Silicone acrylate polymers, copolymers, and related methods and compositions

Abstract

A liquid composition is disclosed. The liquid composition includes a silicone acrylate polymer. The silicone acrylate polymer includes acrylate-derived monomer units including a siloxane moiety, an optional epoxide-functional moiety, and an optional hydrocarbyl moiety. Methods for preparing the silicone acrylate polymer and the liquid composition are also disclosed.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of priority and all advantages of U.S. Provisional Patent Application No. 62 / 964,439, filed on January 22, 2020, the content of which is incorporated herein by reference.

[0002] The present disclosure generally relates to siloxane - functionalized polymers, and more particularly to liquid compositions comprising silicone - functionalized acrylate polymers, as well as compounds and methods for preparing them.

Background Art

[0003] Silicones are polymeric materials used in many commercial applications, mainly because their advantages are prominent over their carbon - based analogs. More precisely, silicones, also called polymeric siloxanes or polysiloxanes, have an inorganic silicon - oxygen backbone (... -Si - O - Si - O - Si - O -...), with organic side groups bonded to silicon atoms. These organic side groups can be used to link two or more of these backbones together. By varying the -Si - O - chain length, side groups, and cross - linking, silicones can be synthesized with a wide variety of properties and compositions, and the consistency of the silicone network can vary from liquid to gel, rubber, and hard plastic.

[0004] Silicone and siloxane-based materials are known in the art and are utilized in numerous end uses and environments. The most common silicone materials are based on linear organopolysiloxane polydimethylsiloxane (PDMS), silicone oil. Such organopolysiloxanes are used in many industrial, home care, and personal care formulations. The second largest group of silicone materials is based on silicone resins formed by branched and cage oligosiloxanes. Unfortunately, the use of siloxane-based materials in certain applications that can benefit from specific inherent properties of organopolysiloxanes (e.g., low-loss and stable optical transmission, thermal and oxidative stability, etc.) has remained limited due to the fragile mechanical properties of conventional silicone networks, which can manifest in materials with insufficient or inappropriate properties such as low tensile strength, low tear strength, etc. Furthermore, conventional silicone networks and carbon-based polymers are often incompatible and / or have antagonistic properties to each other.

Summary of the Invention

[0005] A liquid composition is provided that includes a silicone acrylate polymer. The silicone polyether copolymer has the following general formula (I),

Chemical Formula

[0006] A method of preparing the liquid composition (the "preparation method") is also provided. The preparation method includes combining a silicone acrylate polymer and optionally a carrier vehicle to obtain the liquid composition.

[0007] A film formed from the liquid composition is also provided.

DETAILED DESCRIPTION OF THE INVENTION

[0008] A liquid composition comprising a silicone acrylate polymer is provided. The liquid composition can be used in a variety of end uses, such as a precursor for preparing a copolymer or other materials as a component in a functional composition, in or as a coating composition, etc. "Liquid" means that the liquid composition is fluid at 25 °C and has a viscosity that can be measured at 25 °C for the liquid composition. In certain embodiments, the liquid composition has a viscosity that can be measured at 25 °C using an Anton Paar MCR-302 rheometer using a 50 mm cone and plate geometry (primary sweep, low to high shear) at a shear rate of 50 - 500 s -1 .

[0009] Silicone acrylate polymers generally contain two or more monomer units derived from acryloxy-functional monomers, which may be the same or different from each other. For example, silicone acrylate polymers can be homopolymers, copolymers, terpolymers, etc. Silicone acrylate polymers can be characterized, defined, or referred to as acrylic or acrylic polymers or copolymers. However, as described below and shown by the examples in this specification, silicone acrylate polymers can contain functional groups that are unrelated to acrylate / acryloxy functional groups or monomers (e.g., other polymer moieties, end-capping groups, etc.). Nevertheless, as understood by those skilled in the art, they can simply be described or referred to as acrylate polymers.

[0010] The silicone polyether copolymer has the following general formula (I): [Chemical formula] In the formula, each Y 1 is a siloxane moiety independently selected, each D 1 is a divalent linking group, each X 1 is an epoxide-functional moiety independently selected, each R 1 is independently selected from H and CH3, each R 2 is independently a substituted or unsubstituted hydrocarbyl group or H, the subscript a ≥ 1, the subscript b ≥ 0, the subscript c ≥ 0, provided that a + b + c ≥ 2, and the units represented by the subscripts a, b, and c can be in any order in the silicone-acrylate polymer.

[0011] Regarding formula (I), as described above, Y 1 represents a siloxane moiety. Generally, the siloxane moiety Y 1includes siloxane and is not particularly limited otherwise. As understood in the art, siloxane includes inorganic silicon-oxygen-silicon groups (i.e., -Si-O-Si-) having organic silicon and / or organic side groups bonded to silicon atoms. As such, siloxane can be represented by the general formula ([R f SiO (4-f) / 2 e ) g (R) 3-g Si-, where the subscript f is independently selected from 1, 2, and 3 of each part indicated by the subscript e, the subscript e is at least 1, the subscript g is 1, 2, or 3, and each R is independently selected from hydrocarbyl groups, alkoxy and / or aryloxy groups, and siloxy groups.

[0012] ​Suitable hydrocarbyl groups for R include monovalent hydrocarbon moieties, as well as their derivatives and modified forms, which can independently be substituted or unsubstituted, linear, branched, cyclic, or combinations thereof, and can be saturated or unsaturated. With respect to such hydrocarbyl groups, the term "unsubstituted" refers to a hydrocarbon moiety composed of carbon and hydrogen atoms, i.e., a hydrocarbon moiety that does not contain heteroatom substituents. The term "substituted" refers to a hydrocarbon in which at least one hydrogen atom is replaced by an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a pendant or terminal substituent), a carbon atom within the hydrocarbon chain / skeleton is replaced by an atom other than carbon (e.g., a heteroatom such as oxygen, sulfur, nitrogen, etc.) (e.g., as part of the chain / skeleton), or both. As such, suitable hydrocarbyl groups include hydrocarbon moieties in which the hydrocarbon group has one or more substituents within and / or on its carbon chain / skeleton (i.e., appended and / or integral) such that the hydrocarbon moiety can include or be an ether, ester, etc. Linear and branched hydrocarbon groups can independently be saturated or unsaturated, and in the case of unsaturation, can be conjugated or non-conjugated. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic and include cycloalkyl groups, aryl groups, and heterocycles, which can be aromatic, saturated and non-aromatic, and / or non-conjugated, etc. Examples of combinations of linear and cyclic hydrocarbyl groups include alkaryl groups, aralkyl groups, etc. General examples of hydrocarbon moieties suitable for use in or as a hydrocarbyl group include alkyl groups, aryl groups, alkenyl groups, alkynyl groups, halocarbon groups, etc., as well as their derivatives, modifications, and combinations. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and / or tert-pentyl), hexyl, octyl (including ethylhexyl), etc. (i.e., other linear or branched saturated hydrocarbon groups).Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethylphenyl, etc., as well as their derivatives and modified forms, which may overlap with alkylaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethylphenyl, etc.). Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl group, etc., as well as their derivatives and modified forms. General examples of halogenated hydrocarbon groups include halogenated alkyl groups (e.g., any of the above alkyl groups in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl), aryl groups (e.g., any of the above aryl groups in which one or more hydrogen atoms are replaced by halogen atoms such as F or Cl), and halogenated derivatives of the above hydrocarbon moieties such as combinations thereof. Examples of halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, etc., as well as their derivatives and modified forms. Examples of halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl group, etc., as well as their derivatives and modified forms.

[0013] Suitable alkoxy and aryloxy groups for R include those having the general formula -OR i and those having the formula, wherein R iis one of the hydrocarbyl groups described above with respect to R. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, benzyloxy, etc., as well as derivatives and modifications thereof. Examples of aryloxy groups include phenoxy, tolyloxy, pentafluorophenoxy, etc., as well as derivatives and modifications thereof.

[0014] Examples of suitable siloxy groups for R include [M], [D], [T], and [Q] units, which, as understood in the art, each represent an individual functional structural unit present in siloxanes such as organosiloxanes and organopolysiloxanes. More specifically, [M] is of the general formula R ii 3SiO 1 / 2 represents a monofunctional unit, [D] is of the general formula R ii 2SiO 2 / 2 represents a difunctional unit, [T] is of the general formula R ii SiO 3 / 2 represents a trifunctional unit, and [Q] is of the general formula SiO 4 / 2 represents a tetrafunctional unit, shown by the following general structural moieties:

Chemical formula

[0015] In these general structural moieties, each R ii is independently a monovalent or polyvalent substituent. As understood in the art, specific suitable substituents for each R ii are not limited and can be monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, and combinations thereof. Typically, each R ii is independently selected from hydrocarbyl groups, alkoxy and / or aryloxy groups, and siloxy groups. Thus, each R ii is independently a hydrocarbyl group of the formula -R i or an alkoxy or aryloxy group of the formula -OR i , wherein R iis as defined above (e.g., includes any of the hydrocarbyl groups described above with respect to R), or is a siloxy group represented by any one or combination of the above [M], [D], [T], and / or [Q] units.

[0016] Siloxane moiety Y 1 For example, can be linear, branched, or a combination thereof, based on the number and arrangement of [M], [D], [T], and / or [Q] siloxy units present therein. When branched, the siloxane moiety Y 1 can be minimally branched or alternatively can be hyperbranched and / or dendritic.

[0017] In certain embodiments, the siloxane moiety Y 1 is a branched siloxane moiety having the general formula -Si(R 3 )3, wherein at least one R 3 is -OSi(R 5 )3 and each other R 3 is independently selected from R 4 and -OSi(R 5 )3. In such embodiments, each R 5 is independently selected from R 4 , -OSi(R 6 )3, and -[-D 2 -SiR 4 2] m OSiR 4 3, wherein each R 6 is independently selected from R 4 , -OSi(R 7 )3, and -[-D 2 -SiR 4 2] m OSiR 4 3, wherein each R 7 is independently selected from R 4 , and -[-D 2 -SiR 4 2] m OSiR 4 3. In each selection, R 4is an independently selected substituted or unsubstituted hydrocarbyl group, such as any of those described above with respect to R, D 2 is a divalent linking group individually selected for each moiety indicated by the subscript m, and each subscript m is individually selected such that 0 ≦ m ≦ 100 (i.e., in each applicable selection).

[0018] Y 1 In such branched siloxane moieties of, each divalent linking group D 2 is typically selected from oxygen (i.e., -O-) and divalent hydrocarbon groups. Examples of such hydrocarbon groups include the above hydrocarbon groups and divalent forms of hydrocarbon groups, such as any of those described above with respect to R. Thus, it will be understood that the hydrocarbon groups suitable for the divalent linking group D 2 can be substituted or unsubstituted, and linear, branched, and / or cyclic. However, typically, when the divalent linking group D 2 is a divalent hydrocarbon group, D 2 is selected from unsubstituted linear alkylene groups such as ethylene, propylene, butylene, etc.

[0019] In certain embodiments, each divalent linking group D 2 is oxygen (i.e., -O-), and as a result, each R 5 is independently selected from R 4 , -OSi(R 6 )3, and -[OSiR 4 2] m OSiR 4 3, each R 6 is independently selected from R 4 , -OSi(R 7 )3, and -[OSiR 4 2] m OSiR 4 3, each R 7 is independently selected from R 4 , and -[OSiR 4 2] m OSiR 4 3, each R 4is as defined and described above, and the subscript m is as defined and described above.

[0020] As introduced above, each R 3 is selected from R 4 and -OSi(R 5 )3, provided that at least one R 3 is of the formula -OSi(R 5 )3. In certain embodiments, at least two R 3 are -OSi(R 5 )3. In certain embodiments, each R 3 is of the formula -OSi(R 5 )3. The greater the number of R 5 that are -OSi(R 3 )3, the higher the branching level of the siloxane moiety Y 1 is understood to be. For example, when each R 3 is -OSi(R 5 )3, the silicon atom to which each R 3 is attached is a [T] siloxy unit. Alternatively, when two R 3 are of the formula -OSi(R 5 )3, the silicon atom to which each R 3 is attached is a [D] siloxy unit. Further, when any R 3 is of the formula -OSi(R 5 )3 and at least one of those R 5 is of the formula -OSi(R 6 )3, additional siloxane linkages and branching are present in the siloxane moiety Y 1 . This further leads to cases where any R 6 is of the formula -OSi(R 7 )3. Thus, one of ordinary skill in the art will understand that each subsequent R 1 portion of the siloxane moiety Y 5+n can impart additional generations of branching depending on its particular selection. For example, at least one R 5 can be of the formula -OSi(R 6 )3, and at least one of those R 6 can be of the formula -OSi(R7 ) It can be 3. Therefore, depending on the selection of each substituent, further branching due to the [T] and / or [Q] siloxane units can be present in the siloxane moiety Y 1 (i.e., beyond the branching of the other substituents / portions described above).

[0021] Each R 5 is independently selected from R 4 , -OSi(R 6 )3, and -[-D 2 -SiR 4 2] m OSiR 4 3, where each R 4 , D 2 , and R 6 are as defined and described above, and each subscript m is as defined and described above. For example, when D 2 is oxygen (i.e., -O-), R 5 is selected from R 4 , -OSi(R 6 )3, and -[OSiR 4 2] m OSiR 4 3, and 0 ≦ m ≦ 100. Depending on the selection of R 5 and R 6 , further branching can be present in the siloxane moiety Y 1 . For example, when each R 5 is R 4 , then each -OSi(R 5 )3 moiety (i.e., each R 5 in the formula -OSi(R 3 )3) is a terminal [M] siloxy unit. In other words, when each R 3 is -OSi(R 5 )3 and each R 5 is R 4 , then each R 3 can be described as -OSiR 4 3 (i.e., the [M] siloxy unit). In such embodiments, the siloxane moiety Y 1 is the group D 1 in formula (I).contains [T] siloxy units bonded thereto, and these [T] siloxy units are capped by three [M] siloxy units. Further, R 5 is of the formula -[-D 2 -SiR 4 2] m OSiR 4 3, and when D 2 is oxygen (i.e., -O-), the siloxane moiety Y 1 contains any [D] siloxane units (i.e., the siloxane units of each moiety denoted by the subscript m) and [M] siloxane units (i.e., represented by OSiR 4 3). Thus, when each R 3 is of the formula -OSi(R 5 )3 and R 5 is of the formula -[-D 2 -SiR 4 2] m OSiR 4 3 and each D 2 is oxygen (i.e., -O-), then each R 3 contains [Q] siloxy units. More specifically, in such embodiments, each R 3 is of the formula -OSi([OSiR 4 2] m OSiR 4 3)3, and as a result, when each subscript m is 0, each R 3 is a [Q] siloxy unit end-capped with three [M] siloxy units. Similarly, when the subscript m is greater than 0, each R 3 contains a linear portion (i.e., a diorganosiloxane portion) having a degree of polymerization resulting from the subscript m.

[0022] As described above, each R 5 may also be of the formula -OSi(R 6 )3. In embodiments where one or more R 5 are of the formula -OSi(R 6 )3, further branching may be present in the siloxane moiety Y 6 depending on the choice of R 1 . More specifically, each R 6 is R 4 , -OSi(R7 )3, and -[-D 2 -SiR 4 2] m OSiR 4 3, each R 7 is R 4 , and -[-D 2 -SiR 4 2] m OSiR 4 3, the subscript m is defined above. For example, in some embodiments, each D 2 is oxygen (i.e., -O-), and as a result, each R 6 is R 4 , -OSi(R 7 )3, and -[OSiR 4 2] m OSiR 4 3, each R 7 is R 4 , and -[OSiR 4 2] m OSiR 4 3, the subscript m is defined above and is as described below.

[0023] As introduced above, for the branched siloxane moiety of Y 1 , the subscript m is 0 to 100, or 0 to 80, or 0 to 60, or 0 to 40, or 0 to 20, or 0 to 19, or 0 to 18, or 0 to 17, or 0 to 16, or 0 to 15, or 0 to 14, or 0 to 13, or 0 to 12, or 0 to 11, or 0 to 10, or 0 to 9, or 0 to 8, or 0 to 7, or 0 to 6, or 0 to 5, or 0 to 4, or 0 to 3, or 0 to 2, or 0 to 1, or 0 (and inclusive). In certain embodiments, each subscript m is 0, and as a result, the siloxane moiety Y 1 does not contain [D] siloxy units.

[0024] Importantly, R 3 , R 4 , R 5 , R 6 , and R7 Each of these is independently selected. Thus, the above description for each of these substituents is not meant to imply or indicate that each substituent is the same. Rather, any of the above descriptions regarding R 5 may relate to, for example, one R 1 in the siloxane moiety Y 5 only or any number of R 5 . In addition, different selections of R 3 , R 4 , R 5 , R 6 , and R 7 can result in the same structure. For example, if a particular R 3 i is -OSi(R 5 )3, each R 5 is -OSi(R 6 )3, and each R 6 is R 4 , then that particular R 3 can be described as -OSi(OSiR 4 3)3. Similarly, if a particular R 3 i is -OSi(R 5 )3, each R 5 is -[-D 2 -SiR 4 2] m OSiR 4 3 and the subscript m is 0, then that particular R 3 can be described as -OSi(OSiR 4 3)3. As shown, these particular selections result in the same final structure for R 5 based on different selections for R 3 . Therefore, any conditions on the final structure of the siloxane moiety Y 1 should be satisfied by alternative selections that result in the same structure required by the conditions.

[0025] In certain embodiments, each R 4 is an alkyl group independently selected. In some such embodiments, each R 4is independently selected from alkyl groups having 1 to 10, or 1 to 8, or 1 to 6, or 1 to 4, or 1 to 3, or 1 to 2 carbon atoms.

[0026] In certain embodiments, each subscript m is 0 and each R 4 is methyl, and the siloxane moiety Y 1 has one of the following structures (i) to (iv)

Chemical formula

[0027] In certain embodiments, the siloxane moiety Y 1 is a linear siloxane moiety having the following general formula

Chemical formula

Chemical formula

[0028] Generally, Y 1Regarding the linear siloxane portion, the subscript n is equivalent to the above-mentioned subscript m and thus represents values from 0 to 100 (including 0 and 100). Similarly, the subscript n can be from 0 to 80, for example, from 0 to 60, or from 0 to 40, or from 0 to 20, or from 0 to 19, or from 0 to 18, or from 0 to 17, or from 0 to 16, or from 0 to 15, or from 0 to 14, or from 0 to 13, or from 0 to 12, or from 0 to 11, or from 0 to 10, or from 0 to 9, or from 0 to 8, or from 0 to 7, or from 0 to 6, or from 0 to 5, or from 0 to 4, or from 0 to 3, or from 0 to 2, or from 0 to 1, or 0. In a particular embodiment, the subscript n is 0, and as a result, the linear siloxane portion Y 1 does not contain [D] siloxy units in the segment indicated by the subscript q (i.e., when q is 1). However, in other embodiments, the subscript q is 1 and the subscript n is ≧1, and as a result, the linear siloxane portion Y 1 of the segment contains at least one [D] siloxy unit. For example, in such embodiments, the subscript n is from 1 to 100, for example, from 5 to 100, or from 5 to 90, or from 5 to 80, or from 5 to 70, or from 7 to 70, and as a result, the linear siloxane portion Y 1 of the segment contains a plurality of [D] siloxane units within one of these ranges.

[0029] The subscript o is from 2 to 6, and the segment indicated by the subscript o is a C2-C6 alkylene group such as an ethylene, propylene, butylene, pentylene, or hexylene group. Similarly, the subscript r is from 0 to 9, and the segment indicated by the subscript r, when r ≧1, is a C1-C9 alkylene group such as those described above for the subscript 0, or a heptylene, octylene, or nonylene group.

[0030] The subscripts s and t are for the linear siloxane portion Y 1represents the substitution of the terminal silicone atoms. Generally, at least one of the subscripts s and t is >0 (i.e., s + t>0). For example, in certain embodiments, the subscript s is 1 and the subscript t is 0. In other embodiments, the subscript s is 0 and the subscript t is 2. In certain embodiments, the above linear siloxane moiety Y 1 follows the condition that when the subscript s is 1, the subscript t is 0, and when the subscript s is 0, the subscript t is 2 in its general formula.

[0031] In some embodiments, the subscript q is 0 and the subscript t is 2, and as a result, Y 1 is an MD’M siloxane of the following general formula,

Chemical formula

Chemical formula

[0032] In certain embodiments, the subscript p is 0, the subscript q is 1, the subscript s is 1, the subscript t is 0, and each R 4 is methyl, and as a result, Y has the following formula, [Chemical formula] In the formula, the subscript letters n and r are as defined and described above. In some such embodiments, the subscript letter r is 4 or 6. In these or other such embodiments, the subscript letter n is ≧1, for example, 5 to 70.

[0033] In certain embodiments, the subscript letter q is 1, the subscript letter p is 1, and the subscript letter n is 1, such that Y 1 has the following formula, [Chemical formula] In the formula, each R 4 as well as the subscript letters o, r, s, and t are as defined above. For example, in certain such embodiments, the subscript letter o is 2, the subscript letter s is 0, the subscript letter t is 2, and each R 4 is methyl. In other such embodiments, the subscript letter o is 2, the subscript letter s is 1, the subscript letter r is 0, the subscript letter t is 2, and each R 4 is methyl. In both of the aforementioned embodiments, Y has the following formula [Chemical formula]

[0034] Regarding formula (I) further, as introduced above, each D 1 is a divalent linking group independently selected. The divalent linking group suitable for D 1 is not particularly limited. Typically, the divalent linking group D 1 is selected from divalent hydrocarbon groups. Examples of such hydrocarbon groups include any of those described above for R, such as the above hydrocarbon groups and the divalent forms of hydrocarbon groups. Thus, it will be understood that the hydrocarbon groups suitable for the divalent linking group D 1 can be substituted or unsubstituted, and can be linear, branched, and / or cyclic.

[0035] In some embodiments, the divalent linking group D 1 comprises or is a straight-chain or branched hydrocarbon moiety such as a substituted or unsubstituted alkyl group, an alkylene group, etc. For example, in certain embodiments, the divalent linking group D 1 has a straight-chain hydrocarbon moiety having the formula -(CH2) d -, etc., and comprises or is a C1-C 18 hydrocarbon moiety, where the subscript d is from 1 to 18. In some such embodiments, the subscript d is from 1 to 16, for example, from 1 to 12, or from 1 to 10, or from 1 to 8, or from 1 to 6, or from 2 to 6, or from 2 to 4. In certain embodiments, the subscript d is 3, and as a result, the divalent linking group D 1 comprises or is propylene (i.e., a chain of 3 carbon atoms). As will be understood by those skilled in the art, each unit represented by the subscript d is a methylene unit, and as a result, the straight-chain hydrocarbon moiety may be defined as or otherwise referred to as an alkylene group. Each methylene group can be independently unsubstituted and unbranched (e.g., the hydrogen atom is not replaced by a non-hydrogen atom or group), or substituted and / or branched (e.g., the hydrogen atom is replaced by an alkyl group). In certain embodiments, the divalent linking group D 1 comprises or is an unsubstituted alkylene group.

[0036] In some embodiments, the divalent linking group D 1 comprises or is a substituted hydrocarbon moiety such as a substituted alkylene group. In such embodiments, the divalent linking group D 1 may comprise a carbon skeleton having at least 2 carbon atoms and at least 1 heteroatom (e.g., O, N, S, etc.), and as a result, the skeleton includes an ether moiety, an amine moiety, etc. For example, in certain embodiments, the divalent linking group D 1 comprises or is an amino-substituted hydrocarbon group (i.e., a hydrocarbon containing a nitrogen-substituted carbon chain / skeleton). For example, in some such embodiments, the divalent linking group D 1 has the formula -D 3 -N(R4 )-D 3 is an amino-substituted hydrocarbon having -, wherein each D 3 is an independently selected divalent hydrocarbon group, and R 4 is as defined above (i.e., an alkyl group (e.g., a hydrocarbyl group such as methyl, ethyl, etc.)). In certain embodiments, R 4 is that of methyl in the amino-substituted hydrocarbon of the foregoing formula. Each D 3 typically contains an independently selected alkylene group such as any of those described above with respect to the divalent linking group D 1 . For example, in some embodiments, each D 3 is independently selected from alkylene groups having 1 to 8 carbon atoms, such as 2 to 8, or 2 to 6, or 2 to 4 carbon atoms. In certain embodiments, each D 3 is propylene (i.e., -(CH2)3-). However, it will be understood that one or both D 3 can be or can include another divalent linking group (i.e., other than the alkylene groups described above). Further, each D 3 can be substituted or unsubstituted, linear or branched, and various combinations thereof.

[0037] Regarding formula (I), as introduced above, X 1 represents an epoxide-functional moiety, i.e., a moiety containing an epoxide group. The epoxide group is not particularly limited and can be any group containing an epoxide (e.g., a 3-membered cyclic ether with 2 carbons). For example, X 1may contain or be a cyclic epoxide or a linear epoxide. As will be understood by those skilled in the art, an epoxide (e.g., an epoxide group) is schematically described in terms of the carbon chain skeleton formed by two epoxide carbons (e.g., an epoxyalkane derived from the epoxidation of an alkene). For example, a linear epoxide generally contains a linear hydrocarbon containing two adjacent carbon atoms bonded to the same oxygen atom. Similarly, a cyclic epoxide generally contains a cyclic hydrocarbon containing two adjacent carbon atoms bonded to the same oxygen atom, and at least one, typically both, of the adjacent carbon atoms are in the ring of the cyclic structure (i.e., form part of both the epoxide ring and the hydrocarbon ring). The epoxide may be a terminal epoxide or an internal epoxide. X 1 Specific examples of epoxides suitable for 1 include epoxyalkyl groups (e.g., epoxyethyl group, epoxypropyl group (i.e., oxiranylmethyl group), oxiranylbutyl group, epoxyhexyl group, oxiranyloctyl group, etc.), epoxycycloalkyl groups (e.g., epoxycyclopentyl group, epoxycyclohexyl group, etc.), glycidyloxyalkyl groups (e.g., 3-glycidyloxypropyl group, 4-glycidyloxybutyl group, etc.), and the like. Those skilled in the art will understand that such epoxide groups can be substituted or unsubstituted.

[0038] In certain embodiments, X 1 is a hydrocarbon group containing an epoxyethyl group of the formula

Chemical formula

Chemical formula

Chemical formula

[0039] Regarding formula (I) further, as introduced above, each R 1 is independently selected from H and CH3. In other words, R 1 is independently H or CH3 in each part indicated by subscript a, independently H or CH3 in each part indicated by subscript b, and independently H or CH3 in each part indicated by subscript c. In certain embodiments, R 1 is CH3 in each part indicated by subscript a. In these or other embodiments, R 1 is CH3 in each part indicated by subscript b. In these or other embodiments, R 1 is CH3 in each part indicated by subscript c. In certain embodiments, R 1 is CH3 in each part indicated by subscripts a and b, and R 1 is H in each part indicated by subscript c. However, it will be understood that the parts indicated by subscripts a, b, and / or c may include a mixture of different R 1 groups. For example, in certain embodiments, R 1 is H in the major amount of the part indicated by subscript c, and R 1 is CH3 in the remaining part of the part indicated by subscript c.

[0040] Regarding formula (I) further, as introduced above, R 2 represents H or a substituted or unsubstituted hydrocarbyl group. Typically, R 2 is a substituted or unsubstituted hydrocarbyl group. Examples of such hydrocarbyl groups include those described above for R.

[0041] In some embodiments, R 2 is a hydrocarbyl group having 1 to 20 carbon atoms. In certain such embodiments, R 2contains or is an alkyl group. Suitable alkyl groups include saturated alkyl groups which can be linear, branched, cyclic (e.g., monocyclic or polycyclic), or combinations thereof. Examples of such alkyl groups include those having the general formula C j H 2j-2k+1 wherein the subscript j is from 1 to 20 (i.e., the number of carbon atoms present in the alkyl group), the subscript k is the number of independent rings / ring loops, and at least one carbon atom represented by the subscript j is bonded to the carboxylic acid oxygen shown to be bonded to R 2 in formula (I) above. Examples of linear and branched isomers of such alkyl groups (i.e., when the alkyl group does not contain a cyclic group such that the subscript k = 0) include those having the general formula C j H 2j+1 wherein the subscript j is as defined above, and at least one carbon atom represented by the subscript j is bonded to the carboxylic acid oxygen shown to be bonded to R 2 in formula (I) above. Examples of monocyclic alkyl groups include those having the general formula C j H 2j-1 wherein the subscript j is as defined above, and at least one carbon atom represented by the subscript j is bonded to the carboxylic acid oxygen shown to be bonded to R 2It binds to the carboxylic oxygen shown to bind. Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups, including their linear, branched, and / or cyclic isomers. For example, the pentyl group includes n-pentyl (i.e., the linear isomer) and cyclopentyl (i.e., the cyclic isomer), as well as branched isomers such as isopentyl (i.e., 3-methylbutyl), neopentyl (i.e., 2,2-dimethylpropyl), tert-pentyl (i.e., 2-methylbutan-2-yl), sec-pentyl (i.e., pentan-2-yl), sec-isopentyl (i.e., 3-methylbutan-2-yl), etc., 3-pentyl (i.e., pentan-3-yl), and active pentyl (i.e., 2-methylbutyl).

[0042] In some embodiments, each R 2 is independently selected from alkyl groups having 1 to 12 carbon atoms, such as 1 to 8, or 2 to 8, or 2 to 6 carbon atoms. In such embodiments, each R 2 is typically selected from methyl, ethyl, propyl (e.g., n-propyl and iso-propyl groups), butyl (e.g., n-butyl, sec-butyl, iso-butyl, and tert-butyl groups), pentyl (e.g., those described above), hexyl, heptyl, etc., as well as their derivatives and / or modified forms. Examples of such derivatives and / or modified forms of alkyl groups include their substituted versions. For example, R 2 may include or be a hydroxyethyl group, which will be understood to be a derivative and / or modified form of the ethyl group described above. Similarly, R 2may contain or be an acetoxyethyl group, which may also be a derivative and / or modification of the ethyl group described above (e.g., as an acetoxy-substituted ethyl group), and derivatives and / or modifications of other hydrocarbyl groups described above (e.g., an ethyl group substituted with esters and ketones, etc.).

[0043] In certain embodiments, each R 2 is independently selected from ethyl, n-butyl, isobutyl, isobornyl, cyclohexyl, neopentyl, 2-ethylhexyl, hydroxyethyl, and acetoxyethyl groups. In certain embodiments, at least one R 2 is a butyl group (e.g., n-butyl).

[0044] The subscripts a, b, and c represent the number of monomer units shown in the above formula (I), and the silicone acrylate polymer comprises at least one moiety represented by the subscript a (i.e., subscript a ≥ 1), optionally one or more moieties represented by the subscript b (i.e., subscript b ≥ 0), and optionally one or more moieties represented by the subscript c (i.e., subscript c ≥ 0). The silicone acrylate polymer comprises at least two monomer units such that a + b + c ≥ 2. In other words, generally, the subscript a is at least 1, or greater than 1, the subscript b is 0, 1, or greater than 1, and the subscript c is 0, 1, or greater than 1. In certain embodiments, the subscript a has a value of from 1 to 100, such as from 1 to 80, or from 1 to 70, or from 1 to 60, or from 1 to 50, or from 1 to 40, or from 1 to 30, or from 1 to 25, or from 5 to 25. In these or other embodiments, the subscript b has a value of from 1 to 100, such as from 1 to 80, or from 1 to 70, or from 1 to 60, or from 1 to 50, or from 1 to 40, or from 1 to 30, or from 1 to 20, or from 1 to 10. In other embodiments, the subscript b is 0. In certain embodiments, the subscript c is 0. In other embodiments, the subscript c is ≥ 1. For example, in some embodiments, the subscript c has a value of from 1 to 100, such as from 1 to 80, or from 1 to 70, or from 1 to 60, or from 1 to 50, or from 1 to 40, or from 1 to 30, or from 1 to 20, or from 1 to 15.

[0045] In some embodiments, the silicone acrylate polymer has a degree of polymerization (DP) or number-average degree of polymerization (Xn) of 2 to 100, such as 2 to 50, or 5 to 50, or 10 to 50, or 1 to 40, or 2 to 35, or 5 to 30, or 5 to 25. Alternatively, it is 5 to 20, or 5 to 15. In certain embodiments, both subscripts b and c are 0, and as a result, the silicone acrylate polymer is a homopolymer. In other embodiments, subscript b is 0 and subscript c is ≥1, and as a result, the silicone acrylate polymer is a copolymer. Each unit represented by c can be independently selected based on R 2 and the copolymer can be a terpolymer considering the different moieties represented by subscript c. Alternatively, still, subscripts a, b, and c can all be ≥1. As understood in the art, DP is based on the number of monomer units in the silicone acrylate polymer, and Xn is the weighted average of the degree of polymerization of the species of the silicone acrylate polymer weighted by the molar fraction (or number of molecules) of the species. Methods for measuring DP and Xn are known in the art.

[0046] It will be understood that the moieties represented by subscripts a, b, and c are independently selected. Thus, for example, when subscript a is at least 2, the silicone acrylate polymer can include more than one moiety that is different from one another (i.e., different by different selections of R 1 , D 1 , and / or Y 1 ). Similarly, when subscript b is at least 2, the silicone acrylate polymer can include more than one moiety that is different from one another (i.e., different by different selections of R 1 and / or X 1 ). Similarly, when subscript c is at least 2, the silicone acrylate polymer can include more than one moiety that is different from one another (i.e., different by different selections of R1 and / or R 2 can include more than one part that is different from each other by different selections of). For example, in certain embodiments, the subscript c is 0, and the silicone acrylate polymer is Y 1 includes more than one part indicated by different subscripts that are different from each other by different selections of, and as a result, the above formula (I) can be rewritten into the following general unit formula,

Chemical formula

Chemical formula

[0047] In certain embodiments, the silicone acrylate polymer has a weight-average molecular weight (Mw) of greater than 0 to 50,000 Da. For example, the silicone acrylate polymer can have an Mw of 100 to 40,000, or 100 to 30,000, or 100 to 20,000, or 100 to 10,000, or 500 to 5,000 Da. In certain embodiments, the silicon acrylate polymer has a number-average molecular weight (Mn) of 500 to 5,000, or 1,000 to 3,000, or 1,500 to 2,500. In these or other embodiments, the silicone acrylate polymer has a polydispersity of 1.1 to 10, or 1.5 to 5, or 1.5 to 4, or 1.5 to 3, or 1.5 to 2, or 1.5 to 1.65. In these or other embodiments, the silicone acrylate polymer has a glass transition temperature (Tg) of -20 to -70, or -20 to -60, or -30 to -70, or -30 to -60 °C. The molecular weight and polydispersity of the silicone acrylate polymer can be readily determined by techniques known in the art via gel permeation chromatography (GPC) relative to polystyrene standards (e.g., using size exclusion chromatography (GPC / SEC)). The glass transition temperature (Tg) can be measured by differential scanning calorimetry (DSC).

[0048] In certain embodiments, the liquid composition further comprises a carrier vehicle. When utilized, the carrier vehicle is non-aqueous. The carrier vehicle typically solubilizes the silicone acrylate copolymer and, in such embodiments, is the solvent. In some embodiments, the carrier vehicle comprises, or is, an organic solvent. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; aliphatic hydrocarbons such as heptane, hexane, octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol methyl ether acetate; alcohols such as methanol, ethanol, isopropanol, butanol, or n-propanol; and other organic compounds that are liquid / fluid at typical reaction temperatures such as dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, white spirit, mineral spirit, naphtha, n-methylpyrrolidone, and their derivatives, modifications, and combinations.

[0049] The liquid composition is liquid regardless of the presence or absence of a carrier vehicle. For example, the viscosity of the silicone acrylate polymer can be controlled such that the silicone acrylate polymer is liquid even in the absence of any carrier vehicle. In certain embodiments, the liquid silicone composition consists essentially of, or alternatively consists of, a silicone acrylate polymer and any carrier vehicle.

[0050] The liquid composition has a volatile organic compound (VOC) content of 0 to 25 wt% based on the total weight of the liquid composition. VOCs are known in the art and typically result from the presence of organic solvents. For the purposes of the present disclosure, the VOCs are not based on any regulatory definition of VOCs as defined, for example, by any administrative agency, but rather are based on VOCs regardless of environmental impact. In various embodiments, the VOCs are organic solvents. In these or other embodiments, the VOCs are organic compounds having a vapor pressure such that the VOCs volatilize (i.e., evaporate or sublime) at room temperature (25 °C) or elevated temperatures (e.g., exceeding 25 to 200 °C).

[0051] In certain embodiments, the liquid composition is VOC-free. In other embodiments, the liquid composition has a VOC content of greater than 0 to 25, or greater than 0 to 20, or greater than 0 to 15, or greater than 0 to 10, or greater than 0 to 5 weight percent based on the total weight of the liquid composition. In contrast, conventional silicone acrylate polymers or copolymers have a significant VOC content because they require a high weight percent of organic solvents to solubilize high molecular weight and often solid silicone acrylate polymers. In contrast, the liquid compositions of the present invention are liquids having a low VOC content or have no VOC content.

[0052] A method for preparing the liquid composition is also disclosed. The method includes combining a silicone acrylate polymer and an optional carrier vehicle. In certain embodiments, the method further includes preparing the silicone acrylate polymer. The method for preparing the silicone acrylate polymer includes obtaining a silicone acrylate polymer by reacting (A) an acryloxy-functional organosilicon component, optional (B) an epoxy-functional acrylate component, and optional (C) an acrylate component.

[0053] As will be understood by those skilled in the art in view of the description herein, each of components (A), (B), and (C) includes monomers that form (e.g., via polymerization / reaction) the units represented by formula (I) of the silicone acrylate polymer. Thus, the above description regarding the specific functional groups and variables of the silicone acrylate polymer (e.g., R 1 D 1 and Y 1 X 1 R 2 ) applies equally to the specific monomers utilized in the preparation method, which are described in order below.

[0054] The acryloxy-functional organosilicon component (A) includes acryloxy-functional organosilicon monomers having the following general formula,

Chemical formula

[0055] For example, in certain embodiments, D 1 includes a linear alkylene group optionally substituted with an alkylamino group, and Y 1 includes a branched siloxane moiety. In such embodiments, the acryloxy-functional organosilicon monomer may have the following general formula,

Chemical formula

Chemical formula

Chemical formula

[0056] Regarding the aforementioned formula of the acryloxy-functional organosilicon monomer, the siloxane monomer can be linear or branched. For example, in some embodiments, Y 1 is a branched siloxane of the formula -Si(R 3 )3 as defined above and described. In some such embodiments, Y 1 is selected from the following branched siloxane moieties (i) to (iv)

Chemical formula

Chemical formula

[0057] In some embodiments, Y 1is a linear siloxane moiety having the following general formula, [Chemical formula] each of the subscripts n, o, p, q, r, s, and t and R 4 are as defined and described above. For example, in some such embodiments, each R 4 is methyl, and as a result, Y 1 is a linear siloxane moiety having the following general formula, [Chemical formula] wherein the subscripts n, o, p, q, r, s, and t are as defined and described above. However, it should be understood that any R 4 can be selected from other hydrocarbyl groups such as those described above. In some such embodiments, Y 1 is selected from the following siloxane moieties (i) to (iii), [Chemical formula] wherein 1 ≦ n ≦ 100 and the subscript r is 3 to 9.

[0058] Regarding the above formula of the acryloxy-functional organosilicon monomer, R 1 is H or CH3. In certain embodiments, R 1 is H (i.e., the acryloxy-functional organosilicon monomer contains an acryloxy group). In other embodiments, R 1 is CH3 such that the acryloxy-functional organosilicon component (A) contains a (meth)acryloxy-functional organosilicon monomer (i.e., the acryloxy-functional organosilicon monomer is further defined as having (meth)acryloxy functionality). In either case, as will be understood by those skilled in the art, the term acryloxy functionality, like the term "acrylate" has been conventionally understood to include acrylate esters, (meth)acrylate esters, etc., refers to an unsubstituted acryloxy functional group (e.g., R 1which is H) and a methyl-substituted acryloxy functional group (e.g., R 1 which is CH3) can be used to indicate a genus encompassing both.

[0059] The acryloxy-functional organosilicon monomer can be utilized in any amount in component (A) selected by those skilled in the art, for example, depending on the specific component selected for the reaction, the reaction parameters used, the scale of the reaction (e.g., the total amount of the acryloxy-functional organosilicon monomer to be reacted and / or the silicone acrylate polymer to be prepared), and the like.

[0060] The acryloxy-functional organosilicon monomer can be prepared or otherwise obtained, i.e., obtained as a prepared compound. Methods for preparing the acryloxy-functional organosilicon monomer are well known in the art, and such compounds and suitable starting materials are commercially available from various suppliers. The preparation of the acryloxy-functional organosilicon monomer can be carried out in part in its presence before combining it with other components of the acryloxy-functional organosilicon component (A).

[0061] Similarly, the acryloxy-functional organosilicon monomer can be in any form in component (A), for example, it may be undiluted (i.e., no solvent, carrier vehicle, diluent, etc. is present), or it can be placed in a carrier vehicle such as a solvent or a dispersant. For example, the acryloxy-functional organosilicon component (A) can include a carrier vehicle such as one of those described herein. It will be understood that the acryloxy-functional organosilicon monomer can be combined with the carrier vehicle before, during, or after combination with any one or more other components of the acryloxy-functional organosilicon component (A) when utilized. In some embodiments, the acryloxy-functional organosilicon component (A) does not contain or substantially does not contain a carrier vehicle. For example, in certain embodiments, the method can include stripping the acryloxy-functional organosilicon monomer of volatile substances and / or solvents, or distilling the acryloxy-functional organosilicon monomer from solvents, volatile substances, etc. to prepare the acryloxy-functional organosilicon component (A).

[0062] The acryloxy-functional organosilicon component (A) can include one type of acryloxy-functional organosilicon monomer, or it can include two or more types of acryloxy-functional organosilicon monomers that are different from each other with respect to at least one of the variables R 1 , D 1 , and Y 1 as defined and described above.

[0063] Any epoxy-functional acrylate component (B) includes an oxiranyl-functional acryloxy monomer (i.e., an oxiranyl acrylate ester monomer) having the following general formula,

Chemical formula

[0064] For example, in certain embodiments, X 1 is an epoxyalkyl group (e.g., an epoxyethyl group, an epoxypropyl group (i.e., an oxiranylmethyl group), an oxiranylbutyl group, an epoxyhexyl group, an oxiranolodithyl group, etc.), or an epoxycycloalkyl group (e.g., an epoxycyclopentyl group, an epoxycyclohexyl group, etc.). For example, in some embodiments, X 1 is a hydrocarbyl group substituted with an epoxyethyl group of the formula

Chemical formula

Chemical formula

Chemical formula

[0065] Regarding the foregoing formula of the oxiranyl-functional acryloxy monomer, R 1 is H or CH3. In certain embodiments, R 1 is H (i.e., the oxiranyl-functional acryloxy monomer contains an acryloxy group). In other embodiments, R 1 ​is CH3 such that the epoxy-functional acrylate component (B) contains an oxiranyl-functional (meth)acryloxy monomer.

[0066] In view of the description herein, those skilled in the art will understand that examples of suitable oxiranyl-functional acryloxy monomers for use in component (B) include glycidyl acrylate, epoxycyclohexyl acrylate, etc. For example, in certain embodiments, the epoxy-functional acrylate component (B) comprises glycidyl acrylate, glycidyl (meth)acrylate, glycidyl oxybutyl acrylate, (3,4-epoxycyclohexyl)methyl acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, (3,4-epoxycyclohexyl)ethyl acrylate, (3,4-epoxycyclohexyl)ethyl (meth)acrylate, or combinations thereof.

[0067] The oxiranyl-functional acryloxy monomer can be utilized in any amount in component (B) when the component (B) selected by those skilled in the art is used, for example, depending on the specific components selected for the reaction, the reaction parameters used, the scale of the reaction (e.g., the total amount of the oxiranyl-functional acryloxy monomer to be reacted and / or the silicone acrylate polymer to be prepared), etc.

[0068] The oxiranyl-functional acryloxy monomer can be prepared or otherwise obtained, i.e., obtained as a prepared compound. Methods for preparing the oxiranyl-functional acryloxy monomer are known in the art, and such compounds and suitable starting materials are commercially available from various suppliers. The preparation of the oxiranyl-functional acryloxy monomer can be carried out, in part, before or in the presence of combining it with other components of the epoxy-functional acrylate component (B).

[0069] Similarly, the oxiranyl-functional acryloxy monomer may, in some cases, be in any form in component (B), for example, it may be undiluted (i.e., without the presence of a solvent, carrier vehicle, diluent, etc.), or it may be placed in a carrier vehicle such as a solvent or a dispersant. For example, the epoxy-functional acrylate component (B) may include a carrier vehicle such as one of those described herein. When the oxiranyl-functional acryloxy monomer is utilized, it will be understood that it can be combined with the carrier vehicle before, during, or after combination with any one or more of the other components of the epoxy-functional acrylate component (B). In some embodiments, the epoxy-functional acrylate component (B) does not contain or substantially does not contain a carrier vehicle. For example, in certain embodiments, the method may include stripping the volatile substances and / or solvent of the oxiranyl-functional acryloxy monomer, or distilling the oxiranyl-functional acryloxy monomer from the solvent, volatile substances, etc. to prepare the epoxy-functional acrylate component (B) (e.g., when the method includes preparing the oxiranyl-functional acryloxy monomer).

[0070] When utilized, the epoxy-functional acrylate component (B) may include one type of oxiranyl-functional acryloxy monomer, or two or more types of oxiranyl-functional acryloxy monomers that are different from each other with respect to at least one of the variables R 1 and X 1 as defined and described above.

[0071] The acrylate component (C) is optional and includes an acrylate monomer having the following general formula,

Chemical formula

[0072] As introduced above, R 1 is H or CH3, and R 2 is H or a hydrocarbyl group, typically a hydrocarbyl group. Thus, the acrylate monomer is generally selected from substituted and unsubstituted acrylic acids, substituted and unsubstituted acrylic esters, such as acrylate esters (i.e., "acrylates") and (meth)acrylate esters (i.e., "(meth)acrylates" or "methacrylates") acrylic esters, etc., which are also referred to as acryloxy or (meth)acryloxy functional hydrocarbon compounds, respectively, and can be monofunctional or polyfunctional (e.g., with respect to the number of acryloxy groups thereon).

[0073] Examples of specific monofunctional acrylates suitable for use as the acrylate monomer of component (C) include, for example, 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, 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-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (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)(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)acrylate, methoxypoly(propylene glycol) (meth)acrylate, and derivatives thereof are included.

[0074] Examples of specific polyfunctional acrylic monomers 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, 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-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanediol dimethacrylate, 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, polyoxyethylene / polyoxypropylene-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, etc., and derivatives thereof are included.

[0075] The above exemplary acrylic monomers are described only with respect to (meth)acrylate species for the sake of brevity, and those skilled in the art will readily understand that other alkyl and / or hydride versions of such compounds can be utilized as well. For example, those skilled in the art will understand that the above monomer “2-ethylhexyl (meth)acrylate” exemplifies both 2-ethylhexyl (meth)acrylate and 2-ethylhexyl acrylate. Similarly, in the above examples, the acrylic monomers are generally described as propenoates (i.e., α,β-unsaturated esters), but it should be understood that the term “acrylate” used in these descriptions can equally refer to the acids, salts, and / or conjugate bases of the exemplified esters. For example, those skilled in the art will understand that the above monomer “methyl acrylate” exemplifies the methyl ester of acrylic acid, as well as acrylic acid, acrylate salts (e.g., sodium acrylate), etc. Further, polyfunctional derivatives / variants of the above acrylic monomers can also be utilized. For example, the above monomer “ethyl (meth)acrylate” exemplifies functionalized derivatives such as substituted ethyl (meth)acrylate and ethyl acrylate (e.g., hydroxyethyl (meth)acrylate and hydroxyethyl acrylate, respectively).

[0076] In certain embodiments, the acrylic ester monomer of component (C), when utilized, is selected from methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (BA), isobornyl acrylate, isobornyl acrylate, cyclohexyl acrylate, neopentyl acrylate, 2-ethylhexyl acrylate (2-EHA), hydroxyethyl acrylate (HEA), methyl (meth)acrylate (MMA), ethyl (meth)acrylate (EMA), n-butyl (meth)acrylate (BMA), isobutyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate (2-EHMA), hydroxyethyl (meth)acrylate (HEMA), and acetoacetoxyethyl (meth)acrylate (AAEM).

[0077] The acrylic ester monomer, when utilized, can be utilized in any amount in component (C) selected by one of ordinary skill in the art and depends, for example, on the particular components selected for the reaction, the reaction parameters used, the scale of the reaction (e.g., the total amount of acrylic ester monomer being reacted and / or the silicone acrylate polymer being prepared).

[0078] The acrylate monomer can be prepared or otherwise obtained, i.e., obtained as a prepared compound. Methods for preparing the acrylate monomer are known in the art, and such compounds and suitable starting materials are commercially available from various suppliers. The preparation of the acrylate monomer can be carried out, in part, before or in the presence of any other component of the acrylate component (C), before combining it with that component. Generally, methods for preparing acrylate-functional compounds utilize at least one acrylic monomer having an acryloyloxy or alkylacryloyloxy group (i.e., acrylate, alkyl acrylate, acrylic acid, alkyl acrylic acid, etc., as well as their derivatives and / or combinations). Such acrylic monomers may be monofunctional or polyfunctional acrylic monomers.

[0079] Similarly, when the acrylate monomer is utilized, it can be in any form in the component (C), for example, undiluted (i.e., in the absence of a solvent, carrier vehicle, diluent, etc.) or placed in a carrier vehicle such as a solvent or dispersant. For example, the acrylate component (C) can include a carrier vehicle such as one of those described herein. It will be understood that the acrylate monomer can be combined with the carrier vehicle before, during, or after combination with any one or more other components of the acrylate component (C) when it is utilized. In some embodiments, the acrylate component (C) does not include or substantially does not include a carrier vehicle. For example, in certain embodiments, the method can include stripping the acrylate monomer of volatile substances and / or solvents, or distilling the acrylate monomer from solvents, volatile substances, etc. to prepare the acrylate component (C) (e.g., if the method includes preparing the acrylate monomer).

[0080] The acrylate component (C), when utilized, can include one type of acrylate monomer, or the variables R defined and described above 1 and R 2It may contain two or more types of acrylate monomers, such as two, three, or more acrylic oxy-functional organic silicon monomers that are different from each other with respect to at least one of them.

[0081] Furthermore, when the acrylate component (C) is utilized, it may contain additional monomers or co-reactants, that is, those other than the acrylate monomers described above. The additional monomers / co-reactants are not particularly limited and may be selected from carboxylic acid monomers, such as acrylic acid (AA), (meth)acrylic acid (MAA), and their derivatives (for example, the acid of any of the above acrylate esters), itaconic acid, and their salts; acrylamide monomers, such as amide derivatives / morphologies of any of the acrylate esters described above (for example, isodecyl acrylamide, 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.); sulfonic acid monomers, such as sodium styrene sulfonate, acrylamide-methyl-propanesulfonate, and their salts; phosphoric acid monomers, such as phosphoethyl methacrylate and its salts; other monomers, such as styrene, acrylonitrile, and copolymerized multi-ethylenically unsaturated monomer groups (for example, allyl (meth)acrylate, diallyl phthalate, 1,4-butylene glycol di(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, divinylbenzene, etc.); and derivatives, modified forms, and combinations thereof. It may also be advantageous to incorporate such monomer groups non-uniformly into the silicone acrylate polymer to form multiphase particles having, for example, a core-shell, hemispherical, or occluded morphology.

[0082] The following description of any component regarding the preparation of a silicone acrylate polymer, based on any components (B) and (C), and thus references to components (A), (B), and (C) should not be construed as requiring components (B) and (C), but rather, it should be understood that they are collective components utilized to prepare a silicone acrylate copolymer that includes any components.

[0083] In certain embodiments, an acryloxy-functional organosilicon component (A), an optional epoxy-functional acrylate component (B), and an optional acrylate component (C) react in the presence of (D) a free radical initiator (i.e., "initiator (D)") to prepare a silicone-acrylate polymer.

[0084] The particular type or particular compound selected within or for use as initiator (D) will be readily selected by one of ordinary skill in the art based on the particular component (A) selected and any (B) and any (C), and any carrier vehicle, if any, present during the reaction. Generally, initiator (D) is not particularly limited and can include or be any compound suitable for promoting the polymerization of the alkenyl functional groups of the various monomers of components (A), (B), and (C) as would be understood by one of ordinary skill in the art considering the description herein (e.g., via radical polymerization, radical coupling, etc.). Thus, initiator (D) is typically a radical polymerization initiator such as any of those conventionally used for the polymerization of vinyl-functional compounds.

[0085] Examples of initiators include various peroxides such as inorganic peroxides (e.g., hydrogen peroxide derivatives such as potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and various organic peroxides including benzoyl peroxide, t-butyl peroxymaleic acid, succinic peroxide, t-butyl hydroperoxide, tert-butyl peroxypivalate (tBPPiv), etc. Additional examples of initiators include compounds that generate free radicals upon exposure to reaction conditions when discharged by, for example, certain types of energy sources (e.g., heat, UV light, etc.). Examples of such compounds include (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), triazine, thiazine, e.g., 10-phenylphenothiazine, 9,9'-bixanthene-9,9'-diol, 2,2-dimethoxy-2-phenylacetophenone, peroxides such as 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane (DBPH), etc., as well as their derivatives, modified forms, and combinations. In some embodiments, the initiator (D) can include or be a photoactivatable catalyst that can initiate polymerization via irradiation and / or heat (e.g., upon exposure to radiation having a wavelength of 150 to 800 nanometers (nm)). For example, in certain embodiments, the initiator (D) can include a fac-tris(2-phenylpyridine)-based catalyst that can be utilized to polymerize the monomers of components (A), (B), and (C) utilized via a reaction involving photo-mediated radical generation. Other examples of suitable initiators as described above (e.g., various peroxy and azo compounds) are known in the art.

[0086] The initiator (D) can be used in any amount selected by those skilled in the art. For example, it depends on the specific initiator (D) selected (e.g., the concentration / amount of its active ingredient, the type of catalyst used, etc.), the reaction parameters used, and the scale of the reaction (e.g., the total amount of components (A), (B), and (C) used). The molar ratio of the initiator (D) to the components (A), (B), and (C) used in the reaction (i.e., their monomers) can affect the rate and / or amount of polymerization for preparing the silicone acrylate polymer. Therefore, the amount of the initiator (D) compared to the monomers of the components (A), (B), and (C), as well as the molar ratio between them, can vary. Typically, these relative amounts and molar ratios are selected to maximize the reaction of the components (A), (B), and (C) while minimizing the loading of the initiator (D) (e.g., for reasons such as increasing the economic efficiency of the reaction and the simplicity of purifying the reaction product formed).

[0087] In certain embodiments, the initiator (D) is used in the range of 0.01 to 20 parts by weight, or 0.1 to 10 parts by weight, based on 100 parts by weight in total of the component (A).

[0088] In certain embodiments, initiator (D) is utilized in the reaction in an amount of 0.01 to 20 wt%, based on the total amount (i.e., weight / weight) of component (A) utilized. For example, initiator (D) can be used in an amount of 0.01 to 15 wt%, such as 0.1 to 15 wt%, or 0.1 to 10 wt%, based on the total amount of component (A). In other embodiments, initiator (D) is utilized in the reaction in an amount of 0.01 to 20 wt%, such as 0.01 to 15 wt%, or 0.1 to 15, or 1 to 10 wt%, based on the total amount of components (A), (B), and (C) utilized. Ratios outside of these ranges can also be utilized, and it will be understood that initiator (D) can be utilized in one or more portions, such as during the reaction of components (A), (B), and (C) (e.g., if additional initiator (D) is introduced during the reaction of components (A), B), and (C) as the reaction progresses towards completion). It should also be understood that initiator (D) itself can comprise more than one initiator compound, such as two, three, or more different initiator compounds, which can be utilized individually or collectively in an amount within one of the above ranges.

[0089] In certain embodiments, the acryloxy-functional organosilicon component (A), optional epoxy-functional acrylate component (B), and optional acrylate component (C) react in the presence of (E) a solvent to prepare a silicone-acrylate polymer. The solvent used herein aids in the fluidization of the starting materials (i.e., components (A), (B), and (C)), but does not essentially react with any of these starting materials and is otherwise not particularly limited. Thus, the solvent will be selected based on the solubility of the starting materials, volatility (i.e., the vapor pressure of the solvent), parameters of the preparation method used, etc. Solubility refers to a solvent sufficient to dissolve and / or disperse components (A), (B), and (C). Examples of specific solvents include any carrier vehicle, fluid, etc. suitable for adequately transporting, dissolving, and / or dispersing any component of the reaction mixture during the preparation of the silicone acrylate polymer.

[0090] In some embodiments, the solvent (E) comprises or is an organic solvent. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; aliphatic hydrocarbons such as heptane, hexane, octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and chloroform; ketones such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, and propylene glycol methyl ether acetate; alcohols such as methanol, ethanol, isopropanol, butanol, or n-propanol; and other organic compounds that are liquid / fluid at typical reaction temperatures such as dimethyl sulfoxide, dimethylformamide, acetonitrile, tetrahydrofuran, white spirit, mineral spirit, naphtha, n-methylpyrrolidone, and their derivatives, modifications, and combinations.

[0091] In certain embodiments, the reaction of components (A), (B), and (C) is carried out in the absence of any carrier vehicle or solvent. For example, the carrier vehicle or solvent may be discretely combined with the acryloxy-functional organosilicon component (A), the epoxy-functional acrylate component (B), the acrylate component (C), and / or the initiator (D). In these or other embodiments, none of components (A), (B), (C), and (D) are disposed in any carrier vehicle or solvent and thus are not present in the reaction mixture during the polymerization reaction (i.e., the reaction mixture does not contain or substantially does not contain a solvent). Nevertheless, in certain embodiments, one of components (A), (B), and (C) may be a carrier, in which case, for example, it can be utilized as a fluid in an amount sufficient to carry, dissolve, or disperse any other component of the reaction mixture.

[0092] The amount of the solvent (E) used may depend on various factors including the type of the solvent selected, the amounts and types of the components (A), (B), (C), and (D) used, etc. Typically, the amount of the solvent (E) may range from 0.1 to 99% by weight based on the total weight of the components (A), (B), and (C). In some embodiments, the solvent (E) is used in an amount of 1 to 99% by weight, such as 2 to 99, or 2 to 95, or 2 to 90, or 2 to 80, or 2 to 70, or 2 to 60, or 2 to 50% by weight based on the total weight of the components (A), (B), and (C). In other embodiments, the solvent (E) is used in an amount of 50 to 99% by weight, such as 60 to 99, or 70 to 99, or 80 to 99, or 90 to 99, or 95 to 99% by weight based on the total weight of the components (A), (B), and (C).

[0093] In certain embodiments, the acryloxy-functional organosilicon component (A), optional epoxy-functional acrylate component (B), and optional acrylate component (C) react in the presence of a (F) chain transfer agent to prepare a silicone acrylate polymer. Compounds suitable for use with the chain transfer agent (F) (i.e., in the radical polymerization of the acryloxy-functional monomers of the components (A), (B), and (C)) are known in the art and are exemplified by various thiol compounds.

[0094] For example, in some embodiments, the chain transfer agent (F) comprises or is a thiol compound having the general formula X-SH, wherein X is a substituted and unsubstituted hydrocarbon moiety, an organosilicon moiety, and combinations thereof, such as any of those described above with respect to R. Examples of such thiol compounds include dodecyl mercaptan (i.e., dodecanethiol), 2-mercaptoethanol, butyl mercaptopropionate, methyl mercaptopropionate, mercaptopropionic acid, etc., and combinations thereof. Other examples of thiol compounds suitable for the chain transfer agent (F) include mercaptotrialkoxysilane, mercaptodialkoxysilane, and mercaptomonalkoxysilane. For example, in some embodiments, the chain transfer agent (F) comprises or is (H3CO)2(H3C)Si(CH2)3SH. In these or other embodiments, the chain transfer agent (F) comprises or is dodecanethiol.

[0095] The chain transfer agent (F) is typically utilized to terminate growing polymer chains (e.g., formed by the polymerization of monomers of components (A), (B), and (C)) and initiate the formation of new polymer chains. In this way, the chain transfer agent (F) can be utilized to control the molecular weight of the silicone acrylate polymer being prepared and to select the end-functionalization of the polymer chains. For example, when the chain transfer agent (F) comprises dodecanethiol, the silicone acrylate polymer prepared may comprise the following general formula,

Chemical formula

[0096] In certain embodiments, the chain transfer agent (F) is used in the reaction in an amount of 0.1 to 20 wt%, based on the total amount (i.e., weight / weight) of one of the components (A), (B), and (C) being utilized. For example, the chain transfer agent (F) can be used in an amount of 0.1 to 15 wt%, based on the total amount of one of the components (A), (B), and (C) being utilized, such as in an amount of 0.5 to 15, or 1 to 15, or 5 to 15 wt%. In other embodiments, the chain transfer agent (F) is used in the reaction in an amount of 0.01 to 20 wt%, based on the total amount of the components (A), (B), and (C) being utilized, such as in an amount of 0.1 to 20, or 1 to 20, or 1 to 15, or 5 to 15 wt%, based on the total amount of the components (A), (B), and (C). Ratios outside of these ranges can also be used, and it will be understood that the chain transfer agent (F) can be used in one or more portions, each within one of the above ranges (e.g., during the reaction of the components (A), (B), and (C), such as when the chain transfer agent (F) moves towards completion during the reaction of the components (A), B), and (C)). It should also be understood that the chain transfer agent (F) itself can include more than one type of compound, such as two, three, or more different such compounds suitable to act / function as a chain transfer agent, and these can be used individually or collectively in an amount within one of the above ranges.

[0097] In certain embodiments, the chain transfer agent (F) is not used.

[0098] In certain embodiments, the method includes combining a silicone acrylate copolymer with a chain terminator (G). Typically, the chain terminator (G) includes an alkyl acrylate having the general formula H2CCHC(O)OR 2 wherein R 2 is independently selected and as defined above. Typically, the chain terminator (G) is used only when the chain transfer agent (F) is also used, and the chain terminator (G) consumes or reacts with any residual amount of the chain transfer agent (F).

[0099] Generally, reacting components (A), (B), and (C) (i.e., when utilized) involves combining an acryloxy-functional organosilicon component (A), an epoxy-functional acrylate component (B), and an optional acrylate component (C) in the presence of an initiator (D) for the reaction and / or other components (e.g., a chain transfer agent (F), a solvent (E), etc.) (collectively referred to as "reaction components"). In other words, generally, beyond simply combining the components, there are generally no prior steps required for the reaction. As introduced above, the reaction can generally be defined as a radical polymerization reaction or otherwise characterized, and the specific parameters and conditions of the reaction can be selected by those well-known in the art of such reactions to prepare a silicone acrylate polymer.

[0100] Typically, the reaction components are reacted in a vessel or reactor to prepare a silicone acrylate polymer. As described below, when the reaction is carried out at an elevated or reduced temperature, the vessel or reactor can be heated or cooled in any suitable manner, e.g., via a jacket, mantle, exchanger, bath, coil, etc. In certain embodiments, these parameters are optimized to achieve a silicone acrylate polymer having the same DP or Xn achievable with a chain transfer agent (F) while avoiding the use of a chain transfer agent (F).

[0101] Any of the reaction components may be supplied to the vessel together or separately, or dispensed into the vessel in any order and in any combination. However, typically, the initiator (D) will be combined with the monomer-containing component (e.g., components (A), (B), and / or (C)) only when the reaction is initiated, as will be understood by those skilled in the art. In certain embodiments, components (B) and (C) are added to the vessel containing component (A). In such embodiments, components (B) and (C) may first be combined with each other prior to addition or may be added sequentially to the vessel (e.g., (B) after (C)). In certain embodiments, component (D) is added to the vessel containing components (A) and (B) as a pre-formed catalyst / initiator or as individual components for forming the initiator (D) in situ. Generally, references herein to the "reaction mixture" generally refer to a mixture of the reaction components (e.g., as obtained by combining the components as described above), i.e., components (A), (B), and (D), and optionally, component (C), (E), and / or (F) if utilized.

[0102] The reaction components can be reacted in various molar ratios depending on the specific silicone acrylate polymer to be prepared (for example, with respect to the above formula (I), specific values and / or ratios of the subscripts a, b, and c are desirable). In addition, the molar ratio between the components depends on the active concentration of the reactive molecules therein, for example, the amount of acryloxy-functional organosilicon monomer in the acryloxy-functional organosilicon component (A). Thus, the molar ratio of the components during the reaction will typically be selected based on the amounts of the reactive monomers utilized. For example, in certain embodiments, the preparation method comprises disposing in the reaction mixture an amount of components (A) and (B) sufficient to react the acryloxy-functional organosilicon monomer and the oxiranyl acrylate ester monomer in a ratio of (A):(B) of 10:1 to 1:10, such as 8:1 to 1:8, or 6:1 to 1:6, or 4:1 to 1:4, or 2:1 to 1:2, or 1:1. In these or other embodiments, the preparation method comprises disposing in the reaction mixture an amount of components (A) and (C) sufficient to react the acryloxy-functional organosilicon monomer and the acrylate ester monomer in a ratio of (A):(C) of 10:1 to 1:10, such as 8:1 to 1:8, or 6:1 to 1:6, or 4:1 to 1:4, or 2:1 to 1:2, or 1:1. In these or other embodiments, the preparation method comprises disposing in the reaction mixture an amount of components (B) and (C) sufficient to react the oxiranyl acrylate ester monomer and the acrylate ester monomer in a ratio of (B):(C) of 10:1 to 1:10, such as 8:1 to 1:8, or 6:1 to 1:6, or 4:1 to 1:4, or 2:1 to 1:2, or 1:1. However, ratios outside of these ranges can also be utilized, and one of ordinary skill in the art will select the specific ratio to be utilized considering, for example, the specific silicone-acrylate polymer to be prepared, the specific monomers utilized, etc. For example, if more than one acryloxy-functional organosilicon monomer is utilized, each such monomer can be utilized at one of the above ratios.

[0103] The components of the reaction can be utilized in any form (e.g., undiluted (i.e., without the presence of a solvent, carrier vehicle, diluent, etc.), disposed in a carrier vehicle, etc.), obtained, or formed. For example, as described above, each compound or component can be provided “as is,” i.e., ready for the reaction to prepare a silicone acrylate polymer. Alternatively, one or more components can be formed before or during the reaction. For example, in some embodiments, the method includes preparing an acryloxy-functional organosilicon component (A), an epoxy-functional acrylate component (B), and / or an acrylate component (C).

[0104] The method can further include stirring the reaction mixture during and / or after formation. Stirring can, for example, facilitate the mixing and contact of the reaction components when combined in their reaction mixture. Such contact can be carried out independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), using other conditions. The other conditions can be adjusted to enhance the contact of components (A), (B), and (C), and thus the reaction (i.e., polymerization) to form a silicone acrylate polymer. The other conditions can be conditions effective to obtain results for improving the reaction yield or minimizing the amount of certain reaction by-products included in the reaction product with the silicone acrylate polymer.

[0105] In some embodiments, the reaction is carried out at an elevated temperature. The elevated temperature will be selected and controlled according to specific reaction components, the reaction parameters selected, the reaction parameters utilized (e.g., whether open to ambient pressure, sealed, under reduced pressure, etc.). Thus, the elevated temperature will be readily selected by those skilled in the art considering the reaction conditions and parameters selected, as well as the description herein. The elevated temperature is typically above 25 °C (ambient temperature) to 250 °C, for example, 30 - 225, or 40 - 200, or 50 - 200, or 50 - 180, or 50 - 160, or 50 - 150, or 60 - 150, or 70 - 140, or 80 - 130, or 90 - 120, or 100 - 120 °C. In certain embodiments, the elevated temperature is selected and / or controlled based on the boiling point of the solvent (E), such as when reflux conditions are utilized.

[0106] It should be understood that the elevated temperature can also be different from the above ranges. For example, when both elevated temperature and reduced or high pressure are utilized, other or alternative reaction conditions can be used. For example, in certain embodiments, reduced pressure or high pressure is utilized to maintain the progress of the reaction while using a lower reaction temperature, which can result in a decrease in the formation of undesirable by-products (e.g., degradation and / or decomposition by-products). Similarly, it should be understood that the reaction parameters can be modified during the reaction of the reaction components. For example, temperature, pressure, and other parameters can be independently selected or modified during the reaction. Any of these parameters can be, independently, ambient parameters (e.g., room temperature and / or atmospheric pressure) and / or non-ambient parameters (e.g., low or high temperature and / or reduced or high pressure). Any parameter can also be modified dynamically, in real time, i.e., changed during the process, or static (e.g., during the duration of the reaction or any part thereof). Oxygen can optionally be removed from the reaction during the preparation method, for example, by bubbling nitrogen or another inert gas into the vessel.

[0107] The time for which the reaction to prepare the silicone acrylate polymer is carried out correlates with the scale, the reaction parameters and conditions utilized, the reaction components selected, etc. At a relatively large scale (e.g., greater than 1, or 5, or 10, or 50, or 100 kg), the reaction can be carried out for a period of several hours such as 2 to 240, or 2 to 120, or 2 to 96, or 2 to 72, or 2 to 48, or 2 to 36, or 2 to 24, or 2 to 12, or 3, 4, 5, 6, 12, 18, 24, 36, or 48 hours (e.g., by monitoring the conversion of components (A), (B), and / or (C), the production of silicone - acrylate polymers etc. by chromatography and / or spectroscopy). In certain embodiments, the time for which the reaction is carried out is greater than 0 or 240 hours, or 1 to 120 hours, or 1 to 96 hours, or 1 to 72 hours, or 1 to 48 hours, or 1 to 36 hours, or 1 to 24 hours, or 1 to 12 hours, or 2 to 12 hours, or 2 to 8 hours after the reaction components are combined.

[0108] Generally, the reaction of components (A), (B), and (C) prepares a reaction product containing the silicone acrylate polymer. In particular, over the course of the reaction, the reaction mixture includes increasing the amount of the silicone acrylate polymer to be prepared and decreasing the amount of the monomers of components (A), (B), and (C) utilized in the reaction. When the reaction is complete (e.g., one or more of components (A), (B), and (C) are consumed and no additional silicone acrylate polymer is being prepared), the reaction mixture can be referred to as a reaction product containing the silicone acrylate polymer. Thus, the reaction product typically includes any residual amounts of reaction components, as well as their decomposition and / or reaction products. If the reaction is carried out in any carrier vehicle or solvent (e.g., solvent (E)), the reaction product can also include such carrier vehicle or solvent.

[0109] In certain embodiments, the method further includes isolating and / or purifying the silicone acrylate polymer from the reaction product. As used herein, isolating the silicone acrylate polymer is typically defined as increasing the relative concentration of the silicone acrylate polymer compared to other compounds combined therewith (e.g., in the reaction product or a purified version thereof). Thus, as understood in the art, isolation / purification can include removing other compounds from such a combination (i.e., reducing the amount of impurities that bind to the silicone-acrylate polymer in the reaction product, for example) and / or removing the silicone acrylate polymer itself from the combination. Any suitable technique and / or protocol for isolation can be utilized. Examples of suitable isolation techniques include distillation, stripping / evaporation, extraction, filtration, washing, partitioning, phase separation, chromatography, and the like. As will be understood by those skilled in the art, any one of these techniques can be used in combination with (i.e., sequentially) any other technique to isolate the silicone acrylate polymer. Isolating can include purifying the silicone acrylate polymer and thus it should be understood that purification can be included. However, purifying the silicone acrylate polymer can include alternative and / or additional techniques compared to those utilized in isolating the silicone acrylate polymer. Regardless of the particular technique selected, isolation and / or purification of the silicone acrylate polymer can be carried out continuously (i.e., in-line) with the reaction itself and thus can be automated. In other examples, purification can be a separate procedure to which the reaction product containing the silicone-acrylate polymer is subjected.

[0110] The silicone acrylate polymer prepared via the preparation method is a reaction product in which reaction components (for example, each acryloxy-functional organosilicon monomer of component (A), each oxiranyl acrylate ester monomer of component (B), each acrylic ester monomer of component (C), each radical polymerization active compound of component (D), and each thiol compound of component (F), etc., when such components are utilized) are utilized. Therefore, it should be understood that, for example, depending on the specific reaction components selected and the reaction conditions utilized, many variations and specific species of the silicone acrylate polymer can be prepared. However, the silicone acrylate polymer prepared by the preparation method corresponds to the above general average unit formula (I).

[0111] In certain embodiments, the liquid composition further comprises one or more additional components such as one or more additives other than components (I) and (II) (for example, drugs, adjuvants, components, modifiers, auxiliary components, etc.).

[0112] Additives suitable for use in the liquid composition can be classified into many different technical terms, and it should be understood that just because an additive is classified into such a term does not mean that it is limited to that function. Further, some additives can be present in specific components of the liquid composition (for example, in the case of a multi-component composition), or alternatively, can be incorporated when forming the liquid composition.

[0113] Typically, a liquid composition can contain any number of additives, for example, depending on the specific type and / or function in the liquid composition. For example, in certain embodiments, the liquid composition contains a filler, a filler treatment agent, a surface modifier, a surfactant rheology modifier, a viscosity modifier, a binder, a thickener, a tackifier, an adhesion promoter, a defoaming agent, a compatibilizer, a bulking agent, a plasticizer, a terminal blocker, a reaction inhibitor, a desiccant, a water releasing agent, a colorant (e.g., pigment, dye, etc.), an anti-degradation additive, a biocide, a flame retardant, a corrosion inhibitor, a catalyst inhibitor, a UV absorber, an antioxidant, a light stabilizer, a catalyst (e.g., other than catalyst (C)), a precursor catalyst, or a catalyst generator, an initiator (e.g., a thermally activated initiator, an electro-magnetically activated initiator, etc.), a photoacid generator, a heat stabilizer, etc., as well as derivatives, modified forms, and combinations thereof, or can contain one or more additives consisting essentially of or consisting of the same.

[0114] One or more additives can be present in an amount of any suitable weight percent (wt%) of the liquid composition, for example, 0.01 wt% to 65 wt%, for example, 0.05 to 35, or 0.1 to 15, or 0.5 to 5 wt%. In these or other embodiments, one or more additives can be present in the liquid composition in an amount of 0.1 wt% or less, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 wt% or more of the liquid composition. A person skilled in the art can easily determine the suitable amount of a specific additive, for example, depending on the type of additive and the desired result.

[0115] In certain embodiments, the liquid composition substantially does not contain or does not contain a reaction catalyst or promoter other than components (I) and (II) (e.g., with respect to the crosslinking reaction of components (I) and (II)). In these or other embodiments, the liquid composition substantially does not contain or does not contain a carrier vehicle, i.e., other than components (I) and (II) (e.g., when one or both of components (I) and (II) can act as a carrier vehicle).

[0116] In certain embodiments, the liquid composition is further defined as (i) a solvent-based composition, (ii) an aqueous composition, (iii) an oil composition, (iv) a film-forming composition, (v) a curable composition, (vi) a coating composition, (vii) a paint composition, (viii) a surface treatment composition, or (ix) an adhesive composition. As understood in the art, such end-use compositions may contain any additional components. For example, when the liquid composition is a curable composition, a curing agent and / or catalyst is typically included in or combined with the liquid composition. Those skilled in the art are immediately aware of how to formulate such end-use compositions with the liquid compositions of the present invention, including based on any functionalization of the silicone acrylate polymer.

[0117] The liquid composition can be used, for example, to prepare a film or a coating. For example, the liquid composition can be at least one of a film-forming agent, a surface treatment agent, an additive for coating, an additive for paint, or an additive for adhesion.

[0118] Polymers are often referred to as "made from", "comprising", or "consisting of" one or more specific monomers, or as "based on", "formed from", or "derived from" a particular monomer or monomer type, or as "containing" a particular monomer content or proportion of a particular monomer. However, in this context, the term "monomer" should be understood to refer not to the monomer units of the polymer itself, i.e., the polymerization residues of the specific monomers used in the preparation of the polymer, or unpolymerized monomer species, but to units that can be prepared. Thus, as used herein, a polymer is generally referred to as having monomer units in polymerized form, each corresponding to an unpolymerized monomer (i.e., even when such a monomer is not used to prepare a particular monomer unit, such as when a particular monomer is used to prepare a particular polymer).

[0119] In any of the above polymers, trace impurities can be incorporated into the polymer structure or otherwise present in the polymer structure without changing the characterization of the polymer itself, which is generally understood to be classified based on the average monomer unit formula (i.e., excluding trace impurities from, for example, catalyst residues, initiators, terminators, etc. that can be incorporated into and / or present in the polymer).

[0120] It should be understood that the appended claims are not limited to the specific compounds, compositions, or methods expressed in and described in the "Detailed Description of the Invention" and may vary among specific embodiments within the scope of the appended claims. For any Markush group relied upon herein to describe a particular feature or aspect of various embodiments, different, special, and / or unexpected results may be obtained from each member of each Markush group independent of all other Markush members. Each element of a Markush group may be relied upon individually and / or in combination and may provide a basis appropriate for a particular embodiment within the scope of the appended claims.

[0121] The following examples showing embodiments of the present disclosure are intended to illustrate the present invention and not to limit it. Unless otherwise specified, all reactions are carried out under air and all solvents, substrates, and reagents are purchased from various commercial suppliers or otherwise obtained.

[0122] The following instruments and property evaluation procedures / parameters are used to evaluate various physical properties of the compounds and compositions prepared in the following examples. In all of the following examples, the resulting silicone acrylate polymers were liquid at room temperature even in the absence of an organic solvent or carrier vehicle.

[0123] Nuclear Magnetic Resonance (NMR) spectroscopy Nuclear magnetic resonance (NMR) analysis was performed on a Varian Unity INOVA 400 (400 MHz) spectrometer using a 10 mm tube without silicon and an appropriate solvent (e.g., CDCl3). Chemical shifts of the spectra were referenced to the internal protium solvent resonance ( 1 H: CDCl3; 29 Si: tetramethylsilane).

[0124] Gel permeation chromatography (GPC) Gel permeation chromatography (GPC) analysis was carried out on an Agilent 1260 Infinity II chromatograph equipped with an Agilent refractive index detector using GPC / SEC software, with a PLgel 5μm Mixed-C column (300x7.5 mm; Polymer Laboratories) equipped in front of a PLgel 5μm guard column. The analysis used a tetrahydrofuran (THF) mobile phase at a standard flow rate of 1.0 mL / min at 35 °C. The sample was dissolved in THF (5 mg / mL) and optionally filtered through a 0.2 μm PTFE syringe filter before injection. Calibration was performed using narrow polystyrene (PS) standards ranging from 580 to 2,300,000 g / mol that fit a third-degree polynomial curve.

[0125] Dynamic Viscosity (DV) Viscosity measurements were performed on an Anton-Paar Physica MCR301 rheometer equipped with a 50 mm stainless steel cone-plate fixture (CP 25, 1.988-inch cone angle with 104 μM truncation) at an operating temperature of 25 °C using the expert flow curve steady-state control method available in the attached software package (Rheoplus 32 V3.40). A shear rate sweep from 0.1 to 500 s -1 was performed, and values at a frequency of 10 radians / second were reported in centipoise (cP).

[0126] Glass transition temperature (Tg) The glass transition temperature was measured via DSC Q2000 V24.10 based on differential scanning calorimetry in accordance with ASTM D7426 with a sample size of approximately 5 - 10 mg in the second heating cycle.

[0127] The various components used in the examples are shown in Table 1 below.

Table 1

[0128] Examples 1 - 6 and Comparative Examples 1 - 2:

[0129] General Procedure 1: Preparation of silicone acrylate polymer

[0130] Examples 1 - 6 and Comparative Examples 1 - 2 follow General Procedure 1. Specifically, solvent (E) (80 g) was added to an oven - dried 500 mL four - neck round - bottom flask equipped with a stirring shaft, condenser, thermocouple port, addition port, and heating mantle. The contents of the flask were heated to 85 °C. Then, the monomer blend described in Table 2 below was prepared and divided into two plastic syringes (except for Example 6 which uses only one plastic syringe) equipped with a supply line to the flask and a Luer - lock connector connected to a syringe pump. The monomer blend was supplied at a rate of 7.267 g / min. Five minutes after starting the supply of the monomer blend to the flask, a mixture of initiator (D1) (11 g) and solvent (E) (20 g) (the "initiator blend") was added to another plastic syringe equipped with a supply line to the flask and a Luer - lock connector connected to a syringe pump. The initiator blend was supplied at a rate of 0.148 mL / min. The monomer blend was supplied for 1 hour and the initiator blend was supplied for 2 hours. Thirty minutes after stopping the supply of the monomer blend, 4 grams of chain end (G1) was placed into the flask. After stopping the supply of the initiator blend, the flask was heated for 80 minutes. The reaction was 1 monitored via 1H NMR. In Table 2 below, the amounts of the components in each monomer blend are in grams, and C.E. indicates comparative examples.

Table 2

[0131] Properties of Examples 1 - 6 and Comparative Examples 1 - 2:

[0132] The silicone acrylate polymers of Examples 1 - 6 were targeted to have a number average molecular weight of 2,000 Da. The number average degree of polymerization (Xn) varies based on the monomers (A1), (C1), and (C2) used when their molecular weights are different. The following Table 3 shows the physical properties of the silicone acrylate polymers of Examples 1 - 6 and Comparative Examples 1 - 2 measured as described above.

Table 3

[0133] Examples 7 - 12 and Comparative Examples 3 - 4:

[0134] General Procedure 2: Preparation of Silicone Acrylate Polymer

[0135] Examples 7 to 12 and Comparative Examples 3 to 4 follow General Procedure 2. In particular, solvent (E) (80 g) was added to an oven-dried 500 mL four-neck round-bottom flask equipped with a stirring shaft, condenser, thermocouple port, addition port, and heating mantle. The contents of the flask were heated to 85 °C. Next, the monomer blends described in Table 4 below were prepared and divided into two plastic syringes (except for Example 12 which utilizes only one plastic syringe) equipped with a supply line to the flask and a Luer lock connector connected to a syringe pump. The monomer blend is supplied at a rate of 7.145 g / min. Five minutes after starting the supply of the monomer blend to the flask, a mixture of initiator (D1) (11 g) and solvent (E) (20 g) (“initiator blend”) was added to another plastic syringe equipped with a supply line to the flask and a Luer lock connector connected to a syringe pump. The initiator blend is supplied at a rate of 0.148 mL / min. The monomer blend was supplied for 1 hour and the initiator blend was supplied for 2 hours. Thirty minutes after stopping the supply of the monomer blend, 4 grams of chain end (G1) was placed in the flask. After stopping the supply of the initiator blend, the flask was heated for 80 minutes. The reaction is 1 monitored via 1H NMR. In Table 4 below, the amounts of the components in each monomer blend are in grams and C.E. indicates a comparative example.

Table 4

[0136] Properties of Examples 7 to 12 and Comparative Examples 3 to 4:

[0137] The silicone acrylate polymers of Examples 7 to 12 were targeted to have a number average degree of polymerization (Xn) of 12.4. The number average molecular weight (Mn) varies based on the monomers (A1), (C1), and (C2) utilized because their molecular weights differ in relation to Xn. Table 5 below shows the physical properties of the silicone acrylate polymers of Examples 7 to 12 and Comparative Examples 3 to 4 measured as described above.

Table 5

[0138] Examples 13 to 17 and Comparative Example 5:

[0139] General Procedure 3: Preparation of a silicone acrylate polymer

[0140] Examples 13 to 17 and Comparative Example 5 follow General Procedure 3. General Procedure 3 is specific to Example 13, and Examples 14 to 17 and Comparative Example 5 modify the molar ratios of the components utilized in the monomer blend as defined below and described in Table 6. In particular, in Example 13 and General Procedure 3, the solvent (E) (10 g) was added to an oven-dried 500 mL four-neck round-bottom flask equipped with a stirring shaft, condenser, thermocouple port, addition port, and heating mantle. The organosilicon monomer (A1) (45 g), organosilicon monomer (A2) (47 g), epoxy-functional mixture, acrylate monomer (B1) (11 g), and chain transfer agent (F1) (5 g) (collectively referred to as the "monomer blend") were prepared in a plastic syringe equipped with a Luer lock connector that was connected to a syringe pump and had a supply line to the flask. A mixture of initiator (D2) (3.15 g) and solvent (E) (30 g) (the "initiator blend") was added to another plastic syringe equipped with a Luer lock connector that had a supply line to the flask and was connected to a syringe pump. The flask was heated to reach the target temperature (110°C) with stirring, at which point the supply of the monomer blend was started (rate: 2 g / min; duration: 54 min). After a 5-minute delay, the supply of the initiator blend was started (duration: 150 min), and the reaction was 1 monitored via 1H NMR. After completion of both supplies, the reaction mixture was maintained at the target temperature (110°C) with stirring for 1 hour and then cooled to room temperature (about 23°C) to obtain a reaction product containing an epoxide-functional silicone acrylate polymer. The reaction product had the solvent removed in vacuo to isolate the epoxide-functional silicone acrylate polymer, which was then characterized according to the above procedure.

[0141] As described above, the molar ratios of components (A1), (A2), and (B1) were modified in Examples 14 to 17 and Comparative Example 5 beyond the specific values used above in Example 13 and General Procedure 3. For Examples 13 to 17 and Comparative Example 5, the molar ratios are shown in Table 6 below. The values in Table 6 are mole fractions based on the total amount of the monomer blend used in each example. [Table 6]

[0142] Properties of Examples 13 to 17 and Comparative Example 5:

[0143] The number average molecular weight, polydispersity, and viscosity of the silicone-acrylate copolymers of Examples 13 to 17 and Comparative Example 5 were measured as described above and are shown in Table 7 below. [Table 7]

Claims

1. A liquid composition comprising a silicone acrylate polymer having the following average unit formula: 【Chemical Formula 1】 In the formula, each R １ is independently H or CH ３ and each R ２ is independently H or a substituted or unsubstituted hydrocarbyl group, X １ is an independently selected epoxide-functional moiety, each D １ is a divalent linking group, and each Y １ is a siloxane moiety containing at least one of [T] and / or [Q] siloxy units represented by the following general structural moieties, which are independently selected: 【Chemical Formula 2】 In the formula, each Rii is independently a monovalent or polyvalent substituent, where a ≥ 1, b ≥ 0, and c ≥ 0, provided that a + b + c ≥ 2, and the moieties represented by the subscripts a, b, and c can be in any order in the silicone acrylate polymer, a silicone acrylate polymer, and Optionally, a carrier vehicle, and the liquid composition contains a total amount of organic solvent in the range of 0 to 25% by weight based on the total weight of the liquid composition, the liquid composition, wherein the silicone acrylate polymer has a number average molecular weight (Mn) of 500 to 5000 Da.

2. The liquid composition according to claim 1, wherein the silicone acrylate polymer comprises (i) a dynamic viscosity of less than 1,000 centipoise (cP) at 25°C, (ii) a mass dispersity (Dm) of 1.1 to 10, (iii) a number average degree of polymerization (Xn) of 2 to 35, (iv) a glass transition temperature (Tg) of -20°C to -60°C, or (v) any combination of (i) to (iv).

3. In the silicone acrylate polymer, (i) each R １ is CH ３and (ii) each R ２ is an independently selected unsubstituted hydrocarbyl group having 1 to 10 carbon atoms, (iii) the subscript a is from 1 to 25, (iv) the subscript b is from 0 to 25, (v) the subscript c is from 1 to 25, and (vi) at least one siloxane moiety Y １ comprises a siloxane group having the following general formula: 【Chemical Formula 3】 In the formula, 0 ≦ n ≦ 100, the subscript o is from 2 to 6, the subscript p is 0 or 1, the subscript q is 0 or 1, the subscript r is from 0 to 9, the subscript s is 0 or 1, and the subscript t is 0 or 2, provided that when the subscript s is 1, the subscript t is 0, and when the subscript s is 0, the subscript t is 2, or (vii) any combination of (i) to (vi), the liquid composition according to claim 1 or 2.

4. A method for preparing the liquid composition according to any one of claims 1 to 3, comprising combining the silicone acrylate polymer and optionally the carrier vehicle to obtain the liquid composition.

5. Further comprising preparing the silicone acrylate polymer by reacting (A) an acryloxy-functional organosilicon compound, optional (B) an epoxy-functional acrylate component, and optional (C) an acrylate component, and obtaining the silicone acrylate polymer, wherein the acryloxy-functional organosilicon component (A) comprises an acryloxy-functional organosilicon monomer having the following general formula: 【Chemical Formula 4】 wherein the epoxy-functional acrylate component (B) comprises an oxiranyl acrylate ester monomer having the following general formula: 【Chemical Formula 5】 wherein the optional acrylate component (C) comprises an acrylate ester monomer having the following general formula: 【Chemical Formula 6】 wherein each R １ , R ２ , D １ , Y １ , and X １ is independently selected and is as defined above, the method according to claim 4.

6. The acrylate component (C) is utilized, each corresponding to the above general formula, and at least two acrylate monomers different from each other with respect to at least one of R １ and R ２ are included, and the acryloxy-functional organosilicon compound (A), any of the epoxy-functional acrylate components (B), and the acrylate component (C) react in the presence of (D) an initiator, (E) a solvent, (F) a chain transfer agent, or any combination of (D) to (F), the method according to claim 5.

7. The acryloxy-functional organosilicon compound (A), any of the epoxy-functional acrylate components (B), and any of the acrylate components (C) react in the presence of a chain transfer agent (F), and the chain transfer agent (F) includes a thiol compound having the general formula Y-SH, and Y is selected from a substituted and unsubstituted hydrocarbon moiety, an organosilicon moiety, and combinations thereof, the method according to claim 5.

8. In the thiol compound of the chain transfer agent (F), (i) Y includes a substituted or unsubstituted hydrocarbyl group having 6 to 12 carbon atoms, (ii) Y includes an alkylene group having 2 to 11 carbon atoms, (iii) Y includes an alkoxysilane group having the formula -Si(OR ３ )( ｃ (R ３ )( ３－ｃ ), each R ３ is an independently selected unsubstituted hydrocarbyl group having 1 to 6 carbon atoms, the subscript c is 1, 2, or 3, or (iv) any combination of (i) to (iii), the method according to claim 7.

9. The method further comprises combining the silicone acrylate polymer with a chain terminator (G), wherein the chain terminator (G) has the general formula H ２ CCHC(O)OR ２ and comprises an alkyl acrylate, where R ２ is independently selected and as defined above. The method according to any one of claims 5 to 8. **Claim 10** A film formed from the liquid composition according to any one of claims 1 to 3.

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