and other mammalian enzymes; Papain, bromelain, and other plant enzymes; subtilisin, epidermin, nisin, naringinase (L-rhamnosidase), urokinase, and other bacterial enzymes are included, but not limited thereto. Lipases include, but are not limited to, triacyl-glycerol lipase, monoacyl-glycerol lipase, lipoprotein lipases, e.g., stearpsin, erepsin, pepsin, other mammalian, plant, and bacterial lipases, and purified ones. In specific embodiments, natural papain is used as an enzyme. Additionally, a stimulating hormone, e.g., insulin, may be used together with the enzyme(s) to enhance efficacy.

[0308] The active ingredient may also be one or more plants or plant extracts. Examples of these ingredients are as follows: Ashitaba extract, avocado extract, hydrangea extract, Althea extract, Arnica extract, aloe extract, apricot extract, apricot kernel extract, Ginkgo biloba extract, fennel extract, turmeric [Curcuma] extract, oolong tea extract, rose fruit extract, Echinacea extract, Scutellaria root extract, Phellodendro bark extract, Japanese Coptis extract, barley extract, Hypericum extract, White Nettle extract, Watercress extract, orange extract, dehydrated brine, seaweed extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, chamomile extract, carrot extract, Artemisia extract, licorice Extract, Hibiscus tea extract, Pyracantha Fortuneana fruit extract, Kiwi extract, Cinchona extract, Cucumber extract, Guanosine, Gardenia extract, Sasa Albo-marginata extract, Sophora root extract, Walnut extract, Grapefruit extract, Clematis extract, Chlorella extract, Mulberry extract, Gentiana extract, Black tea extract, Yeast extract, Burdock extract, Fermented rice bran extract, Rice germ oil, Compri extract, Collagen, Cowberry extract, Gardenia extract, Asiasarum root extract, Family of Bupleurum extract, Salvia extract, Saponaria extract, Bamboo extract, Crataegus fruit extract, Zanthoxylum fruit extract, Shiitake mushroom extract,Rehmannia root extract, Gromwell extract, Perilla extract, Linden extract, Filipendula extract, Peony extract, Acorus calamus root extract, White birch extract, Equisetum extract, Hedera helix extract, Crataegus extract, Sambucus nigra extract, Achillea millefolium extract, Peppermint extract, Sage extract, Malva extract, Cnidium officinale root extract, Japanese green gentian extract, Soybean extract, Jujube extract, Thyme extract, Tea extract, Clove extract, Gramineae imperata cyrilosa Imperata cyrillo extract, tangerine peel extract, Japanese Angelica root extract, calendula extract, peach seed extract, bitter orange peel extract, Houttuynia cordata extract, tomato extract, natto extract, ginseng extract, green tea extract (Camelliea sinesis), garlic extract, wild rose extract, hibiscus extract, Ophiopogon tuber extract, lotus (Nelumbo nucifera) extract, parsley extract, honey, hamamelis extract, Parietaria extract, Isodonis herba extract, bisabolol extract, loquat extract, Tussilago farfara extract, butterbur extract, Poria cocos wolf extract, Butcher's broom extract, grape extract, beeswax extract, loofah extract, safflower extract, peppermint extract,Linden tree extract, peony extract, hop extract, pine extract, horse chestnut extract, Mizu-bashou (Lysichiton camtschatcese extract, Mukurossi bark extract, Melissa extract, peach extract, cornflower extract, eucalyptus extract, saxifrage extract, citron extract, coix extract, mugwort extract, lavender extract, apple extract, lettuce extract, lemon extract, Chinese milk vetch extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract, and combinations thereof.

[0309] Representative, non-limiting examples of healthcare active agents useful as drugs in the present composition are described below. One or more of the drugs may be used alone or in combination with the aforementioned active agents and / or personal care ingredients.

[0310] The composition may include an antiparasitic agent. The antiparasitic agent may be of any type. Examples of antiparasitic agents include, but are not limited to, hexachlorobenzene, carbamate, naturally occurring pyrethroid, permethrin, allethrin, malathion, piperonyl butoxide, and combinations thereof.

[0311] The composition may include an antimicrobial agent, also referred to as a disinfectant. The antimicrobial agent may be of any type. Examples of antimicrobial agents include, but are not limited to, phenols including cresol and resorcinol. Such a composition may be used to treat skin infections. A very common example of a skin infection is acne, which involves the intrusion of the sebaceous glands by Staphylococcus aureus or Pseudomonas as well as p. acnes. Examples of useful anti-acne active agents include keratolytic agents, such as salicylic acid (o-hydroxybenzoic acid), derivatives of salicylic acid, such as 5-octanoyl salicylic acid, and resorcinol; retinoids, such as retinoic acid and derivatives thereof (e.g., cis and trans); Sulfur-containing D and L amino acids and their derivatives and salts, in particular their N-acetyl derivatives, e.g., N-acetyl-L-cysteine; lipoic acid; antibiotics and antimicrobial agents, e.g., benzoyl peroxide, octopirox, tetracycline, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,4'-trichlorovanillide, azelaic acid and its derivatives, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, ethyl acetate, clindamycin and methloscycline; sevostates, e.g., flavonoids; and bile salts, e.g., schemnol sulfates and their derivatives, deoxycholates and cholates; parachlorometaxylenol; and combinations thereof are included.

[0312] Phenols at concentrations of 0.2, 1.0, and 1.3 wt% are generally bacteriostatic agents, bactericidal agents, and fungicidal agents, respectively. Some phenol derivatives are more potent than phenol itself, the most important of which are halogenated phenols and bis-phenols, alkyl-substituted phenols, and resorcinols. Hydrophobic antibacterial agents include triclosan, triclocarbons, eucalyptol, menthol, methyl salicylates, thymol, and combinations thereof.

[0313] The composition may include an antifungal agent. The antifungal agent may have any type. Examples of antifungal agents include, but are not limited to, azoles, diazoles, triazoles, miconazole, fluconazole, ketoconazole, clotrimazole, itraconazole, griseofulvin, ciclopirox, amorolfine, terbinafine, amphotericin B, potassium iodide, flucytosine (5FC), and combinations thereof. U.S. Patent No. 4,352,808 discloses a 3-aralkyloxy-2,3-dihydro-2-(1H-imidazolylmethyl)benzo[b]thiophene compound having antifungal and antibacterial activity, which is incorporated herein by reference.

[0314] The composition may include a steroidal anti-inflammatory agent. The steroidal anti-inflammatory agent may be of any type. Examples of steroidal anti-inflammatory drugs include corticosteroids, such as hydrocortisone, hydroxyltriamcinolone, alpha-methyl dexamethasone, dexamethasone phosphate, beclomethasone dipropionate, clobetazole valerate, desonide, desoximethasone, desoxicorticosterone acetate, dexamethasone, dichlorison, diflorasone diacetate, diflucortolone valerate, fluadrenolone, fluclarolone acetonide, fludrocortisone, flumethasone pivalate, fluocinolone acetonide, fluocinonide, flucortin butyl ester, flucortolone, flupredniden (fluprednylidene) acetate, flulandrenolone, halcinonide, hydrocortisone acetate, Hydrocortisone butyrate, methylprednisolone, triamcinolone acetonide, cortisone, cortodoxone, flucetonide, fludrocortisone, difluorosone diacetate, fluradrenalone acetonide, medrisone, amk, amsinafid, balance of betamethasone and its esters, chlorprednisone, chlorprednisone acetate, clocortellone, clescinolone, dichlorison, difluprednate, fluchloronide, flunisolide, fluoromethalone, fluferolone, fluprednisolone, hydrocortisone valerate, hydrocortisone cyclopentylpropionate, hydrocortamate, meprednisone, paramethasone, prednisolone, prednisone, beclomethasone dipropionate, betamethasone Dipropionate, triamcinolone, and combinations thereof are included, but not limited to.

[0315] Currently available topical antihistamine preparations include 1% and 2% diphenhydramine (Benadryl (registered trademark) and Caladryl (registered trademark)), 5% doxepin (Zonalon (registered trademark)) cream, prilamine maleate, chlorpheniramine and tripelennamin, phenothiazine, promethazine hydrochloride (Phenergan (registered trademark)), and dimethindene maleate. In addition to these drugs, additional antihistamines may also be included in the composition. Additionally, so-called "natural" anti-inflammatory agents may be useful. For example, candelilla wax, alpha bisvabolol, aloe vera, Manjistha (extracted from plants of the genus Rubia, particularly Rubia cordifolia), and Guggal (extracted from plants of the genus Commiphora, particularly Commiphora mukul) may be used as active agents in the composition.

[0316] The composition may include a non-steroidal anti-inflammatory drug (NSAID). The NSAID may have any type. Examples of NSAIDs include, but are not limited to, the following NSAID categories: propionic acid-acid derivatives; acetic acid derivatives; fenamic acid derivatives; biphenylcarboxylic acid derivatives; and oxycam. Such NSAIDs are described in U.S. Patent No. 4,985,459, which is incorporated herein by reference. Additional examples include, but are not limited to, acetylsalicylic acid, ibuprofen, naproxen, benoxaprofen, flurbiprofen, fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxaprozine, pranoprofen, emniroprofen, thioxaprofen, surprofen, alminoprofen, tiaprofenic acid, fluprofen, bucloxic acid, and combinations thereof.

[0317] The composition may include an antioxidant / radical scavenger. The antioxidant may be of any type. Examples of antioxidants include, but are not limited to, ascorbic acid (vitamin C) and its salts, tocopherol (vitamin E) and its derivatives, e.g., tocopherol sorbate, other esters of tocopherol, butylated hydroxybenzoic acid and its salts, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (available under the trade name Trolox®), gallic acid and its alkyl esters, in particular propyl gallate, uric acid and its salts and alkyl esters, sorbic acid and its salts, ascorbyl esters of fatty acids, amines (e.g., N,N-diethylhydroxylamine, amino-guanidine), sulfhydryl compounds (e.g., glutathione), and dihydroxy fumaric acid and its salts, as well as EDTA, BHT, etc. and combinations thereof.

[0318] The composition may include antibiotics. Antibiotics may have any type. Examples of antibiotics include, but are not limited to, chloramphenicol, tetracycline, synthetic and semi-synthetic penicillins, beta-lactams, quinolones, fluoroquinolones, macrolide antibiotics, peptide antibiotics, cyclosporine, erythromycin, clindamycin, and combinations thereof.

[0319] The composition may include a local anesthetic. The local anesthetic may be of any type. Examples of local anesthetics include, but are not limited to, benzocaine, lidocaine, bupivacaine, chlorprocaine, daibucaine, etidocaine, mepivacaine, tetracaine, diclonin, hexylcaine, procaine, cocaine, ketamine, pramoxine, phenol, pharmaceutically acceptable salts thereof, and combinations thereof.

[0320] The composition may include an antiviral agent. The antiviral agent may be of any type. Examples of antiviral agents include, but are not limited to, proteins, polypeptides, peptides, fusion proteins, antibodies, nucleic acid molecules, organic molecules, inorganic molecules, and small molecules that inhibit or reduce the attachment of the virus to its receptor, the internalization of the virus into a cell, the replication of the virus, or the release of the virus from a cell. In particular, antiviral agents include, but are not limited to, nucleoside analogs (e.g., zidovudine, acyclovir, acyclovir prodrugs, famciclovir, ganciclovir, vidarabine, idoxulidine, trifluridine, and ribavirin), n-docosanol foscarnet, amantadine, rimantadine, saquinavir, indinavir, ritonavir, idoxulidine, alpha-interferon and other interferons, AZT, and combinations thereof.

[0321] Additional examples of active agents include analgesics and antihypertensive agents. Analgesics are known in the art and are colloquially referred to as painkillers. Analgesics may be selected from any known analgesics, specific examples of which include paracetamol (acetaminophen), morphine, codeine, heroin, methadone, devine, orphiarine, buprenorphine, morphinan, benzomorphan, acetaminophen, butorphanol, diflunisal, fenoprofen, fentanyl, fentanyl citrate, hydrocodone, aspirin, sodium salicylate, ibuprofen, oxymorphone, pentaxicin, naproxen, nalbuphine, mefenamic acid, meperidine, and dihydroergotamine, non-steroidal anti-inflammatory drugs, such as salicylates, and opioids, such as morphine and oxycodone. Antihypertensive agents are known in the art to treat or lower hypertension, that is, high blood pressure. Antihypertensive agents may be selected from any known antihypertensive agents, specific examples of which include diuretics, adrenergic receptor antagonists (e.g., beta-blockers), benzodiazepines, calcium channel blockers, renin inhibitors, etc.

[0322] A typical opioid antagonist is Haloxone. Exemplary antitussives include, without limitation, diphenhydramine, guaifenesin, hydromorphone, ephedrine, phenylpropanolamine, theophylline, codeine, noscapine, levofoxyphen, carbetapentane, chlorphendianol, and benzonatate.

[0323] Among the sedatives available for use are, without limitation, chloral hydrate, butabarbital, alprazolam, amobarbital, chlordiazepoxide, diazepam, mephobarbital, secobarbital, diphenhydramine, etinamate, flurazepam, halasepam, haloperidol, prochlorperazine, oxazepam, and talbutal.

[0324] Examples of cardiac drugs include, without limitation, quinidine, propranolol, nifedipine, procaine, dobutamine, digitoxin, phenyloine, sodium nitroprusside, nitroglycerin, verapamil HCl, digoxin, nicardipine HCl, and isosorbide dainitrate.

[0325] Antiemetics are exemplified, without limitation, by thiethylperazine, metoclopramide, cyclizine, meclizine, prochlorperazine, doxylamine succinate, promethazine, triflupromazine, and hydroxyzine.

[0326] A typical dopamine receptor agonist is bromocriptine mesylate. Exemplary amino acid, peptide, and protein hormones include, without limitation, thyroxine, growth hormone (GH), interstitial cell-stimulating hormone (ICSH), follicle-stimulating hormone (FSH), thyroid hormone (TSH), adrenocorticotropic hormone (ACTH), gonadotropin-releasing hormone (GnRH), e.g. leuprolide acetate, vasopressin, and their active degradation products. Some products have sufficiently high molecular weights that absorption through the stratum corneum or mucous membranes may be difficult. Therefore, the present invention is applicable only to hormones having a molecular weight and stereochemical structure that allow passage through the skin.

[0327] Female sex hormones that may be used include, without limitation, estradiol, diethylstilbestrol, conjugated estrogen, estrone, norethindrone, medroxyprogesterone, progesterone, and norgestrel. Typical male sex hormones that may be used may be, without limitation, testosterone, methyltestosterone, and fluoxymesterone.

[0328] As described above, the emulsion may contain various additives (e.g., those added during the preparation of the emulsion) so that the emulsion itself functions as a final-use composition. However, the emulsion may also be combined with various additional ingredients as described above (e.g., after its preparation) and thus can be formulated into various final-use compositions, such as personal care compositions. Such compositions may be in any form, such as a cream, gel, powder, paste, or free-flowing liquid. Compositions comprising or formed therefrom the emulsion of the present invention may exhibit improved application and cosmetic properties (including reduced tackiness and stickiness), and improved transparency / low residue properties.

[0329] In some embodiments, the emulsion itself may be a personal care composition or may be formulated as a personal care composition. In such embodiments, the personal care composition may be formulated to be cosmetic, therapeutic, functional, or some combination thereof for a part of the body to which the personal care composition is applied. Examples of personal care compositions include antiperspirants and deodorants, skin care creams, skin care lotions, moisturizers, facial treatments (e.g., acne or wrinkle removers), personal cleansers and facial cleansers, bath oils, fragrances, colognes, sachets, sunscreens, pre- and post-shaving lotions, shaving soaps and shaving lathers, shampoos, conditioners, hair dyes, hair relaxants, hairsprays, mousses, hair gels, permanent products, depilatory products, cuticle coats, makeup, color cosmetics, foundations, concealers, blushes, lipsticks, eyeliners, mascaras, oil removers, color makeup removers, and medicinal creams, pastes, or sprays (e.g., This includes anti-acne agents, dental hygiene products, antibiotics, healing promoters, etc. Generally, personal care compositions comprising emulsions are formulated with a carrier that enables application in conventional forms, such as liquids, rinses, lotions, creams, pastes, gels, foams, mousses, ointments, sprays, aerosols, soaps, sticks, soft solids, or solid gels, for example, depending on the intended use. It is self-evident to those skilled in the art to constitute a carrier suitable for formulating a personal care composition and may be selected from these carriers exemplified herein.

[0330] Personal care compositions may be in any form of liquid or non-liquid (semi-solid, soft solid, solid, etc.). For example, personal care compositions may be pastes, solids, gels, or creams. Additionally, regardless of how the emulsion is prepared, personal care compositions formed from the emulsion may be solids, rigid or flexible gels comprising emulsions such as oil-in-water or water-in-oil emulsions, multiple emulsions such as oil-in-water-in-oil emulsions or water-in-oil-in-water emulsions, or anhydrous gels. Personal care compositions may also be in a form selected from translucent anhydrous gels and clear anhydrous gels. Personal care compositions may comprise, for example, an external or continuous fatty phase. Personal care compositions may be anhydrous. In some cases, personal care compositions may be molded compositions or cast as sticks or dishes. In certain embodiments, a personal care composition comprising an emulsion is a molded infusion stick. In such an embodiment, the personal care composition (e.g., in stick form) can act as a deformable flexible elastic solid having increased elastic softness upon application.

[0331] A personal care composition comprising an emulsion may be used by application to the human body (e.g., skin or hair) by any method, such as by hand or using an applicator (e.g., a brush or a spray). In some embodiments, the personal care composition may be intended to be removed after such application by, for example, washing, wiping, and peeling, or a combination thereof.

[0332] As mentioned above, specific embodiments of copolymers in general, and specifically acrylic copolymers, have excellent utility when used or applied as cosmetic ingredients or film-forming agents, including quasi-drug formulations or topical formulations. Although not limited to these specific end-use applications, the copolymers of the present invention may be used instead of or in combination with any conventional copolymer having a carbosiloxane dendrimer structure common in existing cosmetic formulations.

[0333] For example, the copolymer may partially or completely replace a silicon acrylate copolymer having a carbosiloxane dendrimer structure in cosmetic formulations in the following patent application publications (e.g., conventional products such as FA4001 CM silicon acrylate, FA4002 ID silicon acrylate, FA4003 silicon acrylate, etc.): International patent application publications WO2012 / 143344, WO2014 / 154701, WO2014 / 154700, WO2015 / 092632, WO2015 / 097110, WO2015 / 097103, WO2017 / 050699, WO2017 / 050922, WO2010 / 026538, WO2014 / 087183, WO2011 / 051323, JP2007-320960, WO2016 / 030842, JP2010-018612, JP2011-016734, JP2011-016732, JP2011-016733, JP2011-016734, JP2011-126807, JP2011-126808, JP2013-001672, JP2014-034568, JP2014-040388, JP2014-227358, JP2015-098451, JP2015-137252, JP2016-008200, JP2016-088848, JP2016-121095, JP2016-160191, JP2018-090495, JP2000-072784, JP07-309714, JP2007-320960, JP2014-040512, WO2017 / 061090, JP2011-149017, JP2014-040512, JP2014-040511, WO / 2018 / 086139, WO / 2018 / 186138, PCT / JP18 / 022412, and PCT / JP18 / 022413.

[0334] Specific intended end-use applications of the copolymer of the present invention are based on cosmetic formulations of the aforementioned patent applications, thereby replacing conventional copolymers having a carbosiloxane dendrimer structure of the patent applications with the copolymer of the present invention. In certain embodiments, the copolymer of the present invention is used in combination with a conventional copolymer having a carbosiloxane dendrimer structure. In other embodiments, the copolymer of the present invention is used instead of (and to replace) a conventional copolymer having a carbosiloxane dendrimer structure.

[0335] Furthermore, an emulsion composition containing a copolymer may be partially or completely replaced with the copolymer of the present invention in the emulsion. For example, copolymer emulsions in cosmetic formulations disclosed in the following literature may be replaced with emulsions containing the copolymer of the present invention: International Patent Applications Publications WO2017 / 061090, WO / 2018 / 086139, WO / 2018 / 186138, PCT / JP18 / 022412, PCT / JP18 / 022413 and Research Disclosure: No.IPCOM000243971D, and No.IPCOM0002457480.

[0336] By replacing a conventional silicone acrylate copolymer having a carbosiloxane dendrimer structure in available and conventional cosmetic formulations with a copolymer containing a branched organosilicon moiety, a person skilled in the art can anticipate and design similar or improved cosmetic formulations using the copolymer containing the branched organosilicon moiety.

[0337] The following examples describing embodiments of the present invention are intended to illustrate the invention, not to limit it.

[0338] Preparation Example 1: Preparation of Si10PrCl

[0339]

[0340] 1,1,1,3,5,5,5-heptamethyltrisiloxane (206.1 g) is loaded into a 1000 mL four-necked flask equipped with a thermocouple, a mechanical stirrer, an addition funnel, and a water-cooled condenser adjusted to an N2 bubbler, and the system is purged with N2 for 3 minutes. Then, a solution of tris(pentafluorophenyl)borane (BCF; 26 mg; 100 ppm) in toluene is added to the flask while stirring. Then, 3-chloropropyltrimethoxysilane (CPTMS; 52.4 g) is added to the addition funnel in portions (about 10 g), which are added slowly into the flask (one drop every about 3 seconds). During addition, the port temperature is gradually increased to about 70°C and maintained at 60 to 70°C over the addition process (about 60 minutes). Next, maintain the pot temperature at 70°C for 1 hour. Add an additional amount of BCF (20 ppm), raise the pot temperature to 90°C and maintain it at that temperature, and the Si-OMe conversion rate 1 It is monitored via H₂NMR spectroscopy. Additional amounts of BCF (20 ppm) were added every 60 minutes until completion (approx. 6 hours). Volatile substances were removed from the product mixture via a rotary evaporator (90°C; < 1 mmHg; 1 hour), and then neutral alumina (18 g) was added to the flask to obtain a slurry, which was stirred overnight. Subsequently, the slurry was filtered through a 0.45 μm membrane into a glass storage vial to obtain the product (Si10PrCl; 210.6 g) as a clear liquid, which 1 H NMR, 13 It is characterized through C NMR, gas chromatography-mass spectrometry (GC-MS), and GC equipped with a flame ionization detector (GC-FID).

[0341] Example 1: Synthesis of Monomethacrylate-Functional Branched Organosilicon Si10PrMA

[0342]

[0343] A three-necked flask is equipped with a mechanical stirrer, a thermocouple, and a water-cooled condenser adjusted to an N2 bubbler. Butylated hydroxytoluene (BHT; 35 mg), potassium iodide (KI; 0.8 g), sodium methacrylate (5.3 g), dimethylformamide (DMF, anhydrous; 50.0 g), and Si10PrCl (30.7 g) are charged into the flask to obtain a mixture, and the system is purged with N2 for 3 minutes. Subsequently, the mixture is heated to 120°C while stirring, maintained at that temperature for 5 hours, then cooled to <50°C, and transferred to a separatory funnel. Subsequently, the mixture is washed with water (DI; 4 × approx. 80 g) to obtain a yellow liquid, which is dried overnight with sodium sulfate (14 g). Subsequently, the generated mixture is filtered to obtain a product (Si10PrMA) as a transparent liquid, which is 1 H NMR, 13 It is characterized through 3C NMR, GC-MS, and GC-FID.

[0344] Example 2: Synthesis of Monoacrylate-Functional Branched Organosilicon Compound Si10PrA

[0345]

[0346] A three-necked flask is equipped with a mechanical stirrer, a thermocouple, and a water-cooled condenser adapted to an N2 bubbler. BHT (20 mg), 4-methoxyphenol (MEHQ; 15 mg); KI (0.7 g), potassium acrylate (1.9 g), DMF (anhydrous; 20.0 g), and Si¹⁰PrCl (12.4 g) were charged into the flask to obtain a mixture, and the system was purged with N2 for 3 minutes. Subsequently, the mixture was heated to 120°C while stirring, maintained at that temperature for 5 hours, then cooled to <50°C, and transferred to a separatory funnel. The mixture was then washed with water (DI; 3 × approx. 60 g) to obtain a yellow liquid, which was dried overnight with sodium sulfate (10 g). Subsequently, the resulting mixture was filtered to obtain the product (Si¹⁰PrA) as a clear liquid, which1 H NMR, 13 It is characterized through 3C NMR, GC-MS, and GC-FID.

[0347] Example 3: Synthesis of Monomethacrylate-Functional Branched Organosilicon Si10PrMA

[0348]

[0349] A 1000 mL 4-neck flask is placed in a dry box and purged with N2. Sodium methacrylate (50.9 g), tetrabutylammonium bromide (TBA-Br; 6.0 g), MEHQ (0.3 g), BHT (0.3 g), Si10PrCl (319.7 g), propylene glycol methyl ether acetate (PGMEA; 180 g), and dimethyl propylene urea (DMPU; 6.2 g) are loaded into the flask to obtain a mixture. Subsequently, the loaded flask is transferred to a fume hood equipped with a mechanical stirrer, a thermocouple, and a water-cooled condenser adjusted to an air bubbler. Then, the mixture is heated to 120°C while stirring, maintained at that temperature for 13.5 hours, then cooled to < 50°C and transferred to a 2 L separatory funnel. Subsequently, the mixture was washed three times with water (156 g, 180 g, and 151 g), the organic matter (upper layer) was collected in a 2 L aqueous flask, and concentrated using a rotary evaporator (100°C; approx. 0.6 Torr; approx. 40 min) to obtain a product (Si10PrMA; 325.0 g recovered) as a pale yellow liquid, which is 1 H NMR, 13 It is characterized through 3C NMR, GC-MS, and GC-FID.

[0350] Example 4: Synthesis of Monomethacrylate-Functional Branched Organosilicon Si10PrMA

[0351]

[0352] A 1000 mL 4-neck flask is placed in a dry box and purged with N2. Sodium methacrylate (31.8 g), TBA-Br (4.4 g), MEHQ (0.2 g), BHT (0.2 g), Si10PrCl (189.3 g), PGMEA (152.1 g), and hexamethylphosphoramide (HMPA; 4.0 g) are loaded into the flask to obtain a mixture. Then, the loaded flask is transferred to a fume hood and equipped with a mechanical stirrer, a thermocouple, and a water-cooled condenser adjusted to an air bubbler. Then, the mixture is heated to 120°C while stirring, maintained at that temperature for 12 hours, then cooled to < 50°C and transferred to a 2 L separatory funnel. Subsequently, the mixture was washed twice with water (DI; 252 g and 260 g), the organic matter (upper layer) was collected in a 2 L aqueous flask, and concentrated using a rotary evaporator (80°C; approx. 0.6 Torr; approx. 35 min) to obtain a product (Si10PrMA; 186.9 g recovered) as a pale yellow liquid, which is 1 H NMR, 13 It is characterized through 3C NMR, GC-MS, and GC-FID.

[0353] Example 5: Synthesis of Monomethacrylate-Functional Branched Organosilicon Si10PrMA

[0354]

[0355] A 2 oz vial equipped with a magnetic stirring bar is placed in a dry box purged with N2, and sodium methacrylate (1.01 g), TBA-Br (0.24 g), MEHQ (0.03 g), Si10PrCl (6.5 g), PGMEA (4.36 g), and dimethyl ethylene urea (DMEU; 0.54 g) are loaded to obtain a mixture. Subsequently, the loaded vial is heated to 120°C while stirring on a heating block and maintained at that temperature for 12 hours. Then, the mixture is cooled to <50°C and washed twice with DI water (DI; 252 g and 260 g). The organic material (upper layer) is collected in the vial, dried with sodium sulfate, and filtered to obtain the product (Si10PrMA), which is 1 H NMR, 13 It is characterized through 3C NMR, GC-MS, and GC-FID.

[0356] The terms “comprising” or “comprising” are used herein in the broadest sense to mean and encompass the concepts of “equipped,” “equipped,” “essentially made (made up),” and “made (made up).” The use of “for example,” “e.g.,” “like,” and “including” to enumerate exemplary examples is not limited to the enumerated examples alone. Accordingly, “for example” or “like” means “for example, but not limited thereto” or “like, but not limited thereto,” and encompasses other similar or equivalent examples.

[0357] Generally, as used herein, in ranges of values, a hyphen "-" or a dash "-" means "~ to ~" or "~ from ~"; ">" means "greater than" or "greater than"; "≥" means "greater than or equal to" or "greater than or equal to"; "<" means "less than" or "less than"; and "≤" means "less than or equal to" or "less than or equal to". Each of the aforementioned patent applications, patents, and / or patent application publications is individually and wholeheartedly incorporated herein by reference in one or more non-limiting embodiments.

[0358] It should be understood that the appended claims are not limited to the specific compounds, compositions, or methods described in the detailed description, and that they may vary among specific embodiments within the scope of the appended claims. With respect to any Markush group required herein in describing specific features or aspects of various embodiments, different, particular, and / or unexpected results may be obtained from each member of an individual Markush group independently of all other Markush members. Each member of a Markush group may be required individually and / or in combination and provides appropriate support for specific embodiments within the scope of the appended claims.

[0359] Furthermore, any ranges and subranges required to describe various embodiments of the present invention are understood to be independently and collectively included within the scope of the appended claims, and to describe and consider all ranges (including integer and / or fractional values ​​within said ranges, even if such values ​​are not explicitly stated in this specification). Those skilled in the art will readily recognize that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and that such ranges and subranges may be further subdivided into related half, 1 / 3, 1 / 4, 1 / 5, etc. As merely one example, the range “0.1 to 0.9” may be further subdivided into the lower third, i.e., 0.1 to 0.3, the middle third, i.e., 0.4 to 0.6, and the upper third, i.e., 0.7 to 0.9, which fall individually and collectively within the scope of the appended claims and may be individually and / or collectively required and may provide appropriate support for specific embodiments within the scope of the appended claims. Additionally, with respect to language limiting or modifying the range, e.g., “greater than,” “greater than,” “less than,” “less than,” etc., such language should be understood to include a sub-range and / or an upper or lower limit. As another example, the range of “10 or more” essentially includes sub-ranges of 10 or more to 35, sub-ranges of 10 or more to 25, sub-ranges of 25 to 35, etc., each sub-range may be required individually and / or collectively and provides appropriate support for specific embodiments within the scope of the appended claims. Finally, individual figures within the disclosed range may be required, which provide appropriate support for specific embodiments within the scope of the appended claims.For example, the range “1 to 9” includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be required and may provide appropriate support for specific embodiments within the scope of the appended claims.

[0360] The present invention has been described in an exemplary manner, and it should be understood that the terms used are intended to be descriptive rather than restrictive by their nature. Clearly, many modifications and variations of the invention are possible in light of the foregoing teachings. The invention may be practiced in ways other than those specifically described.

Claims

Claim 1 A method for preparing an acrylate-functional branched organosilicon compound, the method comprising the step of (C) reacting (A) a branched organosilicon compound having one halogen-functional moiety and (B) an acrylate compound in the presence of a catalyst to provide said acrylate-functional branched organosilicon compound; said branched organosilicon compound (A) having the following general chemical formula: or (In the above formula, X is -[CH2] n- Cl, and n is 2 to 6; and each R 5 is R, -OSi(R 6 )3 and -[OSiR2] m Selected from OSiR3; each R 6 R and -[OSiR2] m Selected from OSiR3; each R is an independently selected substituted or unsubstituted hydrocarbyl group; 0 ≤ m ≤ 100); the acrylate compound (B) has the following general chemical formula: (In the above formula, M is an alkali metal, and R 7 A method comprising: (i) sodium iodide; (ii) potassium iodide; (iii) N,N′-dimethylpropylene urea; (iv) hexamethylphosphoramide; (v) N,N′-dimethylethylene urea; (vi) tetrabutylammonium bromide; or (vii) any combination of (i) to (vi). Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 The method according to claim 1, wherein the acrylate compound (B) comprises (i) sodium methacrylate; (ii) potassium acrylate; or (iii) both of (i) and (ii). Claim 10 delete Claim 11 delete Claim 12 A method according to claim 1, wherein the reaction is also carried out in the presence of at least one additive selected from the group consisting of solvents, stabilizers, and combinations thereof. Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 A method for manufacturing a copolymer, the method comprising: a step of manufacturing an acrylate-functional branched organosilicon compound according to the method of claim 1; and a step of reacting the acrylate-functional branched organosilicon compound with a second compound that is reactive to the acrylate-functional branched organosilicon compound to provide the copolymer. Claim 17 delete Claim 18 delete Claim 19 A method according to claim 1, wherein the acrylate-functional branched organosilicon compound is used as at least one of a surfactant, a dispersant, a wetting agent, an anti-blocking additive, a surface tension modifier, a surface treatment agent, an additive for agricultural compositions, an additive for coatings, an additive for paints, a cosmetic ingredient, a siloxane modifier, and an aqueous film-forming foam ingredient. Claim 20 A method according to claim 16, wherein the copolymer is used as at least one of a surface treatment agent, a paint additive, a coating additive, and a cosmetic ingredient.

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