WO2024094511A1

WO2024094511A1 - Coating compositions having improved properties comprising a polymer formed from polymerizable surfactants

Info

Publication number: WO2024094511A1
Application number: PCT/EP2023/079736
Authority: WO
Inventors: Lichang Zhou; Dongchul Lee; Derek Pakenham; Eugene J. Anderson; Changheon Kang; Céline BUREL
Original assignee: Specialty Operations France
Priority date: 2022-11-02
Filing date: 2023-10-25
Publication date: 2024-05-10

Abstract

The present invention generally relates to coating compositions comprising a polymer formed from at least one polymerizable surfactant, in which the coating compositions have improved performance properties, such as improved dirt pick-up resistance (DPUR), improved hardness, and improved blocking resistance.

Description

Coating Compositions Having Improved Properties Comprising a Polymer Formed From Polymerizable Surfactants

Field of Invention

[001] The present invention generally relates to coating compositions comprising a polymer formed from at least one polymerizable surfactant. More specifically, the present invention generally relates to coating compositions comprising a polymer formed from at least one polymerizable surfactant, in which the coating compositions have improved performance properties, such as improved dirt pick-up resistance (DPUR), improved hardness, and improved blocking resistance. The present invention also relates to methods for making such coating compositions and using polymerizable surfactants, as well as using such coating compositions on the surface of a substrate in which the coating compositions provide improved DPUR, hardness, and blocking resistance thereof.

Background

[002] Surfactants are used in various applications and for different purposes, including for example in dispersions and emulsifications across numerous industries. For instance, surfactants are used in coatings, paints, adhesives, home care products, personal care products, construction, paper, inks, and the like. Many times products contain surfactants to help stabilize the same, or to improve certain properties, such as foaming, viscosity, or wettability of the products. However, surfactants can also be used in processes and industrial reactions. For example, surfactants can be used in polymerization reactions through a process called emulsion polymerization.

[003] In emulsion polymerization processes, polymers are formed in micelles, which are formed by the surfactants. In particular, the surfactants can help stabilize the micelles, which allow the reaction to continue, and therefore, allow the polymer to form and propagate. With respect to preparing latexes (e.g., aqueous latexes) in conventional emulsion polymerization processes, the non-polymerizable surfactant often times is an anionic surfactant or a mixture of anionic surfactant with nonionic surfactant. The non-polymerizable surfactant(s) is present in the emulsion polymerization process in a sufficient concentration to allow and promote polymerization of the monomer(s) to form the latex polymer, which results in the formation of latex particles. These non-polymerizable surfactants, along with reaction conditions, determine the properties of the polymer, such as the particle size of the latex particles. For example, anionic surfactants can provide shear stability to prevent loss due to coagulation. Nonionic surfactants can provide electrolyte or chemical stability to the growing latex particles. The type and structure of the surfactant or surfactants used during the emulsion polymerization process can dramatically impact the emulsion properties, which in turn can dramatically impact the formation of latex (and whether even the latex is formed), including the latex particle size, latex particle size distribution, and latex viscosity. Accordingly, surfactants not only play a critical role in emulsion polymerization processes generally, but also more specifically in emulsion polymerization processes for making latex.

[004] Yet, while surfactants may play a critical role in forming polymers during emulsion polymerization processes, surfactants remaining in or associated with the polymer, or surfactants that are otherwise transferred to the products from the process, can negatively affect the properties of the products. That is, while the surfactants may be needed in the polymerization process, the same surfactants can decrease the performance of the resulting products. For example, in paints and other coatings, the presence of excessive surfactants may contribute to increased water-sensitivity and water whitening, and may negatively affect the resulting coating or film. DPUR, hardness, blocking resistance, weatherability, durability, and adhesion can also be affected. In particular, surfactants in paints, adhesives, including pressure sensitive adhesives (PSA), inks, stains, and other coatings can make the resulting coating or film less resilient and durable.

[005] It is generally understood that the reduction in beneficial properties of the coating or film is largely due to the mobility of the surfactant. That is, conventional surfactants used in polymerization processes can be free or separate surfactant molecules within the coating or film. For example, locally high concentrations of surfactant molecules can form in the coating or film from the coalescence of surfactant-coated micelle spheres. When the coating is exposed to water, the surfactant molecules can be extracted or washed away from the coating or film, thereby making the coating or film more porous. Simply put, when the surfactants are washed away, the coating or film is no longer uniform, but rather can have pinholes, thin spots, or pathways to the substrate surface, which can be penetrated by water or other solvents or liquids. This can result in water, or other solvents or liquids, not only compromising the integrity of the coating or film, but can lead to degradation or damage to the underlying substrate surface (e.g., rust, damage, deterioration, etc.). Whitening, blooming, or blushing can also occur when surfactants are in the coating or film. As a result, the coating or film can become hazy or whiten, which reduces the original sheen of the coating or film.

[006] In order to address these problems, surfactants that are polymerizable (i.e., polymerizable surfactants) - also known as reactive surfactants - can be used in the polymerization process. Unlike conventional surfactants that are used in the polymerization process, which in general are only used to form the micelles, polymerizable surfactants also act as monomers or form part of the resulting polymer in the reaction. This minimizes and reduces the undesirable result of having free or separate surfactant molecules within the coating or film, which can then weaken and make the resulting coating or film less resilient and durable.

[007] Yet, even when generally using polymerizable surfactants in polymerization processes, the coatings or films having the polymers formed from the processes still may not have the desired properties. For instance, the coatings or films may still lack certain properties, such as sufficient DPUR, hardness, and blocking resistance. This is because the polymerizable surfactants act as monomers or form part of the resulting polymer in the polymerization process, and therefore, become part of the resulting polymer(s), which are then used in the coatings or films. Further, in order to increase certain properties in coatings, such as increasing the DPUR and hardness, benzophenone typically can be added. However, the use of benzophenone in coatings is facing more regulatory scrutiny, and therefore, there is a push to limit or even stop using benzophenone in coatings. In such situations, coatings without benzophenone may not have sufficiently desirable properties compared to coatings with benzophenone.

[008] Given the challenges above, there remains a need in the art for coating compositions having polymers formed from polymerizable surfactant(s), which provide improved properties, such as improved DPUR, hardness, and blocking resistance. There also remains a need in the art for coating compositions having polymers formed from polymerizable surfactant(s), which not only provide improved properties, such as improved DPUR, hardness, and blocking resistance, but also have sufficient or improved adhesion (e.g., adhesion to a substrate surface, including metal surfaces), durability, weatherability, while having minimal or reduced watersensitivity, water whitening resistance, blooming, and blushing. Moreover, there remains a need in the art for coating compositions having the aforementioned properties without the need of benzophenone. That is, there remains a need in the art for coatings that do not need or that can reduce the need of benzophenone while maintaining, or even increasing, the properties of the coatings, including but not limited to increased DPUR and hardness.

Summary of Invention

[009] In general, the present invention relates to coating compositions comprising a polymer formed from at least one polymerizable surfactant. In one embodiment, the present invention generally relates to a coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (I):

wherein:

Ri is a C₈-Ci4 alkyl group, preferably a C10-C14 alkyl group, a bicyclic group, or combinations thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; and M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof.

[0010] In another embodiment, the present invention generally relates to methods of making a coating composition comprising a polymer formed from at least one polymerizable surfactant, the method comprising emulsion polymerizing the at least one polymerizable surfactant with at least one other monomer, wherein the at least one polymerizable surfactant has formula (I):

wherein:

[0011] In yet another embodiment, the present invention generally relates to the use of a polymerizable surfactant of formula (I):

wherein:

Ri is a C₈-Ci4 alkyl group, preferably a C10-C14 alkyl group, a bicyclic group, or combinations thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; and M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof, to form a polymer for coating compositions.

[0012] In further embodiments, the present invention generally relates to the use of a coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (I):

wherein:

Ri is a C₈-Ci4 alkyl group, preferably a C10-C14 alkyl group, a bicyclic group, or combinations thereof; x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; and

M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof, to coat at least a part of the surface of a substrate, preferably wherein the coating composition provides improved dirt pick-up resistance (DPUR), hardness, blocking resistance, or a combination thereof.

[0013] Other aspects of certain embodiments include methods of preparing a polymer, including but not limited to latex polymer emulsions and paints, utilizing the polymerizable surfactant of formula (I).

Brief Description of Figures [0014] FIG. 1 shows the pendulum hardness of elastomeric paint comprising latex polymers prepared from polymerizable surfactants and elastomeric paint comprising latex polymers prepared by using conventional, non-polymerizable surfactants before curing.

[0015] FIG. 2 shows the pendulum hardness of elastomeric paint comprising latex polymers prepared from polymerizable surfactants and elastomeric paint comprising latex polymers prepared by using conventional, non-polymerizable surfactants after curing.

[0016] FIG. 3 shows the blocking resistance results of test panels coated with elastomeric paint comprising latex polymers prepared from polymerizable surfactants and elastomeric paint comprising latex polymers prepared by using conventional, non-polymerizable surfactants, in which the panels were tested at 50°C under conditions of 1 kg for 30 mins, based on ASTM D4946.

[0017] FIG. 4 shows the DPUR of elastomeric paint comprising latex polymers prepared from polymerizable surfactants and elastomeric paint comprising latex polymers prepared by using conventional, non-polymerizable surfactants.

[0018] FIG. 5 shows the blocking resistance results of test panels coated with an acrylic paint comprising latex polymers prepared from polymerizable surfactants and an acrylic paint comprising latex polymers prepared by using conventional, non-polymerizable surfactants, in which the panels were tested at 50°C under conditions of 1 kg for 30 mins, based on ASTM D4946.

[0019] FIG. 6 shows the DPUR of an acrylic paint comprising latex polymers prepared from polymerizable surfactants and an acrylic paint comprising latex polymers prepared by using conventional, non-polymerizable surfactants.

Detailed Description of Invention

[0020] General Definitions

[0021] The term and phrases “invention,” “present invention,” “instant invention,” and similar terms and phrases as used herein are non-limiting and are not intended to limit the present subject matter to any single embodiment, but rather encompasses all possible embodiments as described.

[0022] Throughout the description, including the claims, the term “a” and the phrase “at least one” are synonymous, and likewise, the phrase "comprising one" or “comprising a" should be understood as being synonymous with the term "comprising at least one," unless otherwise specified. Additionally, "between" should be understood as being inclusive of the limits. Further, throughout the description, including the claims, the terms “comprising” and “having” can be used interchangeably, and should be understood as being synonymous.

[0023] It should be noted that in specifying any range of concentration, weight ratio or amount, any particular upper concentration, weight ratio or amount can be associated with any particular lower concentration, weight ratio or amount, respectively.

[0024] As used herein, the term “alkyl” or "alkyl group" means a saturated hydrocarbon radical, which may be straight, branched or cyclic, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl.

[0025] As used herein, the term “bicyclic” or “bicyclic group” means a radical containing at least two joined rings with at least two common atoms. In certain embodiments, the bicyclic group can contains at least two rings that can be fused, bridged, or both.

[0026] As used herein, the term "cycloalkyl" or “cycloalkyl group” means a saturated hydrocarbon radical that includes one or more cyclic alkyl rings, such as, for example, cyclopentyl, cyclooctyl, and adamantanyl.

[0027] As used herein, the term "hydroxyalkyl" or “hydroxyalkyl group” means an alkyl radical, more typically an alkyl radical, that is substituted with a hydroxyl groups, such as for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

[0028] As used herein, the term "alkylene" or “alkylene group” means a bivalent acyclic saturated hydrocarbon radical, including but not limited to methylene, polymethylene, and alkyl substituted polymethylene radicals, such as, for example, dimethylene, tetramethylene, and 2- methyltrimethylene.

[0029] As used herein, the term "alkenyl" or “alkenyl group” means an unsaturated straight chain, branched chain, or cyclic hydrocarbon radical that contains one or more carbon-carbon double bonds, such as, for example, ethenyl, 1 -propenyl, 2-propenyl.

[0030] As used herein, the term "aryl" or “aryl group” means a monovalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted one or more of carbons of the ring with hydroxy, alkyl, alkenyl, halo, haloalky I , or amino, such as, for example, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl. [0031] As used herein, the term "aralkyl" or “aralkyl group” means an alkyl group substituted with one or more aryl groups, such as, for example, phenylmethyl, phenylethyl, triphenylmethyl. [0032] As used herein, “AGE” is allyl glycidyl ether.

[0033] As used herein, the terminology "(C_n-C_m)" in reference to an organic group, wherein n and m are each integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.

[0034] As used herein, the terminology “ethylenic unsaturation”, “ethylenic unsaturated”, or similar terms means a terminal (that is, e.g., a, p) carbon-carbon double bond.

[0035] As used herein, “DPUR” means dirt pick-up resistance.

[0036] Coating Compositions

[0037] It has been found that coating compositions comprising a polymer formed from at least one polymerizable surfactant according to the present invention can have unexpectedly superior benefits. For instance, in one embodiment, coating compositions comprising a polymer formed from at least one polymerizable surfactant according to the present invention can have unexpectedly superior DPUR, hardness, or blocking resistance. In certain embodiments, the coating compositions comprising a polymer formed from at least one polymerizable surfactant according to the present invention can have a combination of the unexpectedly superior aforementioned properties, such as unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties.

[0038] Notably, the coating compositions according to the present invention can have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, in comparison to not only coating compositions having a polymer formed from emulsion polymerizations processes using conventional (i.e., non-polymerizable) surfactants, but also in comparison to coating compositions having a polymer formed from emulsion polymerization processes using different polymerizable surfactants than those of the present invention. That is, the currently claimed coating compositions having a polymer comprising polymerizable surfactants of the present invention can have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, when compared to coating compositions having a polymer comprising polymerizable surfactants that are different than those of the present invention. The currently claimed coating compositions can also have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, when compared to coating compositions having a polymer formed by using conventional, non-polymerizable surfactants.

[0039] In addition to the above, the coating compositions of the present invention can also have various desirable properties, which are in addition to the unexpectedly better DPUR, hardness, blocking resistance, or a combination of the properties. In other words, in various embodiments, the coating compositions of the present invention can have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, without having to sacrifice, reduce, or diminish other desirable properties of the coating compositions. This is important since many times increasing certain desirable properties comes at the expense of having to sacrifice other properties. In this respect, the coating compositions of the present invention can not only have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, but the coating compositions can have such properties without significantly reducing other beneficial properties of the coating compositions.

[0040] In addition to the above, the coating compositions of the present invention can provide unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, without the need of adding benzophenone. Benzophenone is a common additive for coatings, which can be used to increase certain properties of the same, such as increasing the DPUR and hardness of the coatings. Yet, there is a desire to reduce or even eliminate the need for benzophenone in coatings. Surprisingly, it has been found that not only can the coating compositions according to the present invention have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, and in particular unexpectedly superior DPUR and hardness, but it has been unexpectedly found that the coating compositions can have such superior properties with or without benzophenone. In this respect, in certain embodiments, the coating compositions according to the present invention have unexpectedly superior DPUR, hardness, blocking resistance, or a combination of the properties, and in particular unexpectedly superior DPUR and hardness, without benzophenone.

[0041] Given the above, in certain embodiments the coating compositions of the present invention can have improved DPUR, as measured by ASTM D3719. In this respect, in certain embodiments the coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention can have improved DPUR, in which the DPUR is increased by about 5% or greater, about 10% or greater, or about 12% or greater, as measured by ASTM D3719, compared to coating compositions comprising a polymer that is not formed from at least one polymerizable surfactant of the present invention. In certain other embodiments, the coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention can have improved DPUR, in which the DPUR is increased by about 8% or greater, about 14% or greater, or about 16% or greater, as measured by ASTM D3719, compared to coating compositions comprising a polymer that is not formed from at least one polymerizable surfactant of the present invention.

[0042] As also discussed above, in certain embodiments the coating compositions of the present invention can have improved hardness, as measured by ASTM D4366, as well as improved blocking resistance, as measured by ASTM D4946. With respect to embodiments having improved hardness, such embodiments include coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention, in which the hardness is increased by about 5% or greater, about 8% or greater, or about 10% or greater, as measured by ASTM D4366, compared to coating compositions comprising a polymer that is not formed from at least one polymerizable surfactant of the present invention. As for embodiments having improved blocking resistance, such embodiments include coating compositions comprising a polymer formed from at least one polymerizable surfactant of the present invention, in which the blocking resistance is increased by about 50% or greater, about 100% or greater, about 150% or greater, about 200% or greater, about 250% or greater, about 300% or greater, about 350% or greater, about 400% or greater, or about 450% or greater, as measured by ASTM D4946, compared to coating compositions comprising a polymer that is not formed from at least one polymerizable surfactant of the present invention.

[0043] And as discussed above, the coating compositions of the present invention can have superior DPUR, hardness, blocking resistance, or a combination of the properties.

[0044] Furthermore, various types of coating compositions of the present invention can comprise a polymer formed from at least one polymerizable surfactant. For example, in some embodiments the coating compositions can be an elastomeric coating, an architectural coating, or both. Additionally, in certain embodiments the coating compositions can be a latex coating. In this respect, in various embodiments, the coating compositions can generally have a glass transition temperature (Tg) of -40°C to 40°C, as measured by ASTM D3418. In certain embodiments, the coating compositions can have a glass transition temperature (Tg) of -40°C to -10°C, preferably a glass transition temperature (Tg) of -40°C to -20°C, as measured by ASTM D3418. In other embodiments, the coating compositions can have a glass transition temperature (Tg) of -5°C to 40°C, preferably a glass transition temperature (Tg) of 10°C to 40°C, as measured by ASTM D3418.

[0045] In embodiments in which the coating composition is an elastomeric coating, the coating composition can have a glass transition temperature (Tg) of -40°C to 40°C, preferably can have a glass transition temperature (Tg) of -40°C to -10°C, and more preferably can have a glass transition temperature (Tg) of -40°C to -20°C, as measured by ASTM D3418. In embodiments in which the coating composition is an architectural coating, the coating composition can have a glass transition temperature (Tg) of -40°C to 40°C, preferably can have a glass transition temperature (Tg) of -5°C to 40°C, and more preferably can have a glass transition temperature (Tg) of 10°C to 40°C, as measured by ASTM D3418.

[0046] Polymerizable Surfactants

[0047] Like non-polymerizable surfactants, polymerizable surfactants are molecules that typically have a hydrophobic group and a hydrophilic group, such as an ionizable and/or polar group. The hydrophobic group preferentially adsorbs onto the surface of the polymer particle during and following particle polymerization. In the context of emulsion polymerization processes to form latex, the hydrophobic group preferentially adsorbs onto the surface of the latex polymer particle during and following the polymerization process. The hydrophilic group on the surfactant extends into the aqueous solution phase and provides a steric barrier or charge repulsion against particle agglomeration and coagulation.

[0048] However, unlike their non-polymerizable counterparts, polymerizable surfactants additionally contain a reactive group on the molecule, such as on the hydrophobic group, which is capable of covalently bonding to the latex surface. Usually this is a moiety such as terminal unsaturated carbon group(s), such as vinyl or an olefin group(s), which can participate in free- radical emulsion polymerization reactions. When used in emulsion polymerization, a large fraction of the polymerizable surfactant molecules becomes irreversibly bound to the emulsion polymer chains and droplets. This can improve both the latex stability and reduce foaming, amongst other desirable properties. It also can reduce or minimize the amount of free or separate surfactant molecules. In context of the current application, a polymer formed from at least one polymerizable surfactant and a polymer comprising at least one polymerizable surfactant are synonymous and equivalent. That is, unlike conventional, non-polymerizable surfactants, the polymerizable surfactants of the present invention form part of the polymer (i.e., the polymer comprises the polymerizable surfactant).

[0049] As discussed above, it has been surprisingly found that coating compositions comprising a polymer formed from at least one polymerizable surfactant according to the present invention can have unexpectedly superior benefits. In this respect, it has been surprisingly found that when the polymerizable surfactants as described herein are used in making the polymer, and in particular are used to make latexes, the coating compositions that have the polymer therein have superior properties, such as superior DPUR, hardness, blocking resistance, or a combination of the properties.

[0050] The polymerizable surfactants as described herein are prepared from readily available raw materials, and their preparation generally does not require any special equipment or special handling. In certain embodiments, the polymerizable surfactants are ethylenically unsaturated salts of allyl (poly)ether sulfates. The polymerizable surfactants described herein may be prepared in a batch mode or a continuous mode. The polymerizable surfactants can be prepared in a variety of forms, including but not limited to, liquids, solutions, flakes, powders, solids, semi-solids, gels, ringing gels, or pastes. In one embodiment, the polymerizable surfactants are prepared by using water as the solvent, but other solvents, such as alcohols or other conventional solvents can be used. Mixtures of solvents can also be used to prepare the polymerizable surfactants of the present invention, including mixtures of water, alcohols or other conventional solvents. A solvent or a mixture of solvents can be used to make an aqueous solution of the polymerizable surfactant. In one embodiment, the polymerizable surfactant as described herein also encompasses surfactants as salts in dry form, and in another embodiment, the polymerizable surfactant as described herein also encompasses surfactants as aqueous solutions. Salts of the polymerizable surfactants may be isolated by drying a solution of the polymerizable surfactants. A solution of polymerizable surfactants can be prepared by dissolving the salt of the polymerizable surfactant in water, solvent, or a mixture thereof.

[0051] Coatings of the present invention can be obtained from an aqueous dispersion comprising at least one polymerizable surfactant according to the present invention. An effective amount of a conventional, non-polymerizable surfactant can also be used with the polymerizable surfactant. In certain embodiments, and in addition to the benefits discussed above, coatings of the present invention comprising at least one polymerizable surfactant can have better water whitening resistance in hot water (90 °C) whitening test. In one specific embodiment, Ci₂/Ci₄-2.6AGE-15EO-sulfate sodium salt, Ci₂/Ci₄-2.6AGE-15EO-sulfate ammonium salt, Nopol-2.6AGE-15EO-sulfate sodium salt, Nopol-2.6AGE-15EO-sulfate ammonium salt, and combinations thereof, demonstrate not only improved hot water whitening resistance in comparison to when nonreactive regular surfactants (i.e., conventional, non- polymerizable surfactants) are used, but also the specific embodiment can provide superior DPUR, hardness, blocking resistance, or a combination of the properties.

[0052] More generally, in an embodiment, the polymerizable surfactant can have formula (I):

wherein:

[0053] In certain embodiments, the polymerizable surfactant can be a mixture of two or more polymerizable surfactants of formula (I), wherein Ri is two or more different C₈-Ci₄ alkyl groups, two or more different bicyclic groups, or mixtures thereof, and wherein both x and y can be within any of the ranges above and can vary for each particular surfactant of formula (I) in the mixture, and M+ can be a mixture and can vary for each particular surfactant of formula (I). As a non-limiting example, in certain embodiments, the polymerizable surfactant can be a mixture of two or more polymerizable surfactants of formula (I), wherein at least one surfactant of formula (I) has Ri that is a C₈-Ci4 alkyl group, preferably a C10-C14 alkyl group, and wherein at least one different polymerizable surfactant of formula (I) has R1 that is a different C₈-C1₄ alkyl group, preferably a different C10-C14 alkyl group, and wherein x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; and M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof.

[0054] When R1 is a bicyclic group, the bicyclic group can be substituted or unsubstituted, and can be connected to the oxygen group by an alkyl group, alkylene group, or alkenyl group. In one embodiment, R1 is a bicyclo_[d ,_e.f]hepty I or bicyclo_[d.e.f]heptenyl group wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1 , and the sum of d + e + f = 5, and which may, optionally, be substituted on one or more of the ring carbon atoms by one or more (C 1 -C₆)al ky I groups (otherwise referred to herein as “Nopol”).

[0055] In another embodiment, R1 is a bicyclic group, or more specifically in one embodiment, a bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C5-C5o)alkyl-polyether group, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may, optionally, be substituted on one or more ring carbon atoms by one or two (Ci-C₆)alkyl groups per carbon atom.

[0056] In one embodiment, R1 is a linear or branched C₈-Ci₄ alkyl group, preferably a linear or branched C10-C14 alkyl group, or mixtures thereof, and in other embodiments, R1 is a linear or branched C₆-Ci₈ alkyl group.

[0057] Furthermore, R1 can be any one of or any combination of:

(i) a bicyclO[3.i.i]heptyl or bicyclo_[3.i .ijheptenyl group that is bonded via its carbon atom at the 2-position and is typically substituted on its carbon atom at the 6-position by one or two (Ci-Ce)alkyl radicals, more typically by two methyl radicals, or

(ii) a bicyclO[3.i.i]heptyl or bicyclo_[2.2.i]heptenyl group that is bonded via its carbon atom at the 2-position or 3-position and is typically substituted on its carbon atom at the 7 position by one or two (Ci-C₆)al ky I radicals, more typically by two methyl radicals.

[0058] Suitable bicyclic groups for R1 include, but are not limited to, bicycloheptyl- and bicycloheptenyl- moieties may be derived from, for example, terpenic compounds having core (non-substituted) 7 carbon atom bicyclic ring systems according to structures (XII) - (XVII):

[0059] For example, Ri can be derived from a bicycloheptenyl intermediate compound (VII), also known as "Nopol":

which can be made by reacting p-pinene with formaldehyde.

[0060] Ri can also be derived from a bicycloheptyl intermediate compound (VIII), known as "Arbanol”:

which can be made by isomerization of a-pinene to camphene and ethoxyhydroxylation of the camphene.

[0061] In one embodiment, Ri can be derived from a bicycloheptyl- or bicycloheptenyl- intermediate that is alkoxylated by reacting the bicycloheptyl- or bicycloheptenyl intermediate with one or more alkylene oxide compounds, such as ethylene oxide or propylene oxide, to form a bicycloheptyl-, or bicycloheptenyl- polyether intermediate. The alkoxylation may be conducted according to well-known methods, typically at a temperature in the range of about 100° to about 250°C and at a pressure in the range of from about 1 to about 4 bars, in the presence of a catalyst, such as a strong base, an aliphatic amine, or a Lewis acid, and an inert gas, such as nitrogen or argon.

[0062] The bicycloheptyl-, or bicycloheptenyl- polyether monomer can then formed by addition of a polymerizable functional group to the bicycloheptyl- or bicycloheptenyl- polyether intermediate, by, for example, esterification, under suitable reaction conditions, of the bicycloheptyl- or bicycloheptenyl- polyether intermediate with, for example, methacrylic anhydride.

[0063] In some embodiments of the polymerizable surfactant, sulfate group includes the corresponding salt forms, wherein the cation includes but not limited to Na+, NH4+, K+ or Li+. In other embodiment, M+ can be, but is not limited to, H+, Na+, NH4+, K+ or Li+. In a certain embodiments, M+ is Na+, NH4+, or combinations thereof. In a preferred embodiment, M+ is NH4+.

[0064] In a more particular embodiment, the polymerizable surfactant can have formula (II):

wherein: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18; and M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof.

[0065] In yet another particular embodiment, the polymerizable surfactant can have formula (III):

wherein: x is at least 2 to 10, preferably at least 2 to 6, more preferably at least 2 to 4; and y is greater than 10 to 30, preferably 12 to 20, more preferably 14 to 18.

[0066] In particularly preferred embodiments, the polymerizable surfactant is Nopol-2.6AGE- 15EO-sulfate sodium salt, which is represented as follows in formula (Illa):

wherein: x averages 2.6; and y is 15.

[0067] In certain embodiments, the polymerizable surfactant can specifically be C12/C14- 2.6AGE-15EO-sulfate ammonium salt, Ci₂/Ci₄-2.6AGE-15EO-sulfate sodium salt, Nopol- 2.6AGE-15EO-sulfate sodium salt, Nopol-2.6AGE-15EO-sulfate ammonium salt, and mixtures thereof. As such, certain embodiments can include polymerizable surfactants of formula (IV):

[0037] In one embodiment, the polymerizable surfactant can be Ci₂/Ci₄-2.6AGE-15EO-sulfate sodium salt. More generally, the polymerizable surfactant can have formula (V):

[0038] In another specific embodiment, the polymerizable surfactant can be CI₂/CI₄-2.6AGE- 15EO-sulfate ammonium salt. More generally, the polymerizable surfactant can have formula (VI):

[0039] With respect to x and y in formulas (I) - (VI), these values can be calculated based on the raw material charges, by NMR analytical analysis, or both.

[0040] It is important to note that the polymerizable surfactants useful in the instant invention can include any combinations of the polymerizable surfactants herein, including not only any combinations of a particular salt of the polymerizable surfactants, but also any combinations of the various polymerizable surfactants in formulas (I) - (VI).

[0041] The polymerizable surfactants as described herein can be used for applications in which reactive surfactants containing one or more polyether groups have been used to date, specifically as emulsifiers for emulsion polymerization, dispersants for suspension polymerization, resin modifiers (for improvements in water repellency, adjustments in hydrophilicity, improvements in antistatic properties, improvements in anti-fogging properties, improvements in waterproofness, improvements in adhesion properties, improvements in dyeability, improvements in film-forming properties, improvements in weatherability, improvements in anti-blocking properties, etc.), fiber processing aids, non-dripping agents, soil resistance finishes, paints, and the like.

[0042] When any one of the polymerizable surfactants as described herein are used as an emulsifier for emulsion polymerization, it can be used in any desired proportion within a proportion range with other emulsifiers (surfactants) for emulsion polymerization. In general, however, it can be used preferably in a proportion of from 0.1 wt. % to 20 wt. %, typically, in a proportion of from 0.2 wt. % to 10 wt. % based on the raw material monomer or monomers, and in other embodiment, in a proportion of from 0.2 wt. % to 5 wt. % based on the raw material monomer or monomers. Further, in another embodiment, conventional, non-reactive surfactants (i.e., non-polymerizable surfactants) aside from the polymerizable surfactant as described herein can be utilized during the emulsion polymerization process. Such conventional, non-reactive surfactants that are commonly used in the emulsion polymerization process include both anionic and nonionic surfactants. In one embodiment, at least one polymerizable surfactant as described herein can be used with one or more anionic surfactants. In another embodiment, at least one polymerizable surfactant as described herein can be used with one or more cationic surfactants. In one embodiment, at least one polymerizable surfactant as described herein can be used with one or more non-ionic surfactants. Furthermore, the polymerizable surfactant or combinations of the polymerizable surfactants as described herein can be used with any combination of one or more anionic surfactants and one or more nonionic surfactants.

[0043] Non-limiting examples of anionic surfactants that can used in connection with the polymerizable surfactants as described herein, including in the emulsion polymerization process, include: sodium alkylbenzene sulfonates, alkyl sulfosuccinates, alkyldiphenyloxide disulfonates, ethoxylated alkylphenol sulfates and phosphates, sulfates and phosphates of fatty alcohols, and the like, or any salt thereof. Non-limiting examples of non-ionic surfactants that can be used in connection with the polymerizable surfactants as described herein, including in the emulsion polymerization process, include: alcohol ethoxylates, alkylphenol ethoxylates, and the like, or any salt thereof. In one embodiment, the anionic surfactant is a C10-16 alcohol ethoxylate sulfate, or any salt thereof.

[0044] Although no particular limitation is imposed on the monomer(s) that can be used in the emulsion polymerization process with the polymerizable surfactant, preferably the polymerizable surfactants herein can be used in emulsion polymerization processes for acrylate emulsions, styrene emulsions, vinyl acetate emulsions, SBR (styrene/butadiene) emulsions, ABS (acrylonitrile/butadiene/styrene) emulsions, BR (butadiene) emulsions, IR (isoprene) emulsions, NBR (acrylonitrile/butadiene) emulsions, vinyl chloride emulsions, and the like. [0045] Non-limiting suitable monomers that may be polymerized under emulsion polymerization conditions as described herein include ethylenically unsaturated monomers, for example, vinyl monomers, acrylic monomers, acrylate monomers, and mixtures thereof. Typical vinyl monomers suitable for use include, but are not limited to, vinyl esters such as vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid, including vinyl versatate, vinyl benzoate, vinyl propionate, vinyl aromatic hydrocarbons such as styrene, methyl styrenes, other vinyl aromatics such as vinyl toluenes, vinyl naphthalenes, divinyl benzene, and mixtures thereof. Olefins, such as C₂-C₄ olefins, including but not limited to ethylene, propylene, butylene, butadiene, and mixtures thereof can also be used. Methacrylates and blends thereof can be used. Halogenated vinyl monomers such as vinyl chloride, vinylidene chloride, and mixtures thereof may also be used.

[0046] Non-limiting suitable acrylic monomers typically include compounds with acrylic functionality such as alkyl acrylates and methacrylates, acrylate acids and methacrylate acids as well as acrylamides and acrylonitrile, and mixtures thereof. Typical acrylic monomers can include, but are not limited to methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, and methacrylate, benzyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl and dodecyl acrylate and methacrylate, and mixtures thereof. Other acrylic monomers include hydroxy alkyl acrylates and methacrylates such as hydroxypropyl and hydroxyethyl acrylate and methacrylate, acrylic acids such as methacrylic and acrylic acid, amino acrylates, and methacrylates, and mixtures thereof.

[0047] Other examples of (co)polymerizable monomers in the acrylate emulsions can include but are not limited to (meth)acrylic acid (acrylate) alone, (meth)acrylic acid (acrylate)/styrene, (meth)acrylic acid (acrylate)/vinyl acetate, (meth)acrylic acid (acrylate)/acrylonitrile, (meth)acrylic acid (acrylate)/butadiene, (meth)acrylic acid (acrylate)/vinylidene chloride, (meth)acrylic acid (acrylate)/allylamine, (meth)acrylic acid (acrylate)/vinylpyridine, (meth)acrylic acid (acrylate)/alkylolamides, (meth)acrylic acid (acrylate)/N,N- dimethylaminoethyl esters, and (meth)acrylic acid (acrylate)/N,N-diethylaminoethyl vinyl ether. [0048] The polymerizable surfactants of the present invention can be used to make a coating composition. That is, the polymerizable surfactants of the present invention can be used to form a polymer for coating compositions. Additionally, the polymerizable surfactants of the present invention can be used to make coating compositions, in which the coating compositions are used to coat at least part of a substrate to provide improved DPUR, hardness, blocking resistance, or a combination thereof, preferably improved DPUR, hardness, and blocking resistance.

[0049] In another aspect, the methods of preparing a polymer (including but not limited to latex polymer emulsions and paints) include using a polymerizable surfactant of the present invention in combination with at least one other surfactant that is not a polymerizable surfactant of the present invention. In one embodiment, the surfactant can be selected sodium alkylbenzene sulfonates, alkyl sulfosuccinates, alkyldiphenyloxide disulfonates, ethoxylated alkylphenol sulfates and phosphates, sulfates and phosphates of fatty alcohols. In another embodiment, the surfactant can be a C10-C16 alcohol ethoxylate sulfate or any salt thereof.

[0050] More generally, in certain embodiments, the polymerizable surfactant can comprise any polymerizable surfactant in combination with at least one other surfactant that is not a polymerizable surfactant of the present invention. In one embodiment, the non-polymerizable surfactant is sodium alkylbenzene sulfonates or any salt thereof, alkyl sulfosuccinates or any salt thereof, alkyldiphenyloxide disulfonates or any salt thereof, ethoxylated alkylphenol sulfates or any salt thereof, ethoxylated alkylphenol phosphates or any salt thereof, sulfates and phosphates of fatty alcohols or any salt thereof. In another embodiment, the surfactant can be an alkyl alcohol ethoxylate sulfate or any salt thereof.

[0051] Other additives or components which are known to those skilled in the art may also be used in accordance with the present invention. These include chain transfer agents, which are used to control molecular weight, additives to adjust pH, and compounds utilized as protective colloids, which provide additional stability to the latex particles.

[0052] In addition to the superior benefits discussed above, including superior DPUR, hardness, blocking resistance, or a combination of the properties, the use of polymerizable surfactants as described herein in emulsion polymerization imparts at least one of the following benefits to a latex and/or coating application: water whitening resistance, high temp whitening resistance, medium reactivity, PME stability, good process control, and excellent application performance (e.g., water sensitivity).

[0053] The following examples are illustrative of preferred embodiments of polymerizable surfactants, coating compositions having a polymer formed form at least one polymerizable surfactant, and methods for making and using the same, and are not intended to be limitations thereon. All composition percentages are based on totals equal to 100% by weight, unless otherwise specified.

Examples

[0054] Preparation of polymerizable surfactants

[0055] Example 1. Preparation of polymerizable surfactant CI₂CI₄-2.6AGE-15EO sulfate ammonium salt

[0056] 10.0g 45% potassium hydroxide solution was added to 320g of Alfol 1214 stirring at 80°C in a reactor with a sub-surface purge of nitrogen gas. After heating to 100°C, the gas flow was stopped and a vacuum pump was used to evacuate the flask by approximately 20"Hg. One hour later the vacuum was broken with nitrogen and a sample was analyzed by Karl- Fischer Titration to be 0.09% water content.

[0057] 470.1 g allyl glycidyl ether was added to the reactor over 120 minutes within a temperature range of 95-105°C. 30 minutes later the reactor contents were heated to 120°C. After a further six hours within a temperature range of 120-123°C a sample of the reactor contents was titrated to naptholbenzein indicator with 0.1 M perchloric acid in acetic acid and showed 0.101 mmol/g alkalinity in the presence of tetrabutylammonium bromide indicating complete reaction of the added epoxy compound. 780g clear liquid product was recovered from the reactor.

[0058] 360g of the previously described adduct was charged to an agitated autoclave reactor and heated to 110°C with a sub-surface purge of nitrogen gas. The reactor was evacuated by approximately 27"Hg and held at those conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive pressure of 1.1 bars nitrogen, the reactor contents were heated to 155°C then 541g ethylene oxide were fed below the surface of the liquid over 140 minutes between 155-156°C reaching a maximum pressure of 5.3bars. One hour later the pressure was released and the reactor contents were cooled to 115°C before purging once more with nitrogen gas for 10 minutes before discharge. 889g clear liquid product was recovered from the reactor.

[0059] 647.3g of the previously described adduct was charged to a 1 liter reactor followed by stirring at 350 RPM, initiation of a ~25 ml/min nitrogen sparge and heating to 65°C. Dicyandiamide (0.36g) was charged to the reactor followed by a 1 hour sparge to help reduce I remove dissolved oxygen, which contributes to color. 71 ,13g of sulfamic acid was charged to the reactor over one hour by dividing the charge into 5 nearly equal additions. The reaction temperature was increased to 90°C where it was maintained for 5 hours. The reaction mass was cooled to <40°C and the dark amber liquid was bottled. The % actives was determined by use of a Hyamine test.

[0060] 1172.22g of deionized water was charged to a two gallon open-top reaction flask with stainless steel turbine agitator. Stirring was initiated at 350 RPM. 18.5g of 29% ammonium hydroxide was charged to the stirring water. 524.9g of the previously described adduct, with an actives level of 100% by Hyamine test, was slowly charged to the water in a steady stream, while ensuring the pH remained >7. An additional 231g of deionized water was charged to give an estimated 27% actives solution. The agitation was maintained for 30 minutes. The clear, amber liquid was bottled. The % actives was determined to be 29.1 %.

[0061] Example 2. Preparation of polymerizable surfactant Nopol-2.6AGE-15EO sulfate ammonium salt

[0062] 11.1g 45% potassium hydroxide solution was added to 283g of Nopol stirring at 100°C in a reactor with a sub-surface purge of nitrogen gas. The gas flow was stopped and a vacuum pump was used to evacuate the flask by approximately 22"Hg. One hour later the vacuum was broken with nitrogen and a sample analyzed by Karl-Fischer Titration to be 0.06% water content.

[0063] 505.8g allyl glycidyl ether was added to the reactor over 120 minutes within a temperature range of 93-96°C. 30 minutes later the reactor contents were heated to 120°C. After a further five hours within a temperature range of 118-120°C, a sample of the reactor contents was titrated to naptholbenzein indicator with 0.1 M perchloric acid in acetic acid and showed 0.125 mmol/g alkalinity in the presence of tetrabutylammonium bromide indicating essentially complete reaction of the added epoxy compound (2% molar residual epoxy = 98% molar conversion of allyl glycidyl ether). 773g clear liquid product was recovered from the reactor.

[0064] 351g of the previously described adduct was charged to an agitated autoclave reactor and heated to 110°C with a sub-surface purge of nitrogen gas. The reactor was evacuated by approximately 27"Hg and held at those conditions for 30 minutes. After breaking the vacuum with nitrogen and applying a positive pressure of 1.0 bars nitrogen the reactor contents were heated to 155°C then 546g ethylene oxide were fed below the surface of the liquid over 130 minutes between 155-156°C reaching a maximum pressure of 5.6bars. One hour later the pressure was released and the reactor contents were cooled to 110°C before purging once more with nitrogen gas for 10 minutes before discharge. 876g clear liquid product was recovered from the reactor.

[0065] 691 ,4g of the previously described adduct was charged to a 1 liter reactor followed by stirring at 350 RPM, initiation of an ~25 ml/min nitrogen sparge and heating to 65°C. Dicyandiamide (0.39g) was charged to the reactor followed by a 1 hour sparge to help reduce I remove dissolved oxygen, which contributes to color. 84.65g of sulfamic acid was charged to the reactor over one hour by dividing the charge into 5 nearly equal additions. The reaction temperature was increased to 90°C where it was maintained for 5 hours. The reaction mass was cooled to <40°C and bottled. The % actives was determined by use of a Hyamine test for use in the dilution to the desired % actives of 25%.

[0066] 1165.61g of deionized water was charged to a two gallon open-top reaction flask with stainless steel turbine agitator. Stirring was initiated at 350 RPM. 16.0g of 29% ammonium hydroxide was charged to the stirring water yielding a pH of 10.62. 529.5g of the previously described adduct, with an actives level of 99.8% by Hyamine test, was slowly charged to the water in a steady stream, while ensuring the pH remained >7. An additional 50.2g of deionized water was charged to give an approximately 30% actives solution. The agitation was maintained for 30 minutes. The clear, amber liquid was bottled. The % actives was determined to be 29.27%.

[0067] Examples 1 and 2. The polymerizable surfactants A and B in Examples 1 and 2 are summarized below in TABLE 1 , adjusted for the molar ratios of starting raw materials accordingly.

TABLE 1 - Polymerizable surfactants in Example 1-2

[0068] Preparation of latex polymer [0069] Example 3. Preparation of latex polymer by using Surfactant A through emulsion polymerization.

[0070] De-ionized water (245.0 g) and the polymerizable Surfactant A (29.10% solids, 7.5 g) were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 31 .50 g monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (103 g), polymerizable Surfactant A (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), and adjusted with a complex solution of 20 g DI water, 2.4 g ammonium bicarbonate, 1.7 g zinc oxide, and 7 g of 28% ammonia. Once the temperature of the reactor had stabilized at 80°C. A solution of ammonium persulfate (0.6 g dissolved in 10 g deionized water) was added to the reactor.

[0071] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion and initiators solution (1.5 g dissolved in 60 g deionized water) started to continuously be added to the reactor within 3 hours at temperature 80-83°C. Monomer pre-emulsion was completed for addition in over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. Then a chaser solution (0.4 g t- butyl hydroperoxide dissolved in 5 g DI water, and 0.2 g Bruggolite FF6 dissolved in 5 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 51 .2%, and the average particle size was 134.2 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer is about -35 degree C. The latex properties were given in TABLE 2.

[0072] Example 4. Preparation of latex polymer by using Surfactant A in the presence of benzophenone through emulsion polymerization.

[0073] A similar latex polymer was prepared by following the same emulsion polymerization procedure described in Example 3, except benzophenone was presence during reaction.

[0074] De-ionized water (248.0 g) and the polymerizable Surfactant A (29.10% solids, 7.5 g) were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 31 .50 g monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (109.6 g), polymerizable Surfactant A (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), and benzophenone (4 g), and adjusted with a complex solution of 20 g DI water, 2.4 g ammonium bicarbonate, 1 .7 g zinc oxide, and 7 g of 28% ammonia. Once the temperature of the reactor had stabilized at 80°C. A solution of ammonium persulfate (0.6 g dissolved in 10 g deionized water) was added to the reactor.

[0075] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion and initiators solution (1.5 g dissolved in 60 g deionized water) started to continuously be added to the reactor within 3 hours at temperature 80-83°C. Monomer pre-emulsion was completed for addition in over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. Then a chaser solution (0.4 g t- butyl hydroperoxide dissolved in 5 g DI water, and 0.2 g Bruggolite FF6 dissolved in 5 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 51 .2%, and the average particle size was 128.3 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer is about -35 degree C. The latex properties were given in TABLE 2.

[0076] Comparative Example 5. Preparation of latex polymer by using a comparative conventional surfactant (i.e., a non-polymerizable surfactant) through emulsion polymerization.

[0077] A comparative latex polymer was prepared by following the same emulsion polymerization procedure described in Example 3, except that a conventional, non- polymerizable surfactant was used instead of a polymerizable surfactant.

[0078] De-ionized water (245.0 g) and surfactant Aerosol EF810 (30% solids, 7.5 g), which is a non-polymerizable surfactant, were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 31.50 g monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (103 g), Aerosol EF810 (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), and adjusted with a complex solution of 20 g DI water, 2.4 g ammonium bicarbonate, 1 .7 g zinc oxide, and 7 g of 28% ammonia. Once the temperature of the reactor had stabilized at 80°C. A 6% solution of ammonium persulfate (0.6 g dissolved in 10 g deionized water) was added to the reactor.

[0079] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion and initiators solution (1.5 g dissolved in 60 g deionized water) started to continuously be added to the reactor within 3 hours at temperature 80-83°C. Monomer pre-emulsion was completed for addition in over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. Then a chaser solution (0.4 g t- butyl hydroperoxide dissolved in 5 g DI water, and 0.2 g Bruggolite FF6 dissolved in 5 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 51.5%, and the average particle size was 131 .1 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer is about -35 degree C. The latex properties were given in TABLE 2.

[0080] Comparative Example 6. Preparation of latex polymer by using a comparative conventional surfactant (i.e. , a non-polymerizable surfactant) in the presence of benzophenone through emulsion polymerization.

[0081] A comparative latex polymer was prepared by following the same emulsion polymerization procedure described in Comparative Example 5 (i.e., by using conventional non-polymerizable surfactant), except that benzophenone was also present during the reaction.

[0082] De-ionized water (245.0 g) and surfactant Aerosol EF810 (30% solids, 7.5 g), which is a non-polymerizable surfactant, were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 31.50 g monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (103 g), Aerosol EF810 (16.4 g), acrylonitrile (81.2 g), butyl acrylate (403.1 g), acrylic acid (9.9 g), and acrylamide (2.5 g), and benzophenone (4 g), and adjusted with a complex solution of 20 g DI water, 2.4 g ammonium bicarbonate, 1.7 g zinc oxide, and 7 g of 28% ammonia. Once the temperature of the reactor had stabilized at 80°C. A 6% solution of ammonium persulfate (0.6 g dissolved in 10 g deionized water) was added to the reactor.

[0083] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion and initiators solution (1.5 g dissolved in 60 g deionized water) started to continuously be added to the reactor within 3 hours at temperature 80-83°C. Monomer pre-emulsion was completed for addition in over 2 hours and 45 minutes. The initiator addition was completed in 3 hours. Then a chaser solution (0.4 g t- butyl hydroperoxide dissolved in 5 g DI water, and 0.2 g Bruggolite FF6 dissolved in 5 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 51.1 %, and the average particle size was 122.1 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer is about -35 degree C. The latex properties were given in TABLE 2.

TABLE 2. Latex properties of Examples 3 and 4 along with Comparative Examples 5 and 6.

[0084] Example 7. The latex polymers that were prepared in Examples 3 and 4 along with Comparative Examples 5 and 6 were formulated in a 45% PVC exterior elastomeric paint for stones or other construction substrates. The paint formulation is given in TABLE 3a.

TABLE 3a. Paint formulation of exterior elastomeric coatings

[0085] The hardness, blocking resistance, and DPUR of the formulated exterior paints containing the latex polymers that were prepared in Examples 3 and 4 along with Comparative Examples 5 and 6 were evaluated according to the following method. Paints were drawdown over different substrates and allowed to dry for 1 to 7 days in accordance with the applicable ASTM methodology. The pendulum hardness properties were measured according to ASTM D4366, and results are given below in Table 3b and illustrated in Figs. 1 and 2. The paints were drawdown over glass plates and the values were averaged based on three (3) tests for each panel. As can be seen, latex polymers prepared using the polymerizable surfactant improved the hardness of the paints, both with or without benzophenone, as compared to paints having latex polymers prepared using conventional, non-polymerizable surfactants.

[0086] Table 3b. Paint film hardness before and after curing

*BP means benzophenone

[0087] The blocking resistance of the formulated exterior paints containing the latex polymers that were prepared in Examples 3 and 4 along with Comparative Examples 5 and 6 were also evaluated. The blocking resistance was measured according to ASTM D4946. The blocking resistance test was performed at both room temperature and at elevated temperature (i.e., 50°C). Hot blocking resistance tests were performed at 50°C under conditions of 1 kg weight for 30 minutes based on the standard method, and the testing panels are illustrated in Figure 3. As can be clearly seen, the test panels coated with paints containing the latex polymers prepared with the polymerizable surfactant show significantly better performance. That is, the latex polymers prepared with the polymerizable surfactant significantly improved the blocking resistance of the paints.

[0088] The DPUR performance was tested by following ASTM D3719. The test panels were painted using the formulated exterior paints containing the latex polymers that were prepared in Examples 3 and 4 along with Comparative Examples 5 and 6. The test panels were then placed outdoors for dirt pick-up resistance testing by visual examination of the paint surfaces over time. The color L value was also measured according to ASTM D5326 at the beginning of the testing and after outdoor exposure. The testing results are given below in Table 3c and illustrated in Fig. 4 after two (2) months of outdoor exposure. As can be seen, paints containing the latex polymers that were prepared using the polymerizable surfactant show lower delta (A) L value changes, which indicates improved DPUR.

[0089] Table 3c. DPUR for outdoor exposure

*BP means benzophenone

[0090] Example 8. Preparation of latex polymer by using Surfactant B in an all acrylic latex through emulsion polymerization.

[0091] De-ionized water (145.6 g) and the polymerizable Surfactant B (29.27% solids, 4.4 g) were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 10.9 g monomer pre-emulsion I was charged to the reactor. The monomer pre-emulsion I was prepared by mixing water (28.2 g), polymerizable Surfactant B (3.5 g), methyl methacrylate (11 g), butyl acrylate (62.2 g), methacrylic acid (0.44 g), and Sipomer PAM600 (3.94 g). Once the temperature of the reactor had stabilized at 80°C. A solution of ammonium persulfate (0.61 g dissolved in 4.87 g deionized water) was added to the reactor.

[0092] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion I [water (28.2 g), polymerizable Surfactant B (3.5 g), methyl methacrylate (11 g), butyl acrylate (62.2 g), methacrylic acid (0.44 g), and Sipomer PAM600 (3.94 g)] and initiators solution (0.31 g dissolved in 30.3 g deionized water) started to continuously be added to the reactor within 1 hour at temperature 80-83°C. Then the monomer pre-emulsion II [water (50.6 g), polymerizable Surfactant A (0.9 g), methyl methacrylate (99.2 g), butyl acrylate (41 .5 g), and methacrylic acid (4.0 g)] started continuous feeding to the reactor within 2 hours. Then a chaser solution (0.18 g t-butyl hydroperoxide dissolved in 2.45 g DI water, and 0.18 g isoascorbic acid dissolved in 2.45 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 45.5%, and the average particle size was 121.8 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer about 10 degree C. The latex properties were given in TABLE 4.

[0093] Example 9. Preparation of latex polymer by using Surfactant B in an all acrylic latex through emulsion polymerization.

[0094] De-ionized water (145.6 g) and the polymerizable Surfactant B (29.27% solids, 4.4 g) were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 10.9 g monomer pre-emulsion I was charged to the reactor. The monomer pre-emulsion I was prepared by mixing water (78.9 g), polymerizable Surfactant A (4.4 g), methyl methacrylate (110.3 g), butyl acrylate (63.9 g), methacrylic acid (5.5 g), and Sipomer PAM600 (3.94 g). Once the temperature of the reactor had stabilized at 80°C. A solution of ammonium persulfate (0.61 g dissolved in deionized 4.87 g water) was added to the reactor.

[0095] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion and initiators solution (0.31 g dissolved in 30.3 g deionized water) started to continuously be added to the reactor within 2 hours at temperature 80-83°C. Then a monomer pre-emulsion (mixing of butyl acrylate [(39.7 g) and pre-emulsion I (26.7 g)] started continuous feeding to the reactor within 1 hours. Then a chaser solution (0.18 g t-butyl hydroperoxide dissolved in 2.45 g DI water, and 0.18 g isoascorbic acid dissolved in 2.45 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 44.0%, and the average particle size was 123.2 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer about 10 degree C. The latex properties were given in TABLE 4.

[0096] Comparative Example 10. Preparation of latex polymer by using a comparative conventional surfactant (i.e., a non-polymerizable surfactant) through emulsion polymerization.

[0097] De-ionized water (240 g) and Rhodapon UB STD Surfactant (30% solids, 6.1 g) were added to a suitable reactor for emulsion polymerization equipped with agitation, heating and cooling means with a slow continuous nitrogen purge. Under continuous agitation, the temperature of the reactor was raised to 80°C. At 80°C, 25.1 g monomer pre-emulsion was charged to the reactor. The monomer pre-emulsion was prepared by mixing water (130 g), Rhodapon UB STD Surfactant (12.2 g), methyl methacrylate (180 g), butyl acrylate (169.2 g), and methacrylic acid (10.8 g). Once the temperature of the reactor had stabilized at 80°C. A solution of ammonium persulfate (1 .0 g dissolved in deionized 8 g water) was added to the reactor.

[0098] Twenty five minutes later a sample was taken from the reactor for particle size analysis. Then the remaining monomer pre-emulsion and initiators solution (0.5 g dissolved in 50 g deionized water) started to continuously be added to the reactor within 3 hours at temperature 80-83°C. Then a chaser solution (0.3 g t-butyl hydroperoxide dissolved in 4 g DI water, and 0.3 g isoascorbic acid dissolved in 4 g DI water) was charged to the reactor. The reactor was kept at 80°C for further 30 minutes until the values of the final solids were constant or near maximum theoretical value. The polymer dispersion obtained had a solid content of 44.7%, and the average particle size was 117.4 d.nm. The reactor was cooled below 40°C and the resulting latex was filtered through a 200um polyester filter. The calculated Tg of this polymer about 10 degree C. The latex properties were given in TABLE 4.

TABLE 4. Latex properties of Examples 8 and 9 along with Comparative Example 10

[0099] Example 11. The latex polymers that were prepared in Examples 8 and 9 along with Comparative Example 10 were formulated in a 22% PVC semi-gloss exterior paint. The paint formulation is given in TABLE 5a.

TABLE 5a. Paint formulation of exterior acrylic paint.

[00100] Similar to the above, the blocking resistance and DPUR of the formulated exterior paints in Table 5a were evaluated according to the following methods. Paints was drawdown over different substrates and let dry for 1 to 7 days in accordance with the applicable ASTM methodology. Blocking resistance was tested according to ASTM D4946. Hot blocking resistance tests were performed at 50°C under conditions of 1 kg weight for 30 minutes based on the standard method. The testing results were reported on a scale of from 1 to 10, with 1 being the worst and 10 being the best. The testing results are given below in Table 5b and illustrated in Fig. 5. As can be seen, paints containing the latex polymers that were prepared using the polymerizable surfactant show significantly better performance. [00101] Table 5b. Paint hot blocking resistance.

[00102] The DPUR performance was tested by following a modified procedure based on ASTM D3719. The test panels were painted using the formulated exterior paints containing the latex polymers that were prepared in Examples 8 and 9 along with Comparative Example 10. After being coated with the respective formulated exterior paints, the test panels dried for seven (7) days. Then a uniform coating of a brown iron oxide (BIO) slurry was brushed onto a portion of the surface on the test panels, but without staining the surface of the test panels. Only a portion of the surface of the test panels were coated with the BIO slurry, while the remaining surface of the test panels were not coated with the BIO slurry for comparison purposes. The brown oxide slurry was formed by dissolving 2 drops of Rhodoline® 111 in 250 grams of water, then adding 125 grams of BIO pigment, and then dispersing the pigment with a benchtop stirrer until homogenous. The test panels coated with the brown oxide slurry were then air-dried until the slurry is completely dry (i.e., a minimum of four (4) hours, or preferably overnight, to ensure the slurry is completely dry). The test panels are then washed under running tepid water while rubbing gently and evenly with a clean piece of cheesecloth, including the area in which the brown oxide slurry was applied and allowed to dry. All excess slurry is removed. The reflectance readings are then reported according to ASTM D5326, making certain to take an average of at least three (3) readings for both treated and untreated areas of the test sample. Record DPUR as % removed - high numbers indicate better DPUR. The testing results are given below in Table 5c and illustrated in Fig. 6. The results show that paints containing the latex polymers that were prepared using the polymerizable surfactant demonstrate improved DPUR.

[00103] Table 5c. DPUR %

[00104] The present subject matter being thus described, it will be apparent that the same may be modified or varied in many ways, including equivalents thereof. Such modifications and variations are not to be regarded as a departure from the spirit and scope of the present subject matter, and all such modifications and variations, including equivalents thereof, are intended to be included within the scope of the following claims.

Claims

1. A coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (I):

wherein:

2. The coating composition of claim 1 , wherein M⁺ is Na⁺, NH4+, or combinations thereof.

3. The coating composition of claim 1 or 2, wherein x is 2 to 4 and y is 14 to 18.

4. The coating composition of any of the preceding claims, wherein the coating composition is an elastomeric coating, architectural coating, or both.

5. The coating composition of any of the preceding claims, wherein the coating composition is a latex coating.

6. The coating composition of claims 1 to 5, wherein the coating composition has a glass transition temperature (Tg) of -40°C to -20°C, as measured by ASTM D3418.

7. The coating composition of claims 1 to 5, wherein the coating composition has a glass transition temperature (Tg) of 10°C to 40°C, as measured by ASTM D3418.

8. The coating composition of any of the preceding claims, wherein Ri is a bicyclo_[d.e.f]heptyl or bicyclO[_d.e.f]heptenyl group wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1 , and the sum of d + e + f = 5, and which may, optionally, be substituted on one or more of the ring carbon atoms by one or more (Ci-C₆)alkyl groups.

9. The coating composition of any of the preceding claims, wherein the coating composition has improved dirt pick-up resistance (DPUR), as measured by ASTM D3719.

10. The coating composition of any of the preceding claims, wherein the coating composition has improved hardness, as measured by ASTM D4366.

11. The coating composition of any of the preceding claims, wherein the coating composition has improved blocking resistance, as measured by ASTM D4946.

12. The coating composition of any of the preceding claims, wherein the coating composition does not contain any benzophenone.

13. A method of making a coating composition comprising a polymer formed from the at least one polymerizable surfactant of claim 1 , the method comprising emulsion polymerizing the at least one polymerizable surfactant with at least one other monomer.

14. The method of claim 13, wherein the at least one other monomer is selected from acrylate monomers, styrene monomers, vinyl ester monomers, or combinations thereof.

15. The method of claims 13 or 14, wherein the at least one other monomer is selected from methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, methacrylates and blends thereof, acrylic acid, methacrylic acid, styrene, vinyl toluene, vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid, including vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and the like, and mixtures thereof.

16. The method of claims 13 to 15 further comprising a surfactant selected from sodium alkylbenzene sulfonates or any salt thereof, alkyl sulfosuccinates or any salt thereof, alkyldiphenyloxide disulfonates or any salt thereof, ethoxylated alkylphenol sulfates or any salt thereof, ethoxylated alkylphenol phosphates or any salt thereof, fatty alcohol sulfates or any salt thereof, fatty alcohols phosphates or any salt thereof, alkyl alcohol ethoxylate sulfate or any salt thereof, and combinations thereof.

17. The method of claims 13 to 16 further comprising at least one ingredient selected from chain transfer agents, additives to adjust pH, compounds utilized as protective colloids, and combinations thereof.

18. The method of claims 13 to 17, wherein the coating composition does not contain any benzophenone.

19. The use of a polymerizable surfactant of formula (I):

wherein:

20. The use of claim 19, wherein the coating composition is an elastomeric coating, architectural coating, or both.

21 . The use of claim 19 or 20, wherein the coating composition is a latex coating.

22. The use of claim 19 to 21 further comprising at least one ingredient selected from chain transfer agents, additives to adjust pH, compounds utilized as protective colloids, and combinations thereof.

23. The use of claims 19 to 22, wherein the coating composition does not contain any benzophenone.

24. The use of a coating composition comprising a polymer formed from at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (I):

wherein:

25. The use of claim 24, wherein the coating composition does not contain any benzophenone.