Comb polymer

Abstract

A comb polymer has the structure (I) wherein a + b + c + d + e = 100 mol%; each of d and e is optional so long as at least one of d and e is greater than zero; n is 1 to 300, wherein when n is > 1, the -O-CHR6-CHR7- groups are the same or different; each of X, X1 and X2 is O or NH; R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; R2 is -S-R11-Si(OR')3; R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; each of R4 and R5 is H or CH3; each of R6 and R7 is H or a C1-10 hydrocarbyl; each of R8 and R9 is H or CH3; R10 is C1-10 hydrocarbyl; R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group; and m is 0 or 1.

Description

PCT PATENT APPLICATION 364.1746PC2 COMB POLYMER CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 675,431 filed on July 25, 2024; U.S. Provisional Application No. 63 / 675,433 filed on July 25, 2024; U.S. Provisional Application No. 63 / 762,782 filed on February 25, 2025; and U.S. Provisional Application No. 63 / 813,355 filed on May 28, 2025, each of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present disclosure generally relates to comb polymers. More particularly, this disclosure relates to a particular comb polymer that can include a silicon atom. BACKGROUND

[0003] Comb polymers are a type of branched polymer that include a linear backbone with approximately regularly spaced side chains attached thereto. The side chains can enhance the solubility of the comb polymer in various solvents and can modify mechanical properties of the comb polymer such as flexibility and toughness. The side chains can also hinder crystallization thereby making the comb polymer more amorphous.

[0004] Comb polymers can be synthesized using several methods, including using preformed side chains that are grafted onto a preformed backbone. Alternatively, side chains can be grown from the backbone by initiating polymerization at specific sites along the backbone. Moreover, the backbone and side chains can be polymerized simultaneously.

[0005] While comb polymers offer numerous advantages, they also present several challenges. For example, the synthesis of comb polymers can be more complex and time-consuming compared to linear polymers. The need to control the structure precisely (e.g., length and density of side chains) can also require sophisticated techniques. Due to the complexity of their synthesis as well as monomer costs, comb polymers can be more expensive to produce than their linear counterparts.

[0006] In addition, achieving uniformity in the molecular weight and distribution of side chains can be difficult, leading to heterogeneity in the polymer, which can affect performance and reproducibility. Furthermore, while side chains can improve solubility, they can also introduce solubility issues if not properly designed, leading to poor performance in certain applications. Depending on the side chain composition, comb polymers might exhibit less thermal and mechanical stability compared to linear polymers.PCT PATENT APPLICATION 364.1746PC2

[0007] Comb polymers, while versatile and beneficial in many applications, present challenges in their synthesis, cost, environmental impact, and specific performance characteristics. Accordingly, there remains an opportunity for improvement.

[0008] Furthermore, other desirable features and characteristics of the present disclosure will become apparent from the subsequent detailed description of the disclosure and the appended claims, taken in conjunction with the background of the disclosure. BRIEF SUMMARY

[0009] This disclosure provides a comb polymer having the formula (I):wherein a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1 and X2 independently is O or NH; (iii) R1is a C1-C32linear or branched hydrocarbyl group or aryl group; (iv) R2is -S-R11-Si(OR’)3;PCT PATENT APPLICATION 364.1746PC2 (v) R3is H a C1-C32linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5is H or CH3; (viii) R6 is H or a C1-10 hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8is H or CH3; (xi) R9 is H or CH3; (xii) R10 is C1-10 hydrocarbyl ; (xiii) R11is a C1-C32linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1. DETAILED DESCRIPTION

[0010] The following detailed description is merely exemplary in nature and is not intended to limit the current composition. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

[0011] Embodiments of the present disclosure are generally directed to polymers, compositions including the same, and methods for forming the same. For the sake of brevity, conventional techniques related to making polymers and such compositions may not be described in detail herein. Moreover, the various tasks and process steps described herein may be incorporated into a more comprehensive procedure or process having additional steps or functionality not described in detail herein. In particular, various steps in the manufacture of polymers and associated compositions are well-known and so, in the interest of brevity, many conventional steps will only be described briefly herein or will be omitted entirely without providing the well-known process details.

[0012] In this disclosure, the terminology “about” can describe values ± 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10%, in various embodiments. Moreover, it is contemplated that, in various non-limiting embodiments, it is to be appreciated that all numerical values as provided herein, save for the actual examples, are approximate values with endpoints or particular values intended to be read as “about” or “approximately” the value as recited. It is also contemplated that all isomers and chiral options for each compound described herein are hereby expressly contemplated for use herein inPCT PATENT APPLICATION 364.1746PC2 various non-limiting embodiments. Moreover, in this disclosure, the subscripts of non-chemical elements, e.g. (R1, R2, etc.) do not indicate that more than 1 group (e.g. R group) is present. They are used merely to differentiate between groups. However, the subscripts for chemical elements such as carbon (e.g. C1-C22) are indicative of the total number of atoms of that chemical element.

[0013] Throughout this disclosure, the terminology percent "actives" is well recognized in the art and means the percent amount of active or actual compound or molecule present as compared to, for example, a total weight of a diluted solution of a solvent and such a compound. Some compounds, such as a solvent, are not described relative to a percent actives because it is well known to be approximately 100% actives. Any one or more of the values described herein may be alternatively described as percent actives as would be understood by the skilled person.

[0014] In various embodiments, the terminology “free of” describes embodiments that include less than about 5, 4, 3, 2, 1, 0.5, or 0.1, weight percent (or weight percent actives) of the compound or element at issue using an appropriate weight basis as would be understood by one of skill in the art. In other embodiments, the terminology “free of” describes embodiments that have zero weight percent of the compound or element at issue.

[0015] The terminology “consists essentially of” may describe various non-limiting embodiments that are free of one or more optional compounds described herein and / or free of one or more polymers, surfactants, additives, solvents, etc.

[0016] It is to be understood that the subscripts of polymers are typically described as average values because the synthesis of polymers typically produces a distribution of various individual molecules.

[0017] The polymer, particles, and compositions disclosed herein may suitably comprise, consist of, or consist essentially of the components, elements, and process delineations described herein. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein. Comb Polymer

[0018] The comb polymer has the formula (I):PCT PATENT APPLICATION 364.1746PC2a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1and X2independently is O or NH; (iii) R1is a C1-C32linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3; (v) R3 is H a C1-C32 linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5 is H or CH3; (viii) R6is H or a C1-10hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl; (x) R8 is H or CH3; (xi) R9is H or CH3; (xii) R10is C1-10hydrocarbyl ;PCT PATENT APPLICATION 364.1746PC2 (xiii) R11is a C1-C32linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1.

[0019] As set forth above, a + b + c + d + e = 100 mol%. The particular amount of any one of a, b, c, d, and e is not particularly limited. For example, any one of a, b, c, d, and / or e can each independently be about 1 to about 99 mol percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0020] In various embodiments, a is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, a is from about 1 to about 25, about 2 to about 24, about 3 to about 23, about 4 to about 24, about 5 to about 25, about 6 to about 24, about 7 to about 23, about 8 to about 22, about 9 to about 21, about 10 to about 20, about 11 to about 19, about 12 to about 18, about 13 to about 17, about 14 to about 16, or about 15 to about 16, mol%. In another embodiment, a is from 3 to about 18, about 4 to about 17, about 5 to about 16, about 6 to about 15, about 7 to about 14, about 8 to about 13, about 9 to about 12, or about 10 to about 11, mol %. In a further embodiment, a is about 6 to about 14, about 7 to about 13, about 8 to about 12, or about 9 to about 11, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0021] In various embodiments, b is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, b is from about 0 to about 95 mol%. In another embodiment, b is from about 60 to about 90, about 65 to about 85, about 70 to about 80, or about 75 to about 80, mol %. In another embodiment, b is from about 70 to about 85, about 70 to about 75, or about 80 to about 85, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and betweenPCT PATENT APPLICATION 364.1746PC2 those set forth above, are hereby expressly contemplated for use herein.

[0022] In various embodiments, c is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, c is from about zero to about 90 mol%. In another embodiment, c is from about 2 to about 20, about 3 to about 19, about 4 to about 18, about 5 to about 17, about 6 to about 16, about 7 to about 15, about 8 to about 14, about 9 to about 13, about 10 to about 12, or about 11 to about 12, mol %. In another embodiment, c is about 5 to about 15, about 6 to about 14, about 7 to about 13, about 8 to about 12, about 9 to about 11, or about 10 to about 11, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0023] In various embodiments, d is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, d is about 0.05 to about 10 mol, about 0.5 to about 10, about 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6, about 0.05 to about 0.5, about 0.1 to about 0.45, about 0.15 to about 0.4, about 0.2 to about 0.35, about 0.25 to about 0.3, about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0024] In various embodiments, e is from about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55, mole percent based on a total number of moles of a, b, c, d, and e in the comb polymer. In one embodiment, e is about 0.05 to about 10 mol, about 0.5 to about 10, about 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6, about 0.05 to about 0.5, about 0.1 to about 0.45, about 0.15 to about 0.4, about 0.2 to about 0.35, about 0.25 to about 0.3, about 0.1 to about 1, about 0.2 to about 0.9, about 0.3 to about 0.8, about 0.4 to about 0.7, or about 0.5 to about 0.6, mol %. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional,PCT PATENT APPLICATION 364.1746PC2 including and between those set forth above, are hereby expressly contemplated for use herein.

[0025] In the comb polymer, each of d and e is optional so long as at least one of d and e is greater than zero. For example, the comb polymer can have d without e or can have e without d, or can have d and e, but cannot be lacking both d and e.

[0026] In still other embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, of each of a, b, c, d, and e, independently, are hereby expressly contemplated for use with each other herein. In other words, in various non-limiting embodiments, all combinations of amounts of a, b, c, d, and e, set forth above, such that a+b+c+d+e = 100%, are hereby expressly contemplated for use herein, even though each combination is not expressly set forth herein.

[0027] In other embodiments, it is contemplated that an additional monomer, apart from a, b, c, d, and e, could be used. This monomer may be any known in the art, e.g. those that may react with acrylate monomers, any of the monomers described herein, the acrylate polymer, the comb polymer, etc. In such embodiments, then the total of a+b+c+d+e+additional monomer(s) = 100%. Just as above, all values and ranges thereof, both whole and fractional, including and between those set forth above, of each of a, b, c, d, e, and any additional monomer(s), independently, are hereby expressly contemplated for use with each other herein. In other words, in various non- limiting embodiments, all combinations of amounts of a, b, c, d, e, and any additional monomer(s) set forth above, such that a+b+c+d+e+additional monomer(s) = 100%, are hereby expressly contemplated for use herein, even though each combination is not expressly set forth herein.

[0028] In other embodiments, n is about 1 to about 300. In various embodiments, n is about 1. In other embodiments, n is greater than 1. When n is > 1, then the individual-O-CHR6-CHR7- groups are the same or different. In still other embodiments, n is from 1 to about 10, about 2 to about 9, about 3 to about 8, about 4 to about 7, about 5 to about 6. In further embodiments, n is about 5 to about 95, about 10 to about 90, about 15 to about 85, about 20 to about 80, about 25 to about 75, about 30 to about 70, about 35 to about 65, about 40 to about 60, about 45 to about 55, or about 50 to about 55. In other embodiments, n is about 10 to about 90, about 20 to about 80, about 30 to about 70, about 40 to about 60, or about 50. In further embodiments, n is about 25 to about 100, about 25 to about 50, about 50 to about 75, about 50 to about 100, about 25 to about 75, or about 75 to about 100. In other embodiments, n is from about 100 to about 300, about 110 to about 290, about 120 to about 280, about 130 to about 270, about 140 to about 260, about 150PCT PATENT APPLICATION 364.1746PC2 to about 250, about 160 to about 240, about 170 to about 230, about 180 to about 220, about 190 to about 210, or about 200 to about 210. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0029] In further embodiment, R6 and R7, which is referenced in the -O-CHR6-CHR7-group described above, is H or a C1-10 hydrocarbyl. In various embodiments, the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0030] Each of X, X1, and X2may independently be O or NH.

[0031] Moreover, R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group. In various embodiments, R1 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments, this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0032] In other embodiments, R2 is -S-R11-Si(OR’)3. In various embodiments, if R2 is not that group then it may be any number of groups that are common to solution polymers including, but not limited to, H, CH3, or an end group derived from an initiator, an alcohol or glycol or non Si containing mercaptans. Relative to R11, in various embodiments, this group is a hydrocarbyl group having 1 to 10 carbon atoms, e.g.1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In other embodiments, R11 is a C1-C32 linear or branched hydrocarbyl group or aryl group. In various embodiments, R11 has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments, this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0033] In further embodiments, R3 is a C1-C32 linear or branched hydrocarbyl group or aryl group. In various embodiments, R3has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, carbon atoms. In various embodiments,PCT PATENT APPLICATION 364.1746PC2 this group has 1 to 10 carbon atoms, 6 to 20 carbon atoms, 6 to 12 carbon atoms, 12 to 20 carbon atoms, etc. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0034] In other embodiments, each of R4and R5is independently H or CH3.

[0035] R6 is H or a C1-10 hydrocarbyl. In various embodiments, the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0036] R7is H or a C1-10hydrocarbyl. In various embodiments, the hydrocarbyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, carbon atoms, any may be branched, linear, or cyclic, and may be an alkyl, alkenyl, or alkynyl group, or may be an aryl or cycloaryl group. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0037] In further embodiments, each of R8 and R9 is independently H or CH3.

[0038] Relative to R10, this group is a hydrocarbyl group having 1 to 10 carbon atoms, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In various non-limiting embodiments, all values and ranges thereof, including and between those set forth above, are hereby expressly contemplated for use herein.

[0039] Moreover, m is 0 or 1.

[0040] In still other embodiments, one or more Si(OH)3groups is optional meaning that one or more may be included or may be excluded from the comb polymer.

[0041] In one embodiment: a is 1-25 mol%; b is 0-95 mol%; c is 0-90 mol%; and d is 0.05-10 mol%. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0042] In another embodiment: a is 0.5-75 mol%;PCT PATENT APPLICATION 364.1746PC2 b is 0-99 mol%; c is 0-99 mol%; d is 0 -10 mol%; and e is 0-10 mol%. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0043] In another embodiment: a is 1-50 mol%; b is 10-90 mol%; c is 10-90 mol%; d is 0-10 mol%; e is 0-10 mol%; n is 1-200, wherein the -O-CHR6-CHR7- groups are the same or different; X is O; R6 is H or CH3; and R7 is H or CH3. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0044] In another embodiment: a is 2-10 mol%; b is 15-85 mol%; c is 15-85 mol%; d is 0.05-10 mol%; n is 5-150, wherein the -O-CHR6-CHR7- groups are the same or different; X is O; R6 is H or CH3; and R7is H or CH3. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0045] In another embodiment, the comb polymer is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 1,000 g / mol;PCT PATENT APPLICATION 364.1746PC2 methyl methacrylate, methacrylic acid and vinyltrimethoxy silane wherein a is from about 10 to about 15 mol%; b is from about 75 to about 80 mol%; c is from about 5 to about 10 mol%; and d is from about 0.5 to about 1.5 mol%.

[0046] In another embodiment, the comb polymer is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 2,000 g / mol; methyl methacrylate, methacrylic acid and vinyltrimethoxy silane wherein a is from about 10 to about 15 mol%; b is from about 75 to about 80 mol%; c is from about 5 to about 10 mol%; and d is from about 0.5 to about 1.5 mol%.

[0047] In another embodiment, the comb polymer is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 5,000 g / mol; isopropyl alcohol; methyl methacrylate, methacrylic acid and vinyltrimethoxy silane wherein a is from about 5 to about 10 mol%; b is from about 75 to about 80 mol%; c is from about 15 to about 20 mol%; and d is from about 0.5 to about 1.5 mol%.

[0048] In another embodiment, the comb polymer is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 750 g / mol;PCT PATENT APPLICATION 364.1746PC2 3-mercapto propionic acid; acrylic acid; styrene; and vinyltrimethoxy silane wherein a is from about 10 to about 15 mol%; b is from about 35 to about 40 mol%; c is from about 45 to about 50 mol%; and d is from about 0.5 to about 1.5 mol%.

[0049] In another embodiment, the comb polymer is the reaction product of: 3-mercapto propionic acid; acrylic acid; styrene; hydroxypropyl acrylate; and vinyltrimethoxy silane wherein a is from about 25 to about 30 mol%; b is from about 35 to about 40 mol%; c is from about 25 to about 30 mol%; and d is from about 0.5 to about 1.5 mol%.

[0050] It is contemplated that the comb polymer itself may be free of, or include less than, 5, 4, 3, 2, 1, 0.5, or 0.1, mol% of one or more other polymers not described herein. For example, such polymers may be graft (co)polymers, (co)polymers, graft comb polymers, comb polymers that are not the comb polymer of this disclosure, etc. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. Method of Making the Comb Polymer

[0051] This disclosure also provides a method of forming the comb polymer that includes the step of (a) mixing monomers A, B, C, D, and / or chain transfer agent E, with water, and preferably an acid which may be any known in the art, to hydrolyze a silane to a silanol and form a mixture. Any method known in the art may be utilized to effect the above reactions.PCT PATENT APPLICATION 364.1746PC2

[0052] The method also includes the step of (b) introducing this mixture along with an initiator to a reactor under starve-fed conditions.

[0053] The individual monomers may be any described herein or known in the art to be used form the comb polymer. In various non-limiting embodiments, Monomers A, B, and C have the following formulas: (Monomer C); andwherein each substituent is as described above. In addition, in other non-limiting embodiments, monomer D has the formula: (Monomer D). In addition, and in oneE has the formula:PCT PATENT APPLICATION 364.1746PC2 (Chain Transfer Agent E).

[0054] In otherchain transfer agents are thiols such as 3- mercaptopropionic acid or 2-mercaptoethanol or lower secondary alcohols, typically isopropanol, can be used. In various embodiments, the chain transfer agent is chosen from mercaptans (e.g., n- dodecyl mercaptan); thiols (e.g., 2-mercaptoethanol); carbon tetrachloride (CCl4); alcohols (e.g., ethanol, isopropanol); sulfides (e.g., dimethyl disulfide); trithiocarbonates (e.g., ethyl xanthate); organic halides (e.g., bromoform); organic acids (e.g., acetic acid); nitro compounds (e.g., nitroethane); silicon-based compounds; and combinations thereof.

[0055] In still other embodiments, the chain transfer agent is a silanol, e.g. -S-R11-Si(OH)3; - S-R11-Si(OCH3)3; -S-R11-Si(OCH2CH3)3, or combinations thereof. For example, the chain transfer agent may be gamma-mercaptopropyl trimethoxy silane or mercaptopropyl trimethoxy silanol or combinations thereof.

[0056] In the above, each of the Monomers is introduced to the reactor in whatever molar ratio is desired. For example, the molar ratio of Monomers A:B:C:(D and / or E) may each independently be from (about 1:about 99). In various embodiments, the molar ratio of Monomers A:B:C:(D and / or E) is (about 1 to about 25) : (about 50 to about 95) : (about 1 to about 25) : (about 1 to about 25). Alternatively, any one or more of Monomers A, B, C, and D and / or E may be utilized as described anywhere in this disclosure in terms of identity and amount. Typically, e.g. at all times of the process, whatever molar ratio that is chosen is substantially unchanging and a total molar ratio of a + b + c + d and / or e = 100 mol%. The method then also includes the step of reacting Monomers A, B, C, and (D and / or E) to form the comb polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0057] The comb polymer is typically prepared from a polymerization mixture in an aqueous medium in the presence of any initiator or initiating system capable of liberating free radicals under the reaction conditions employed. The free radical initiators can be present in an amount of from about 0.01% to about 10 mol% based on total moles of monomer. In a typical embodiment, anPCT PATENT APPLICATION 364.1746PC2 initiating system is soluble in water to at least 0.1 weight percent, typically to at least 1 weight percent and most typically to at least 10 weight percent at 25°C. Suitable initiators include, but are not limited to, peroxides, azo initiators as well as redox systems, such as erythorbic acid, and metal ion based initiating systems. Initiators may also include both inorganic and organic peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide. In an embodiment, the inorganic peroxides, such as sodium persulfate, potassium persulfate and ammonium persulfate, are typical. In another embodiment, the initiators comprise metal ion based initiating systems including Fe and hydrogen peroxide, as well as Fe in combination with other peroxides. Organic peracids such as peracetic acid can be used. Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine, and the like. A typical system is persulfate alone such as sodium or ammonium persulfate or a redox system with iron and persulfate with hydrogen peroxide. Azo initiators, especially water-soluble azo initiators, may also be used. Water soluble azo initiators include, but are not limited to, 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'- Azobis(2-methylpropionamidine)dihydrochloride, 2,2'-Azobis[N-(2-carboxyethyl)-2- methylpropionamidine]hydrate, 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2- yl]propane}dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis(1-imino-1- pyrrolidino-2-ethylpropane)dihydrochloride, 2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)- 2-hydroxyethl]propionamide}, 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and others. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0058] The molecular weight of the comb polymer may be controlled by various compounds used in the art including, for example, chain transfer agents such as mercaptans, ferric and cupric salts, bisulfites, and lower secondary alcohols, typically isopropanol. Typically, the comb polymer starts to be more and more water insoluble as the content of monomer b increases over 75 mol%. Higher molecular weight comb polymers tend to acerbate the water insolubility. Therefore, a chain transfer agent can be used to minimize the effect on water insolubility by lowering the molecular weight of the comb polymer, e.g. when b is > 75 mol% or 79 mol%. As described above, typicalPCT PATENT APPLICATION 364.1746PC2 chain transfer agents are thiols such as 3-mercaptopropionic acid or 2-mercaptoethanol or lower secondary alcohols, typically isopropanol. In various embodiments, the chain transfer agent is chosen from mercaptans (e.g., n-dodecyl mercaptan); thiols (e.g., 2-mercaptoethanol); carbon tetrachloride (CCl4); alcohols (e.g., ethanol, isopropanol); sulfides (e.g., dimethyl disulfide); trithiocarbonates (e.g., ethyl xanthate); organic halides (e.g., bromoform); organic acids (e.g., acetic acid); nitro compounds (e.g., nitroethane); silicon-based compounds; and combinations thereof. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0059] The terminology “starve-fed” as used herein typically means introducing monomers gradually to a reactor at a rate sufficiently slow enough that the majority of each monomer introduced is consumed by the reaction before additional monomer is added. In a typical embodiment, at least 50% of the monomers are consumed by the reaction before more monomers are added, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 76%, or at least 77%, or at least 78%, or at least 79%, or at least 80%, or at least 81%, or at least 82%, or at least 83%, or at least 84%, or at least 85%, or at least 86%, or at least 87%, or at least 88%, or at least 89%, or at least 90%, or at least 91%, or at least 92%, or at least 93%, or at least 94%, or at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 99% of the monomers are consumed by the reaction before more monomers are added to the reactor. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein.

[0060] The terminology that describes that the feed molar ratio of monomers is “substantially unchanging” typically means that the feed moles of each monomer is at all times within about 10% by moles, typically about 5% by moles, more typically about 2% by moles, most typically about 0.5% by moles of the anticipated final molar amount of that monomer in the final polymer. In various non-limiting embodiments, all values and ranges thereof, both whole and fractional, including and between those set forth above, are hereby expressly contemplated for use herein. Compositions / Formulations

[0061] This disclosure also provides a composition or formulation that includes the comb polymer. The composition is not particularly limited and may be any known in the art. For example, the composition may be a paint or coating. In one embodiment, the composition is aPCT PATENT APPLICATION 364.1746PC2 lubricant. In another embodiment, the composition is an adhesive. In a further embodiment, the composition is a pharmaceutical composition. In another embodiment, the composition is a hydrogel. In a further embodiment, the composition is an ink or a cosmetic.

[0062] The composition may be formed using any method chosen by one of skill in the art. For example, the method may include the steps of combining one or more of the aforementioned components with one another in one or more parts and in a batch or continuous process.

[0063] The disclosure will now be described in greater detail with reference to the following non-limiting examples. EXAMPLES Example 1

[0064] An initial charge of 134.3.g of deionized water and 266.0.g of isopropyl alcohol was added to a reactor with inlet ports for an agitator, water cooled condenser, thermocouple, and adapters for the addition of monomer and initiator solutions. The reactor contents were heated to 80°C. A solution of 217.7 g of methoxy polyethylene glycol 1000 methacrylate (50% in water, Bisomer S10W) was fed into the reactor over 120 minutes. Simultaneously, a second monomer feed of 63 g of methyl methacrylate, 6.5.g of methacrylic acid and 1.2 grams of vinyltrimethoxy silane was added into the reactor over 120 minutes. An initiator solution of 3.5 grams of sodium persulfate was dissolved in 51.6 grams water was concurrently added, starting at the same time as the monomer solutions, for a period of 135 minutes. The reaction product was then held at 80°C for 60 minutes. The reactor was then set up for distillation and 6.8 g of 50% aqueous solution of sodium hydroxide in 230 g of water was then added. An azeotropic of 467 g of a mixture of water and isopropyl alcohol was then distilled.

[0065] The final comb polymer solution had b = 77.3 mol% of methyl methacrylate, a = 12.4 mol% of methoxy polyethylene glycol 1000 methacrylate (where n is approximately 23), c = 9.3 mol% of methacrylic acid and d = 1 mol% vinyltrimethoxy silane with a pH of 7.1 and 31.6% solids. Example 2

[0066] An initial charge of 95.1 g of deionized water and 201.5 g of isopropyl alcohol was added to a reactor with inlet ports for an agitator, water cooled condenser, thermocouple, and adapters for the addition of monomer and initiator solutions. The reactor contents were heated to 80°C. A solution of 299.6 g of methoxy polyethylene glycol 2000 methacrylate (50% in water,PCT PATENT APPLICATION 364.1746PC2 Bisomer S20W) was fed into the reactor over 120 minutes. Simultaneously, a second monomer feed of 45 g of methyl methacrylate, 4.7 g of methacrylic acid and 0.9 grams of vinyltrimethoxy silane was added into the reactor over 120 minutes. An initiator solution of 3.9 grams of sodium persulfate was dissolved in 47.4 grams water was concurrently added, starting at the same time as monomer solutions, for a period of 135 minutes. The reaction product was then held at 80°C for 60 minutes. The reactor was then set up for distillation and 1.2 g of 50% aqueous solution of sodium hydroxide and 280 g of water was then added. An azeotropic of 367 g of a mixture of water and isopropyl alcohol was then distilled.

[0067] The final comb polymer solution had b = 77.3 mol% of methyl methacrylate, a = 12.4 mol% of methoxy polyethylene glycol 2000 methacrylate (where n is approximately 46) and c = 9.3 mol% of methacrylic acid and d = 1 mol% vinyltrimethoxy silane with a pH of 4.0 and 33.6% solids. Example 3

[0068] An initial charge of 95.1 g of deionized water and 156.4 g of isopropyl alcohol was added to a reactor with inlet ports for an agitator, water cooled condenser, thermocouple, and adapters for the addition of monomer and initiator solutions. The reactor contents were heated to 80°C. A mixed monomer solution of 335 g of methoxy polyethylene glycol 5000 methacrylate (50% in water), 38.8 g of isopropyl alcohol, 42 g of methyl methacrylate, 7.7 g of methacrylic acid and 0.86 grams of vinyltrimethoxy silane was added into the reactor over 120 minutes. An initiator solution of 3.9 grams of sodium persulfate was dissolved in 47.4 grams water was concurrently added, starting at the same time as the mixed monomer solution, for a period of 135 minutes. The reaction product was then held at 80°C for 60 minutes. The reactor was then set up for distillation and 1.9 g of 50% aqueous solution of sodium hydroxide and 280 g of water was then added. An azeotropic of 353 g of a mixture of water and isopropyl alcohol was then distilled.

[0069] The final comb polymer solution had b = 76.5 mol% of methyl methacrylate, a = 6.1 mol% of methoxy polyethylene glycol 5000 methacrylate (where n is approximately 113) and c =16.3 mol% of methacrylic acid and d = 1.1 mol% vinyltrimethoxy silane with a pH of 4.1 and 30.4% solids.

[0070] Without intending to be bound by theory, it is contemplated that the silane could hydrolyze to silanol in this feed or when added to the reactor because both the acidic pH and temperature and water should hydrolyze the silane. Therefore, the comb polymer may be in aPCT PATENT APPLICATION 364.1746PC2 silanol form. Example 4

[0071] An initial charge of 150 g of deionized water, 0.049 grams of ferrous ammonium sulfate hexahydrate and 150 g of isopropyl alcohol was added to a reactor with inlet ports for an agitator, water cooled condenser, thermocouple, and adapters for the addition of monomer and initiator solutions. The reactor contents were heated to 82-85°C which is reflux. A monomer solution of 176.2 g of methoxy polyethylene glycol 750 methacrylate dissolved in 170 grams of water and 5.7 grams of 3-mercapto propionic acid (e.g. d is not zero) was fed into the reactor over 195 minutes. Simultaneously, a second monomer feed of 59.0 g of acrylic acid, 72.1 g of styrene and 2.6 g of vinyltrimethoxy silane was added into the reactor over 210 minutes. An initiator solution of 6.6 grams of sodium persulfate, 19.5 grams of 35% hydrogen peroxide dissolved in 80.0 grams water was concurrently added, starting at the same time as the monomer solutions, for a period of 240 minutes. The reaction product was then held at 85°C for 60 minutes. The reactor was then set up for distillation. 150 g of 2-Amino-2-methyl-1-propanol 50% dissolved in 350 g of water was fed during the distillation and an azeotropic of 327 g of a mixture of water and isopropyl alcohol was then distilled.

[0072] The final comb polymer solution had b = 39.7 mol% of styrene, a = 12.3 mol% of methoxy polyethylene glycol 750 methacrylate (where n is approximately 113) and c = 47.0 mol% of acrylic acid and d = 1.0 mol% vinyltrimethoxy silane with a pH of 7.4 and 35.3% solids. Example 5

[0073] An initial charge of 176 g of deionized water, 0.0784 grams of ferrous ammonium sulfate hexahydrate and 176 g of isopropyl alcohol was added to a reactor with inlet ports for an agitator, water cooled condenser, thermocouple, and adapters for the addition of monomer and initiator solutions. The reactor contents were heated to 82-85°C which is reflux. A solution of 9.2 grams of 3-mercapto propionic acid dissolved in 96 grams of water and was fed into the reactor over 195 minutes. Simultaneously, a monomer feed of and 59.6 g of acrylic acid, 115.4 g of styrene, 107.7 g of hydroxypropyl acrylate and 4.3 g of vinyltrimethoxy silane was added into the reactor over 195 minutes. An initiator solution of 10.6 grams of sodium persulfate, 3-1.5 grams of 35% hydrogen peroxide dissolved in 6 / 4.0 grams water was concurrently added, starting at the same time as the monomer solutions, for a period of 240 minutes. The reaction product was then held at 85°C for 60 minutes. The reactor was then set up for distillation. 147.2 g of 2-Amino-2-PCT PATENT APPLICATION 364.1746PC2 methyl-1-propanol 50% dissolved in 144 g of water was fed during the distillation and an azeotropic of 354 g of a mixture of water and isopropyl alcohol was then distilled. 160.0 g of water was then added during cooling.

[0074] The final comb polymer solution had b = 38.7 mol% of styrene, a = 29.6 mol% of methoxy hydroxypropyl acrylate (n=1 and R7 is CH3) and c = 29.6 mol% of acrylic acid and d = 1.03 mol% vinyltrimethoxy silane with a pH of 7.4 and 39.4% solids.

[0075] In various non-limiting embodiments, any compound, component, method step, physical property description, example, formulation, composition, etc. as described in the US provisional patent application filed on the same day, and designated as Attorney Docket: 364.1746P1, which is expressly incorporated herein in its entirety by reference, may be used herein.

[0076] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims.

Claims

PCT PATENT APPLICATION 364.1746PC2 CLAIMS What is claimed is:

1. A comb polymer having the formula (I):a + b + c + d + e = 100 mol%; wherein each of d and e is optional so long as at least one of d and e is greater than zero; (i) n is 1 to 300, wherein when n is > 1, then the individual -O-CHR6- CHR7- groups are the same or different; (ii) each of X, X1and X2independently is O or NH; (iii) R1 is a C1-C32 linear or branched hydrocarbyl group or aryl group; (iv) R2 is -S-R11-Si(OR’)3; (v) R3is H a C1-C32linear or branched hydrocarbyl group or aryl group; (vi) R4 is H or CH3; (vii) R5is H or CH3; (viii) R6is H or a C1-10hydrocarbyl; (ix) R7 is H or a C1-10 hydrocarbyl;PCT PATENT APPLICATION 364.1746PC2 (x) R8is H or CH3; (xi) R9 is H or CH3; (xii) R10 is C1-10 hydrocarbyl ; (xiii) R11is a C1-C32linear or branched hydrocarbyl group or aryl group; and (xiv) m is 0 or 1.

2. The comb polymer of claim 1 wherein: a is 0.5-75 mol%; b is 0-99 mol%; c is 0-99 mol%; d is 0-10 mol%; and e is 0-10 mol%.

3. The comb polymer of claim 1 wherein: a is 1-50 mol%; b is 10-90 mol%; c is 10-90 mol%; d is 0-10 mol%; e is 0-10 mol%; n is 1-200, wherein the -O-CHR6-CHR7- groups are the same or different; X is O; R6 is H or CH3; and R7is H or CH3.

4. The comb polymer of claim 1 wherein: a is 2-10 mol%; b is 15-85 mol%; c is 15-85 mol%; d is 0.05-10 mol%; n is 5-150, wherein the -O-CHR6-CHR7- groups are the same or different;PCT PATENT APPLICATION 364.1746PC2 X is O; R6 is H or CH3; and R7 is H or CH3.

5. The comb polymer of claim 1 that is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 1,000 g / mol; methyl methacrylate, methacrylic acid and vinyltrimethoxy silane wherein a is from about 10 to about 15 mol%; b is from about 75 to about 80 mol%; c is from about 5 to about 10 mol%; and d is from about 0.5 to about 1.5 mol%.

6. The comb polymer of claim 1 comprising the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 2,000 g / mol; methyl methacrylate, methacrylic acid and vinyltrimethoxy silane wherein a is from about 10 to about 15 mol%; b is from about 75 to about 80 mol%; c is from about 5 to about 10 mol%; and d is from about 0.5 to about 1.5 mol%.

7. The comb polymer of claim 1 that is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 5,000 g / mol; isopropyl alcohol; methyl methacrylate, methacrylic acid andPCT PATENT APPLICATION 364.1746PC2 vinyltrimethoxy silane wherein a is from about 5 to about 10 mol%; b is from about 75 to about 80 mol%; c is from about 15 to about 20 mol%; and d is from about 0.5 to about 1.5 mol%.

8. The comb polymer of claim 1 that is the reaction product of: methoxy polyethylene glycol methacrylate having a Mn of about 750 g / mol; 3-mercapto propionic acid; acrylic acid; styrene; and vinyltrimethoxy silane wherein a is from about 10 to about 15 mol%; b is from about 35 to about 40 mol%; c is from about 45 to about 50 mol%; and d is from about 0.5 to about 1.5 mol%.

9. The comb polymer of claim 1 that is the reaction product of: 3-mercapto propionic acid; acrylic acid; styrene; hydroxypropyl acrylate; and vinyltrimethoxy silane wherein a is from about 25 to about 30 mol%; b is from about 35 to about 40 mol%; c is from about 25 to about 30 mol%; and d is from about 0.5 to about 1.5 mol%.PCT PATENT APPLICATION 364.1746PC2 10. A method of forming the comb polymer of any preceding claim wherein said method comprises the steps of: introducing Monomers A, B, and C and optionally Monomer D and / or Chain Transfer Agent E to a reactor under starve-fed conditions; and polymerizing the Monomers and / or Chain Transfer Agent to form the comb polymer, wherein Monomer A has the following structure: (Monomer A);Monomer B has the following structure: ;Monomer C has the following structure:PCT PATENT APPLICATION 364.1746PC2 (Monomer C);Monomer D has the following structure: (Monomer D); andChain Transfer Agent E has the following structure: (Chain Transfer Agent E).

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