WO2025026728A1

WO2025026728A1 - Coating compositions having improved properties comprising a polymer formed from polymerizable surfactants

Info

Publication number: WO2025026728A1
Application number: PCT/EP2024/070135
Authority: WO
Inventors: Nemesio Martinez-Castro; Eugene J. Anderson; Dongcheel Lee; Changheon Kang; Brian VEST; Lichang Zhou; Zhicheng YUAN
Original assignee: Specialty Operations France
Priority date: 2023-08-03
Filing date: 2024-07-16
Publication date: 2025-02-06

Abstract

A polymer composition produced by polymerization utilizing polymerizable phosphate mono-ester compound or a salt thereof, and polymerizable phosphate di-ester compound or a salt thereof and at least one polymerizable surfactant. A coating composition including the polymer formed from phosphate ester composition including polymerizable phosphate mono-ester compound or a salt thereof, and polymerizable phosphate di-ester compound or a salt thereof and at least one polymerizable surfactant. The coating composition is suitable for use, for example, on metal or ceramic substrates. Methods of making and using such polymer compositions, for example for use as waterborne coating compositions, and coating compositions having improved adhesion and water resistance. Methods of improving adhesion and water resistance by employing the polymer composition in the coating composition.

Description

COATING COMPOSITIONS HAVING IMPROVED PROPERTIES COMPRISING A POLYMER FORMED FROM POLYMERIZABLE SURFACTANTS

FIELD OF THE INVENTION

[0001] This invention relates to an emulsion polymer composition produced by emulsion polymerization utilizing polymerizable phosphate mono-ester compound or a salt, and polymerizable phosphate di-ester compound or a salt thereof and polymerizable surfactants. The present invention generally relates to coating compositions comprising a polymer formed from polymerizable phosphate mono-ester compound or a salt, and polymerizable phosphate di-ester compound or a salt thereof and at least one polymerizable surfactant. This invention also relates to methods of making and such emulsion polymer composition. This invention relates to methods of improving adhesion, corrosion resistance, water resistance, gloss, gloss retention, and hiding of a coating composition employing the emulsion polymer composition. This is especially useful in Direct to Metal or Direct to Ceramic uses with improved adhesion, improved gloss, improved corrosion resistance and improved water resistance as well as uses on ceramic surfaces. This invention provides water based paint and industrial coating formulations to avoid solvent based formulations.

BACKGROUND OF THE INVENTION

[0002] 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.

[0003] 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.

[0004] 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 hardness, weatherability, durability, and adhesion can also be affected. In particular, surfactants in paints or other coatings can make the resulting coating or film less resilient and durable.

[0005] 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.

[0006] 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.

[0007] 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 hardness 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 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.

[0008] It is therefore desirable that there be available polymerizable monomers that enable one to eliminate or decrease the amount of such emulsifiers required in the emulsion polymerization process.

SUMMARY OF THE INVENTION

[0009] This invention provides a polymerizable composition comprising:

(A) a phosphate ester composition comprising:

(a) at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I):

R’-C(O)- R² -X¹ (I) wherein:

R¹ is an substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical, typically the vinyl radical is methyl substituted;

R² is a divalent polyoxyalkylene radical having one to five, preferably one to three, oxyethylene units, oxypropylene units, or a mixtures thereof, further preferably one to five, or one to three, oxyethylene units;

X¹ is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and

(b) at least one polymerizable phosphate di-ester compound or a salt thereof having the formula (II):

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

R³ is an substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical, typically the vinyl radical is methyl substituted;

R⁴ is a divalent polyoxyalkylene radical having one to five, preferably one to three oxyethylene units, oxypropylene units, or a mixtures thereof, further preferably one to five, or one to three, oxyethylene units;

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4- 2.1:1, 1.5-2.1:1, 1.5-2.0:!, 1.6-1 9:1, 1.7-1 9:1, or 1.8-1 9:1; and

(B) a polymerizable surf actant of formula (III):

wherein Ri is a Cs-Ci4 alkyl group or a bicyclic group; wherein “x” is an integer from 1-20, wherein “y” is an integer from 1-30; wherein M⁺ is H⁺, Na⁺, NH4⁺, K⁺ or Li⁺; and one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers, or vinyl ester monomers, butadiene, ethylene, or vinyl chloride and optionally, at least one additional surfactant.

[0010] This invention provides a coating composition comprising a polymer formed from:

(A) the at least one polymerizable phosphate mono-ester compound or salt thereof and the at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition as described in this specification comprising:

(a) the at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I):

R’-C(O)- R² -X¹ (I) wherein:

R¹ is a substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical, preferably the vinyl radical is methyl substituted;

R² is a divalent polyoxyalkylene radical having one to five, preferably one to three oxyethylene units, oxypropylene units, or a mixtures thereof, further preferably one to five, or one to three, oxyethylene units;

(b) the at least one polymerizable phosphate di-ester compound or a salt thereof having the formula (II):

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

R³ is a substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical; R⁴ is a divalent polyoxyalkylene radical having one to five, preferably one to three oxyethylene units, oxypropylene units, or a mixtures thereof, further preferably one to five, or one to three, oxyethylene units;

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt, wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1:1, or typically 1.4-2.1:1, 1.5-2.1 : 1, 1.5-2.0: 1, 1.6-1 9:1, 1.7-1.9: 1, or 1.8-1 9:1; and

(B) at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (III)

wherein:

Ri is a Cs-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; and

(C) at least one other polymerizable monomer.

[0011] 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 (A) the phosphate ester composition described herein, (B) the at least one polymerizable surfactant, wherein the at least one polymerizable surfactant has formula (I), with (C) at least one other monomer.

[0012] In yet another embodiment, the present invention generally relates to the use of:

R’-C(O)- R² -X¹ (I) wherein: R¹ is a substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical, preferably the vinyl radical is methyl substituted;

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

R³ is a substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical;

(B) a polymerizable surfactant of formula (III):

wherein:

Ri is a Cs-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. [0013] In further embodiments, the present invention generally relates to the use of a coating composition comprising a polymer formed from: (A) the at least one polymerizable phosphate mono-ester compound or salt thereof and the at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition as described in this specification, (B) at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (III):

wherein:

Ri is a Cs-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, and

(C) at least one other monomer; to coat at least a part of the surface of a substrate, preferably wherein the coating composition provides improved hardness.

[0014] Typically the polymer composition is a polymer composition further comprising a surfactant in addition to the polymerizable surfactant. For purposes of the present description this additional surfactant is termed as a secondary surfactant. The secondary surfactant is preferably an anionic surfactant, most preferably a phosphate ester anionic surfactant, and the polymerization is by emulsion polymerization. However, the polymerization may be polymerization in the presence of polymerizable phosphate monoester compound, polymerizable phosphate di-ester compound and polymerizable monomer without added surfactant, for example polymerization of these ingredients in solvent.

[0015] Preferably the polymerizable phosphate mono-ester compound or a salt thereof and the polymerizable phosphate di-ester compound or a salt thereof have an absence of oxypropylene units. [0016] The polymerizable phosphate mono-ester compounds and the polymerizable phosphate di-ester compounds act as polymerizable “monomers”. These monomers can be used in acid and basic form. For the basic form sodium hydroxide or potassium hydroxide or ammonium hydroxide are typically used for the neutralization. [0017] The present invention has beneficial results especially to provide performance improvement for waterborne Industrial Coatings. The present invention preferably provides industrial coatings that meet ISO12944 CLASSIFICATION C3 and C4. Industrial coatings are generally for coating metal.

[0018] The high mono/di-ester polymerizable phosphated monomers of this invention and polymerizable surfactant makes it possible to eliminate or reduce traditional emulsifiers (surfactants) employed in emulsion polymerization and eliminate or reduce the problems or drawbacks associated with their presence in the resulting latices (emulsions) to be used for paints or coatings.

[0019] Other aspects of certain embodiments include methods of preparing a polymer, including but not limited to latex polymer emulsions and paints, utilizing the A) the at least one polymerizable phosphate mono-ester compound or salt thereof and the at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition as described in this specification, and polymerizable surfactant of formula (I).

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG. 1 shows a standard classification of adhesion test results according to the ASTM D3359-23 Cross Hatch Method.

[0021] FIG. 2 shows the results of testing paints for Metal Adhesion according to the ASTM D3359-23 method.

[0022] FIG. 3 compares Adhesion on CRS (cold rolled steel) and aluminum after Weathering with either 240 hours of salt spray or 4 hours dray and 24 horns soaked in deionized water for Comparative Paint A including Comparative Latex Polymer A made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Phosphate Ester Emulsifier A vs. Inventive Paint Bl including Inventive Latex Polymer Bl made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Polymerizable Surfactant Monomer BL

[0023] FIG. 4 shows results of tests for blistering resistance of Comparative Paint A including Comparative Latex Polymer A made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Phosphate ester emulsifier A vs. Inventive Paint B2 including Inventive Latex Polymer B2 made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Polymerizable surfactant monomer B2. [0024] FIG. 5 shows results of tests for water resistance of Comparative Paint A including Comparative Latex Polymer A made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Phosphate ester emulsifier A vs. Inventive Paint Bl including Inventive Latex Polymer Bl made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Polymerizable Surfactant Monomer BL

[0025] FIG. 6 shows results of tests for ceramic adhesion of Comparative Coating Formulation C including Comparative Latex Polymer C made from the emulsified latex blend with Phosphate Ester Emulsifier A and no Specialty Phosphate Ester Monomer Mixture A vs. Inventive Coating Formulation D including Inventive Latex Polymer D made from the emulsified latex blend with Polymerizable Surfactant Monomer B2 and Specialty Phosphate Ester Monomer Mixture A.

DETAILED DESCRIPTION OF THE INVENTION

[0026] General Definitions

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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, iso-propyl, n-butyl, secbutyl, t-butyl, pentyl, n-hexyl, cyclohexyl.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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. [0035] 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.

[0036] 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, haloalkyl, or amino, such as, for example, phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl.

[0037] 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.

[0038] As used herein, “AGE” is allyl glycidyl ether.

[0039] 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. [0040] 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.

[0041] Coating Compositions

[0042] 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. 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 hardness with or without benzophenone.

[0043] As also discussed above, in certain embodiments the coating compositions of the present invention can have improved hardness, as measured by ASTM D4366-16. 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 D4366-16, compared to coating compositions comprising a polymer that is not formed from at least one polymerizable surfactant of the present invention.

[0044] And as discussed above, the coating compositions of the present invention can have superior hardness resistance.

[0045] 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 D4946-89(2019). 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 D3418-21. 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 D3418-21.

[0046] 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 temperatine (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 D3418-21. 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 D3418-21.

[0047] Phosphate ester composition

[0048] In one aspect, this invention relates to a phosphate ester composition comprising:

R’-C(O)- R² -X¹ (I) wherein:

(b) at least one polymerizable phosphate di-ester compound or a salt thereof having the formula

(II):

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4- 2.1:1, 1.5-2 1:1, 1.5-2.0T, 1.6-1 9:1, 1.7-1.9T, or 1.8-1.9T.

[0049] Typically the parts by weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, furthermore preferably 64:36 to 67:33, wherein the total of the parts by weight of the polymerizable phosphate mono-ester compound and the polymerizable phosphate di-ester compound equals 100 parts by weight. For example, the parts by weight ratio range from 55:45 to 67:33 encompasses 55:45, 60:40, or 67:33, However, the parts by weight ratio range from 55:45 to 67:33 does not encompass 55:33 or 67:45.

[0050] The polyoxyalkylene unit can be derived from a variety of epoxyalkane compounds including ethylene oxide, propylene oxide, butylene oxide, styrene oxide, other alkyl, cycloalkyl or aryl substituted alkyl oxides or alkyl or aryl glycidyl ethers. It may additionally include hydrocarbon chain segments such as might be derived from ring opening of caprolactone by 2 -hydroxy ethyl methacrylate.

[0051] Typically R¹ of the phosphate ester composition is selected from the group consisting of CH₂=CH- , CH₂=C(CH₃)-, or cis-CH(COOH)=CH.

[0052] Typically R² of the phosphate ester composition has one to five, preferably one to three oxy ethylene units.

[0053] Typically R² of the phosphate ester composition has at least one oxyethylene unit.

[0054] Typically R² of the phosphate ester composition has R² has an absence of oxypropylene units.

[0055] Typically R³ of the phosphate ester composition has is selected from the group consisting of CH₂=CH-, CH₂=C(CH₃)-, or cis-CH(COOH)=CH-.

[0056] Typically R⁴ of the phosphate ester composition has is a divalent polyoxyalkylene radical having at least one oxyethylene unit.

[0057] Typically R⁴ of the phosphate ester composition has is a divalent polyoxyalkylene radical having one to three oxyethylene units.

[0058] Preferably the polymerizable phosphate mono-ester compound or a salt thereof and the polymerizable phosphate di-ester compound or a salt thereof of the ester composition have an absence of oxypropylene units.

[0059] A typical polymerizable phosphate mono-ester compound of formula (I), also known as a mono alkyl phosphate (MAP), has the structural formula (la):

la wherein R is an optionally substituted vinyl radical, preferably a C₂-Cs, more preferably a C₂-C₃ vinyl radical; n is moles of ethylene oxide, M is H, NH4, Na, K.

[0060] A typical polymerizable phosphate di-ester compound of formula (II), also known as a dialkyl phosphate (DAP), has the structural formula (Ila):

Ila wherein R is an optionally substituted vinyl radical, preferably a C₂-Cs, more preferably a C₂-C₃ vinyl radical; n is moles of ethylene oxide, M is H, NH4, K. [0061] A typical polymerizable phosphate mono-ester compound of formula (I), also known as a mono alkyl phosphate (MAP), has the structural formula (Ib):

wherein R is H or Me, Ri is H or Me, n is 1-5, each R2 is independently H, NH4, Na, or K, typically H.

Preferably, each Ri is H, or at least 2 Ri are H and at least one Ri is Me.

[0062] A typical polymerizable phosphate di-ester compound of formula (II), also known as a di alkyl phosphate (DAP), has the structural formula (lib):

wherein R is H or Me, Ri is H or Me, n is 1-5, R2 is H, NH4, Na, or K, typically H. Preferably, for the moiety on each side of the phosphate group each Ri is H, or at least 2 Ri are H and at least one Ri is Me. [0063] Typically ((2 -methyl- 1 -oxopropane- 1 ,3 -diyl)bis(oxy))bis(ethane-2, 1 -diyl)bis(2-methacrylate) is 10 to 20 wt.%, more typically 15-20 wt% of the phosphate ester composition.

[0064] Typically ethylene glycol dimethacrylate is 1 to 10 wt.%, more typically 3-7 wt% of the phosphate ester composition.

[0065] Typically the phosphate ester composition further comprises phosphoric acid, preferably the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) is 10:90 to 25:75, more preferably 10:90 to 20:80, and more preferably 10:90 to 20:70.

[0066] The at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I) and polymerizable phosphate di-ester compound of formula (Il)may be neutralized with one or more of sodium hydroxide, potassium hydroxide or ammonium hydroxide, preferably ammonium hydroxide.

Method for the Production of the Above-Described Phosphate Ester Composition

[0067] In another aspect, this invention also provides a method for the production of the above-described phosphate ester composition having the high ratio of polyalkylene oxide (meth)acrylate polymerizable phosphate mono-ester to polyalkylene oxide (meth)acrylate polymerizable phosphate di-ester.

[0068] The polymerizable phosphate mono-ester compound and polymerizable phosphate di-ester compound can be made by different routes. For example, a preferred polymerizable phosphate mono- or di-ester compound wherein X is a phosphate -OPO3H2 group can be made by phosphation of the product of esterification of a polyalkylene glycol with a vinyl-functional carboxylic acid, or anhydride or acid halide thereof. The phosphation may be conducted as disclosed in US Patents 5,463,101, 5,550,274 and 5,554,781, as well as in EP Patent publication number EP 0 675,076 A2. A polymerizable phosphate mono- or di-ester compound wherein X is a sulfate -OSO3H2 group or sulfonate -SO3H group can be made by sulfating one of the hydroxyl groups of a polyalkylene glycol, or replacing said hydroxyl group with a sulfonate group, and then esterifying the remaining hydroxyl group of said polyalkylene glycol with a vinyl-functional carboxylic acid, or anhydride or acid halide thereof.

[0069] In particular, the present invention relates to a method for the production of the phosphate ester composition comprising:

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the weight ratio of the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1:1, or typically 1.4-2.1 : 1, 1.5-2.1 : 1, 1.5-2.0: 1, 1.6-1 9:1, 1.7-1.9: 1, or 1.8-1 9:1; and said method comprising the steps of:

A) preparing a phosphoric acid-alcohol reactant solution by i) dissolving in a reactor: a) from about 75 weight % to about 117 weight % phosphoric acid or polyphosphoric acid in b) at least one alcohol medium of the formula R'-C(O)- R² -O-H, wherein R¹ and R² are as defined above, for example hydroxyethyl methacrylate, under essentially non- reactive temperature conditions;

B) then ii) blending a stoichiometrically effective amount of phosphoric anhydride into said reactant solution and

Hi) reacting the phosphoric acid in said reactant solution with the stoichiometrically effective amount of phosphoric anhydride; and

C) reacting the phosphation reagent so produced with the alcohol medium, typically at from about 75 °C. to about 100 °C. for a reaction hold time of from about 4 to about 20 hours. Following the hold, typically adding deionized water to the reactor to hydrolyze any residual pyrophosphates, followed by an additional 1-4 horn hold, and then cooling. To inhibit unwanted homopolymerization, methoxyhydroquinone (MEHQ) or other suitable inhibitor may be charged to the reactor and allowed to dissolve in the reactant solution.

[0070] For the purposes of the present description, the term stoichiometrically effective amount of phosphoric anhydride means an amount sufficient, in combination with the other ingredients, to make the phosphate ester composition.

[0071] Typically the parts by weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, furthermore preferably 64:36 to 67:33, wherein the total of the parts by weight of the polymerizable phosphate mono-ester compound and the polymerizable phosphate di-ester compound equals 100 parts by weight. For example, the parts by weight ratio range from 55:45 to 67:33 encompasses 55:45, 60:40, or 67:33, However, the parts by weight ratio range from 55:45 to 67:33 does not encompass 55:33 or 67:45.

[0072] Preferably the polymerizable phosphate ester composition has a residual of the phosphoric acid wherein the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) is 10:90 to 25:75, typically 10:90 to 20:80, more typically 10:90 to 10:70, and more typically 10:90 to 18:82, for example 11:89-16:84. For example, the polymerizable phosphate ester composition has a residual of the phosphoric acid is 10-16 wt.% of the polymerizable phosphate ester composition.

[0073] Preferably the polymerizable phosphate ester composition has a residual of the alcohol which is less than 6 weight percent of the polymerizable phosphate ester composition.

[0074] Preferably the polymerizable phosphate mono-ester compound or a salt thereof and the polymerizable phosphate di-ester compound or a salt thereof have an absence of oxypropylene units. [0075] The polymerizable phosphate mono-ester compounds and the polymerizable phosphate di-ester compounds act as polymerizable “monomers”. These monomers can be used in acid and basic form. For the basic form sodium hydroxide or potassium hydroxide or ammonium hydroxide are typically used for the neutralization.

[0076] Polymerizable Surfactants

[0077] 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.

[0078] 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).

[0079] 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. [0080] 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.

[0081] 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 hardness resistance.

[0082] More generally, in an embodiment, the polymerizable surfactant can have formula (III):

wherein:

Ri is a Cs-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.

[0083] 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 Cs-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 Cs-Ci4 alkyl group, preferably a C10-C14 alkyl group, and wherein at least one different polymerizable surfactant of formula (I) has Ri that is a different Cs-C I4 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.

[0084] When Ri 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, Ri is a bicyclo[d _e qheptyl or bicyclo[d _e ijheptenyl 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-Ce)alkyl groups (otherwise referred to herein as “Nopol”).

[0085] In another embodiment, Ri is a bicyclic group, or more specifically in one embodiment, a bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (CV-CVjalkyl-polycthcr 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-Ce)alkyl groups per carbon atom.

[0086] In one embodiment, Ri is a linear or branched Cs-Ci4 alkyl group, preferably a linear or branched C10-C14 alkyl group, or mixtures thereof, and in other embodiments, Ri is a linear or branched Ce-Cis alkyl group.

[0087] Furthermore, Ri can be any one of or any combination of:

(i) a bicyclop 1 ijheptyl or bicyclo[3 1 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 bicyclop 1 ijheptyl or bicyclop 2 ijheptenyl 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- Ce)alkyl radicals, more typically by two methyl radicals.

[0088] Suitable bicyclic groups for Ri 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):

[0089] For example, Ri can be derived from a bicycloheptenyl intermediate compound (VII), also known as "Nopol":

(VII), which can be made by reacting P-pinene with formaldehyde.

[0090] 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. [0091] 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.

[0092] 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.

[0093] 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+.

[0094] In a more particular embodiment, the polymerizable surfactant can have formula (Illa):

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.

[0095] In yet another particular embodiment, the polymerizable surfactant can have formula (Illb):

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.

[0096] In particularly preferred embodiments, the polymerizable surfactant is Nopol-2.6AGE-15EO- sulfate sodium salt, which is represented as follows in formula (Illd):

wherein: x averages 2.6; and y is 15.

[0097] 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):

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.

[0098] In another specific embodiment, the polymerizable surfactant can be C12/C14-2.6AGE-15EO- sulfate ammonium salt. More generally, the polymerizable surfactant can have formula (VI):

[0099] 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.

[00100] 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).

[00101] 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), fiber processing aids, non-dripping agents, soil resistance finishes, paints, and the like. [00102] 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. For purposes of this description these additional surfactants are termed secondary surfactants. 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 non-ionic surfactants.

[00103] Polymer Composition Comprising Units From the Above-Described Polymerizable Phosphate Mono-Ester Compound and Polymerizable Phosphate Di-Ester Compound and Polymerizable Surfactant

[00104] The invention also relates to a polymer composition made from units from the abovedescribed polymerizable phosphate mono-ester compound, polymerizable phosphate di-ester compound and polymerizable surfactant. [00105] In particular, the invention provides a coating composition comprising a polymer comprising monomeric units from:

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt, wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1:1, typically 1.4-2.1:1, 1.5- 2.1:1, 1.5-2.0:1, 1.6-1 9:1, 1.7-1.9:!, or 1.8-1 9:1;

(B) a polymerizable surf actant of formula (III):

wherein Ri is a Cs-Ci4 alkyl group or a bicyclic group; wherein “x” is an integer from 1-20, wherein “y” is an integer from 1-30; wherein M⁺ is H⁺, Na⁺, NH4⁺, K⁺ or Li⁺; and one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers, or vinyl ester monomers, butadiene, ethylene, or vinyl chloride and (C) at least one other polymerizable monomer; and optionally, at least one surfactant.

[00106] Typically the parts by weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, furthermore preferably 64:36 to 67:33, wherein the total of the parts by weight of the polymerizable phosphate mono-ester compound and the polymerizable phosphate di-ester compound equals 100 parts by weight. For example, the parts by weight ratio range from 55:45 to 67:33 encompasses 55:45, 60:40, or 67:33, However, the parts by weight ratio range from 55:45 to 67:33 does not encompass 55:33 or 67:45.

[00107] 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. (Termed herein as secondary 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 non-ionic surfactants.

[00108] The mixture typically further comprises a surfactant, wherein the composition comprises 0.5 to 3 wt.% said surfactant based on total monomer including the polymerizable phosphate mono-ester compound, polymerizable phosphate di-ester compound, and other polymerizable monomer. The secondary surfactant is preferably anionic surfactant, more preferably a phosphate ester anionic surfactant. The polymer composition is typically an emulsion polymer composition.

[00109] 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 Cio-ie alcohol ethoxylate sulfate, or any salt thereof.

[00110] 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.

[00111] 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.

[00112] 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.

[00113] 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)Zbutadiene, (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.

[00114] The other polymerizable monomer is typically selected from methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, other acrylates, methacrylates and their blends, acrylic acid, methacrylic acid, cyclohexyl methacrylate, styrene, vinyl toluene, vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid, e.g. vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and the like, and mixtures thereof.

[00115] The invention may also provide a waterborne coating comprising the polymer composition.

[00116] The above-described polymerizable phosphate mono-ester compound and polymerizable phosphate di-ester compound and polymerizable surfactants of the present invention can be used to make a coating composition. That is, the above-described polymerizable phosphate mono-ester compound and polymerizable phosphate di-ester compound and polymerizable surfactants of the present invention can be used to form a polymer for coating compositions. Additionally, the above-described polymerizable phosphate mono-ester compound and polymerizable phosphate di-ester compound and 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 hardness.

[00117] Methods of Improving Properties

[00118] The invention may also provide a method of improving the corrosion resistance of a metal substrate comprising contacting at least a portion of the surface of the metal substrate with the coating composition, wherein the coating composition comprises the polymer composition, compared to coating the metal substrate with a coating composition which is the same but does not include monomeric units from said polymerizable phosphate mono-ester compound or a salt thereof and said polymerizable phosphate di-ester compound or a salt thereof.

[00119] The invention may also provide a method of improving the water resistance of a coating composition to a substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition, compared to coating the substrate with a coating composition which is the same but does not include monomeric units from said polymerizable phosphate mono-ester compound or a salt thereof and said polymerizable phosphate di-ester compound or a salt thereof.

[00120] The invention may also provide a method of improving any one or more of gloss, gloss retention, and hiding of a coating composition on a substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the emulsion polymer composition, compared to coating the substrate with a coating composition which is the same but does not include monomeric units from said polymerizable phosphate mono-ester compound or a salt thereof and said polymerizable phosphate di-ester compound or a salt thereof.

[00121] The invention may also provide a method of improving the adhesion of a coating composition to a metal substrate or ceramic substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition. The substrate is typically a metal, for example, aluminum, steel or galvanized steel.

[00122] The invention may also provide a method of improving the adhesion of a coating composition intended to be coated to a metal substrate or ceramic substrate comprising contacting at least a portion of the surface of the substrate with a coating composition, called conversion coating, wherein the conversion coating comprises the polymer composition of the invention. The substrate is typically a metal, for example, aluminum, steel or galvanized steel.

[00123] As mentioned above the invention relates to different methods of improving some properties of the substrate thanks to the coating composition of the invention.

[00124] In some of these situations, the coating composition of the invention may be used as an undercoat or under layer in a pre-treatment of the substrate, and is called “conversion coating”, because the polymer reacts with the metal and adheres to it, thereby improving the properties, such as the corrosion resistance of the substrate and/or the adhesion of a coating composition to be applied thereafter, over the conversion coating.

[00125] According to an embodiment, the conversion coating is applied on the metal or ceramic surface to be treated, by reaction of said surface with the corresponding conversion composition (in other words, the conversion composition is applied on the metal or ceramic surface for forming a conversion coating thereon).

[00126] Contacting the metal surface with the conversion coating may be made by any means known per se, such as dip coating in a conversion bath or spray coating for example.

[00127] The coating composition of the invention may thus be used both as a conversion coating (in a pre-treatment) and as a coating composition (such as a paint, a varnish or an adhesive) to treat the same substrate.

[00128] When the coating composition is used as a conversion coating, the latter is first applied on the metal or ceramic surface of the substrate. A coating composition including the polymer composition (the same or different but still according to the invention) is then applied on the pretreated substrate. In other words, the polymer composition of the invention is used both in the conversion coating and in the coating composition applied on the conversion coating. [00129] The material obtained comprises a metal or ceramic surface which covered by: a first layer comprising a conversion coating, and a second layer comprising a coating composition, in particular a paint, a varnish or an adhesive.

[00130] An additional layer may be applied between the treated metal or ceramic surface and the coating. This is for example the case for the treatment of metal foil on a first site, that have then to be coated, for example painted, on a second site: in that case, a lubricant may be applied on the treated foil, in order to allow to roll the foil and ease its transportation.

[00131 ] Any metal surface may be treated with the conversion composition of the invention, but the invention is especially suitable for treating metal surfaces of: aluminum or an aluminum-based alloy ; or steel, for example galvanized steel (hot dip galvanized HDG or electrogalvanized EG) ; or cold rolled steel (CRS) ; or magnesium or magnesium-based alloys ; or zinc or zinc-based alloys, titanium or titanium-based alloys.

[00132] The invention is especially interesting for metal surface of aluminum and aluminum alloys, such as Aluminum Alloy AA 5005 tested in the appended examples, or other alloys such as those of Series Ixxx, 2xxx, 3xxx, 4xxx, 5xxxx, 6xxx, such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182, 7075.

[00133] The conversion composition used according to the invention may typically contain fluorides anions and cationic metals, e.g. compounds such as H2CrF6, or more preferably chromium free compounds such as H2TiF6, H2ZrF6, H2HfF6, H2A1F6, H2SiF6, H2GeF6, H2SNF4, HBF4, or TiZr. [00134] The conversion composition may also include other compounds, such as silane precursors for example, and/or cerium salts, and/or terbium molybdate.

[00135] The invention also relates to a method of treating a first metal or ceramic surface S 1 of a first substrate intended to be bonded to a second surface S2 of a second substrate by adhesive bonding, and of imparting a resistance to the adhesive failure to the bonding, said method comprising contacting at least a portion of the first metal surface S 1 with the coating composition.

[00136] An additional advantage of the adhesive bonding obtained according to the invention is that it is highly resistant to corrosive atmospheres and to wet atmospheres, which lead to long lasting adhesive bonding. In most cases, the coating composition is also used for obtaining this additional effect (namely for further imparting to the bonding a resistance to corrosive atmospheres and to wet atmospheres, in other words for obtaining both a very effective, but also long lasting adhesion). In other words, this method also provides a very good resistance to ageing of the adhesive bonding. Such a property can be measured according to tensile tests on so-called “Single Lap Shear” (SLS) assemblies, such as defined in ASTM D- 1002 10, performed on freshly bonded SLS assemblies and performed on SLS assemblies after ageing in corrosive atmospheres, wet atmospheres, or repeated cycles of corrosive atmospheres followed by wet atmospheres, such as ASTM G85 A3. Other tests simultaneously combine a corrosion stress and a mechanical stress (eg compression load), such as the Bv 101-07, known as Ford Durability Stress Test For Adhesive Lap-shear Bonds or Arizona Proven Ground Exposure (APGE).

[00137] Preferably, the metal or ceramic surface SI is a surface comprising a metal selected from aluminum, steel, zinc, magnesium titanium, copper and their alloys, or cobalt-nickel alloys.

[00138] The metal surface SI is preferably made of: aluminum or an aluminum-based alloy ; or steel, for example galvanized steel (hot dip galvanized HDG or electrogalvanized EG) ; or cold rolled steel (CRS) ; or magnesium or magnesium-based alloys ; or zinc or zinc-based alloys, titanium or titanium-based alloys.

[00139] The invention is especially interesting for metal surface of aluminum and aluminum alloys, such as Aluminum Alloy AA 5005 tested in the appended examples, or other alloys such as those of Series Ixxx, 2xxx, 3xxx, 4xxx, 5xxxx, 6xxx, such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182, 7075.

[00140] Preferably, the second surface S2 is a metal surface. The second surface S2 may, however, be a non-metal surface, for example a plastic surface or a composite surface.

[00141 ] According to an embodiment, the second surface S2 is a surface comprising a metal, advantageously selected from aluminum, steel, zinc, magnesium titanium, copper and their alloys, or cobalt-nickel alloys.

[00142] According to one embodiment, the nature of the surfaces S 1 and S2 is the same, but they can also be distinct according to other possible embodiments of the invention. According to a variant, both surfaces SI and S2 are metal surface of aluminum or aluminum alloys.

[00143] According to another possible embodiment, the second surface S2 is a non-metallic surface, for example a plastic surface e.g. based on polyamide, PEEK or ABS ; or a composite surface based e.g on CFRP or Glass Fiber Reinforced Plastics.

[00144] Typically, but not necessarily, the second surface S2 is also a metal surface, having or not the same nature as the first surface SI. According to an advantageous embodiment, the second surface S2 is a metal surface also treated with a coating composition, generally but not necessarily identical to the coating composition used in the treatment of the first surface SI.

[00145] More generally, the polymer coating used in the method according to the invention is preferably used for treating both surfaces SI and S2 before the adhesive bonding of the two surfaces, especially when S2 is a metal surface.

[00146] Method of Making the Above-Described Polymer

[00147] In another aspect, the methods of preparing a polymer (including but not limited to latex polymer emulsions and paints) include using the above-described polymerizable phosphate mono-ester compound and polymerizable phosphate di-ester compound and 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 Cio-Cie alcohol ethoxylate sulfate or any salt thereof.

[00148] 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.

[00149] 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.

[00150] In another aspect, this invention relates to a method of making the above-described polymer comprising the steps of: combining:

(A) a phosphate ester composition of:

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

R³ is an substituted or unsubstituted vinyl radical, preferably a C2-C5, more preferably a C2-C3 vinyl radical, typically the vinyl radical is methyl substituted; R⁴ is a divalent polyoxyalkylene radical having one to five, preferably one to three oxyethylene units, oxypropylene units, or a mixtures thereof, further preferably one to five, or one to three, oxyethylene units;

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4- 2.1:1, 1.5-2.1 : 1, 1.5-2.0: 1, 1.6-1 9:1, 1.7-1.9: 1, or 1.8-1 9:1, and

(B) a polymerizable surfactant of formula (III):

wherein Ri is a Cs-Ci4 alkyl group or a bicyclic group; wherein “x” is an integer from 1-20, wherein “y” is an integer from 1-30; wherein M⁺ is H⁺, Na⁺, NH4⁺, K⁺ or Li⁺; and one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers, or vinyl ester monomers, butadiene, ethylene, or vinyl chloride

(C) at least one other polymerizable monomer to form a mixture, and optionally, at least one surfactant; and polymerizing the at least one polymerizable phosphate mono-ester compound or salt thereof, the at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition, the polymerizable surfactant, and the at least one other polymerizable monomer.

[00151 ] Typically the parts by weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, furthermore preferably 64:36 to 67:33, wherein the total of the parts by weight of the polymerizable phosphate mono-ester compound and the polymerizable phosphate di-ester compound equals 100 parts by weight. For example, the parts by weight ratio range from 55:45 to 67:33 encompasses 55:45, 60:40, or 67:33, However, the parts by weight ratio range from 55:45 to 67:33 does not encompass 55:33 or 67:45.

[00152] Typically combining (A) the phosphate ester composition of the invention, (B) the polymerizable surfactant, and (C) at least one other polymerizable monomer to form a mixture, wherein the weight ratio of phosphate ester monomers to the at least one other polymerizable monomer is typically 1-10:99-90, more typically 1-5:99-95, wherein the total of the parts by weight of the phosphate ester monomers and the at least one other polymerizable monomer equals 100 parts by weight. Thus, a parts by weight ratio of 1-10:99-90 means 1-10 parts by weight phosphate ester monomers per 100 parts by weight of total monomers of phosphate ester monomers and the at least one other polymerizable monomer.

[00153] Typically the mixture further comprises phosphoric acid, preferably wherein the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) 10:90 to 25:75, preferably 10:90 to 20:80, and more preferably 12:88 to 20:80.

[00154] Preferably the polymerizable phosphate mono-ester compound or a salt thereof and the polymerizable phosphate di-ester compound or a salt thereof produced by the method have an absence of oxypropylene units.

[00155] The phosphate ester may be neutralized with (NTL^OH, KOH, or NaOH to convert some phosphate ester to salt.

[00156] The polymerizable phosphate mono-ester compounds and phosphate di-ester compounds are ethylenically unsaturated monomers and, thus, are polymerizable through this unsaturation. The monomer may be useful in a variety of homopolymers and copolymers, e.g. those produced by solution, bulk or suspension polymerization, but should be most useful as a comonomer in the production of latices of low crosslinking density through emulsion polymerization. Emulsion polymerization is discussed in G. Pohlein, “Emulsion Polymerization”, Encyclopedia of Polymer Science and Engineering, vol. 6, pp. 1-51 (John Wiley & Sons, Inc., NY, NY, 1986), the disclosure of which is incorporated herein by reference. Emulsion polymerization is a heterogeneous reaction process in which unsaturated monomers or monomer solutions are dispersed in a continuous phase with the aid of an emulsifier system and polymerized with free-radical or redox intiators. The product, a colloidal dispersion of the polymer or polymer solution, is called a latex.

[00157] 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 combinationof one or more anionic surfactants and one or more non-ionic surfactants.

[00158] The mixture typically further comprises a surfactant, wherein the composition comprises 0.5 to 3 wt.% said surfactant based on total monomer including the polymerizable phosphate moio-cstcr compound, polymerizable phosphate di-ester compound, and other polymerizable monomer. The surfactant is preferably anionic surfactant, more preferably a phosphate ester anionic surfactant. The polymer composition is typically an emulsion polymercomposition.

[00159] Suitable surfactants which may be used with the polymerizable phosphate mono-ester compound and polymerizable phosphate di-ester compound include ionic and nonionic surfactants such as alkyl polyglycol ethers such as ethoxylation products of lauryl, tridecyl, oleyl, and stearyl alcohols; alkyl phenol polyglycol ethers such as ethoxylation products of octyl or nonylphenol, diisopropyl phenol, triisopropyl phenol; alkali metal or ammonium salts of alkyl, aryl or alkylaryl sulfonates, sulfates, phosphates, and the like, including sodium lauryl sulfate, sodium octylphenol glycolether sulfate, sodium dodecylbenzene sulfonate, sodium lauryldiglycol sulfate, and ammonium tritertiarybutyl phenol and penta and octa-glycol sulfonates, sulfosuccinate salts such as disodium ethoxylated nonylphenol half ester of sulfosuccinic acid, disodium n-octyldecyl sulfosuccinate, sodium dioctyl sulfosuccinate, and the like. Preferably the surfactant is anionic surfactant, most preferably phosphate ester anionic surfactant.

[00160] Typical phosphate ester surfactants have the structures (Illa) and (IVa):

Diester (jy_a)

[00161] wherein R is an alkyl group, typically C10-20 alkyl, preferably C12-C16; n is moles of ethylene oxide, typically n is 4-20; and M is H, Na, K, or NIR

[00162] 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, alkyldiphenybxide 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 Cio-ie alcohol ethoxylate sulfate, or any salt thereof. [00163] 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.

[00164] 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.

[00165] 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.

[00166] 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.

[00167] 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)Zbutadiene, (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.

[00168] The comonomers which are typically employed include such monomers as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethyl hexyl acrylate, other acrylates, methacrylates and their blends, acrylic acid, methacrylic acid, cyclohexyl methacrylate, styrene, vinyl toluene, vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid, e.g., vinyl versatate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride and the like, and mixtures thereof. Typical polymers (copolymers) are any such as styrene, methylmethacrylate, methacrylic acid, cyclohexyl methacrylate, ethylhexyl acrylate, and/or acetoacetoxyethyl methacrylate.

[00169] The polymerization method may be by emulsion polymerization. In the above method, suitable initiators, reducing agents, catalysts and surfactants are well known in the art of emulsion polymerization. Typical initiators include ammonium persulfate (APS), hydrogen peroxide, sodium, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, ditertiary butyl peroxide, 2,2'-azobisisobutyronitrile, t-butyl hydroperoxide, benzoyl peroxide, and the like.

[00170] Suitable reducing agents are those which increase the rate of polymerization and include for example, sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, and mixtures thereof.

[00171] Suitable catalysts are those compounds which increase the rate of polymerization and which, in combination with the above-described reducing agents, promote decomposition of the polymerization initiator under the reaction conditions. Suitable catalysts include transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.

[00172] 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.

[00173] A typical method of emulsion polymerization preferably involves charging water to a reactor and feeding as separate streams a pre-emulsion of the monomers and a solution of the initiator. A small amount of the pre-emulsion and a portion of the initiator may be charged initially at the reaction temperature to produce a “seed” latex. The “seed” latex procedure results in better particle-size reproducibility. Under “normal” initiation conditions, that is initiation conditions under which the initiator is activated by heat, the polymerization is normally carried out at about 60-90°C. A typical “normal” initiated process, for example, could employ ammonium persulfate as initiator at a reaction temperature of 80±2°C. Under “redox” initiation conditions, that is initiation conditions under which the initiator is activated by a reducing agent, the polymerization is normally carried out at 60-70°C. Normally, the reducing agent is added as a separate solution. A typical “redox” initiated process, for example, could employ potassium persulfate as the initiator and sodium metabisulfite as the reducing agent at a reaction temperature of 65 ± 2°C. [00174] In the above emulsions, the polymer preferably exists as a generally spherical particle, dispersed in water, with a diameter of about 50 nanometers to about 500 nanometers. Gel content can be determined using the method taught in U.S. Pat. No. 5,371,148, incorporated herein by reference. Glass transition temperature (T_g) is a calculated number based on the proportion of each monomer utilized and the corresponding T_g for a homopolymer of such a monomer. In addition to making emulsion polymers, it is contemplated that the polymerizable surfactants of the present invention can be used to form solution copolymers.

[00175] In particular, the phosphate mono-ester compounds and phosphate di-ester compounds of this invention may be incorporated in effective amounts in aqueous polymer systems, for example paints, to enhance the stability of emulsions of the polymers. The commonly used monomers in making acrylic paints are butyl acrylate, methyl methacrylate, ethyl acrylate, cyclohexyl methacrylate and the like. In acrylic paint compositions the polymer is comprised of one or more esters of acrylic or methacrylic acid, typically a mixture, e.g. about 50/50 by weight, of a high T_g monomer (e.g. methyl methacrylate) and a low T_g monomer (e.g. butyl acrylate), with small proportions, e.g. about 0.5% to about 2% by weight, of acrylic or methacrylic acid. The vinyl-acrylic paints usually include vinyl acetate and butyl acrylate and/or 2-ethyl hexyl acrylate and/or vinyl versatate. In vinyl-acrylic paint compositions, at least 50% of the polymer formed is comprised of vinyl acetate, with the remainder being selected from the esters of acrylic or methacrylic acid. The styrene/acrylic polymers are typically similar to the acrylic polymers, with styrene substituted for all or a portion of the methacrylate monomer thereof. The phosphate mono-ester compounds and phosphate di-ester compounds of this invention may copolymerize with the typical monomers used to make latex for paint to produce paints having enhanced stability and adhesion to surfaces.

[00176] Example 1- Making The Specialty Phosphate Ester Monomer Mixture A [00177] A 500 mL round bottom, 4-neck flask was fitted with a thermocouple, paddle stirrer, pressure equalizing addition funnel and two-head CLAISEN adapter with a dry air needle inlet and a water condenser venting to silicone oil filled bubbler. The flask was charged with 214.72g of hydroxy ethyl methacrylate. Stirring and a slow flow (20ml/min) of subsurface dry air into the liquor were initiated. To inhibit unwanted homopolymerization, 1.75g of methoxyhydroquinone (MEHQ) was charged to the reactor and allowed to completely dissolve. The addition funnel was charged with 61.14g of 105 % polyphosphoric acid, followed by controlled addition over 35 minutes, during which the liquor temperature increased from 35°C to 42°C. The liquid addition funnel was replaced by an auger-type powder addition funnel containing 70.64g of phosphoric anhydride, which was slowly charged over 2.5 hours with a maximum reaction temperature of 55°C. The liquor temperature was increased to 80°C and maintained for 18 horns. Following the hold, 1.75g of deionized water was charged to the reactor to hydrolyze any residual pyrophosphates, followed by an additional 2 hour hold. The reaction mass was cooled and bottled as is. [00178] The Specialty Phosphate Ester Monomer Mixture A contained a first monomer monoester phosphate (MAP), a second monomer di-ester phosphate (DAP), residual alcohol, and residual phosphoric acid.

[00179] The mono-ester phosphate was Ethylene glycol methacrylate phosphate having the structural formula (V):

[00180] The di-ester phosphate was Bis(ethylene glycol methacrylate) phosphate having the structural formula (VI):

[00181] By NMR, the average ratio of the Phosphate mono and Phosphate diester of five samples was measured to be 74.4:25.6 molar ratio, 65.4:34.6 mass ratio (1.89: 1 mass ratio). In particular, by NMR, the average proportion of MAP : DAP in Specialty Phosphate Ester Monomer Mixture A was measured to have a MAP:DAP 74.4 : 25.6 (± 0.7) mol. %; 65.4 : 34.6 (± 0.8) wt. %. Also, the range of mass ratios of the Phosphate mono and Phosphate diester for the five samples was 1.82-1.98:1. MAP was Ethylene glycol methacrylate phosphate. DAP was Bis(ethylene glycol methacrylate) phosphate.

[00182] Example 2 - Preparation of Polymerizable Surfactant Monomer Bl

[00183] Preparation of polymerizable surfactant C12C14-2.6AGE-15EO sulfate ammonium salt. [00184] 10.0g 45% potassium hydroxide solution was added to 320g ofALFOL 1214 stirring at

80°C in a reactor with a sub-surface purge of nitrogen gas. After heating to 100°C, the gasflow 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.

[00185] 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 0.1M 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 reactcr. [00186] 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.

[00187] 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 / 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.

[00188] 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%.

[00189] Example 3 Preparation of Polymerizable Surfactant Monomer B2

[00190] Preparation of polymerizable surfactant Nopol-2.6AGE-15EO sulfate ammonium salt. [00191] 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.

[00192] 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 0.1M 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.

[00193] 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 546 g ethylene oxide were fed below the surface of the liquid over 130 minutes between 155-156°C reaching a maximum pressure of 5.6 bars. 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.

[00194] 691.4 g 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 / 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%.

[00195] 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%.

[00196] INDUSTRIAL COATINGS MATERIALS AND TESTING ON METALS [00197] Example 4 - Comparative Latex Polymer A Production with 2% Specialty Phosphate Ester Monomer Mixture A and Conventional Phosphate Ester Emulsifier A for testing in Direct to Metal Properties

[00198] Testing Paints comprising the inventive polymer made from the mono- and di-phosphate monomer mixture and the polymerizable polymer.

[00199] Comparative Latex Polymer A was made from a mixture of Specialty Phosphate Ester Monomer Mixture A, conventional Phosphate Ester Emulsifier A, and a monomer composition. The resulting composition was Sty 42.2 / MMA 23.5 / 2EHA 29.3 / MAA 3.0 / Specialty monomer mixture 2.0, with all amounts wt% BOTM (based on total monomers), and the phosphate ester emulsifier was included in an amount of 1.0 wt% BOTM (based on total monomers).

[00200] The Phosphate Ester Monomer Mixture A is described above.

[00201] The conventional Phosphate Ester Emulsifier A was a phosphated anionic surfactant (potassium salt) which is APE (alkyl phenol ethoxylate)-free. Phosphate Ester Emulsifier A had a structure within the structures (Illa) and/or (IVa):

Diester _(IVa)

[00202] wherein R is an alkyl group, typically Cl 0-20 alkyl, preferably C12-C16; n is moles of ethylene oxide, typically n is 4-20; and

M is H, Na, K, or NH₄.

[00203] This example demonstrates that the Phosphate Ester Monomer Mixture A stabilizes a preemulsion of monomers such as styrene, methyl methacrylate (MMA), 2-Ethylhexyl Acrylate (2HEA), and methacrylic acid (MAA). Comparative Latex Polymer A had a glass transition temperature of about 36 °C, average particle size of 100 to about 120 nm, solids content of about 40.0 wt.%, a pH of about 7.0 to about 8.0.

[00204] The recipe for the pre-emulsion is shown in TABLE 1.

TABLE 1 - Pre-emulsification of Monomer Blendfor Comparative Latex Polymer A

* Monomer composition: ST Y/MMA/2EHA/MMA/Specialty monomer in a 42.2/23.5/29.3/3.0/2. Oweight ratio.

** Monomer composition was dispersed in water at 50/50 weight ratio, and neutralized to pH = 7 by concentrated ammonia. The total PEMA amount is 2.0% based on total monomer (BOTM).

[00205] The Pre-emulsification of the Monomer Blendfor Comparative Latex Polymer Al was combined with the Phosphate Ester Emulsifier Ain an amount of 1.0 wt.% BOTM (based on total materials).

[00206] A small lab homogenizer (ULTRA- TURRAX T25 Homogenizer by IKA-Labortechnik), was used and a stable pre-emulsion was obtained which was useful for emulsion polymerization (>3 hours without separation). Some Specialty Phosphate Ester Monomer Mixture A is still needed for the nucleation step. In the initial charge 0.2 % BOTM of the Specialty Phosphate Ester Monomer Mixture A was used. The complete list of ingredients is given in TABLE 2. The pre-emulsion containing the Specialty Phosphate Ester Monomer Mixture A was then used to make the Comparative Latex Polymer A.

TABLE 2 - Emulsion Polymerization Ingredients to Make Comparative Latex Polymer A

[00207] Procedure to make a Comparative Latex Polymer A using Specialty Phosphate Ester

Monomer Mixture A and Phosphate Ester Emulsifier A:

1. Heat the kettle charge to 78-80 °C; Add Initiator solution C and 29.4 g of Monomer emulsion B (5%); Hold the temperature at 80 °C for 15 minutes.

2. Add the remainder D and B over 3 hrs. Keep 80°C during the addition.

3. After the addition is completed, hold at 80 °C for 60 minutes.

4. Cool down to room temperature and adjust the pH to 8.0 using 28% ammonia solution.

[00208] The emulsification of the Monomer Blend for Comparative Latex Polymer A resulted in a styrene acrylic latex polymer having the following properties:

[00209] a glass transition temperature Tg of about 36°C. For purposes of this description T_s is calculated by the Fox equation (1):

1 1 T_g,_mix ~ Xi (Ot I T_&i (1) where Tg_mix and Tg, are the glass transition temperature of the mixture / copolymer and of the components, respectively, and co, is the mass fraction of component i. For two components A and B, the Fox equation reduces to the simplified Fox equation (2) used to calculate T_g:

[00210] Particle size of 100 to about 120 nm, Latex particle size measurements are generally conducted by dynamic light scattering (DLS) which arrive at substantially the same results (within 1 %). The particle size in the present disclosure is the “Z average”, unless otherwise indicated. The Z average is the intensity weighted mean hydrodynamic size of the ensemble collection of particles measured by dynamic light scattering (DLS). The Z average is derived from a Cumulants analysis of the measured correlation curve, wherein a single particle size is assumed and a single exponential fit is applied to the autocorrelation function. Particle size can also be determined by electron microscopy.

[00211] 40.0 % solids (is this wt.%), and

[00212] has a pH of about 7.0 to about 8.0.

[00213] Example 5 - Inventive Latex Polymer Bl and B2 Production for Metal Coating [00214] Inventive Latex Polymer Bl was made from a monomer composition including a mixture of Polymerizable Surfactant Monomer Bl, and Specialty Phosphate Ester Monomer Mixture A and a monomer mixture. Inventive Latex Polymer B2 was made from a mixture of Polymerizable Surfactant Monomer B2, Specialty Phosphate Ester Monomer Mixture A and the monomer mixture.

[00215] The procedure to make Inventive Polymers Bl and B2 was similar to that for Comparative Polymer A except 1 wt. % BOTM Polymerizable Surfactant Monomer Bl or B2, respectively, was substituted for the 1 wt. % BOTM Phosphate Ester Emulsifier A. Thus, Inventive Polymers Bl and B2 were each Sty 42.2 / MMA 23.5 / 2EHA 29.3 / MAA 3.0 / Specialty Phosphate Ester Monomer Mixture A 2.0 with all amounts wt% BOTM (based on total monomers), and the Polymerizable Surfactant Bl or B2 in an amount of 1.0 wt% BOTM).

[00216] The procedure for emulsion polymerization to produce Inventive Latex Polymers Bl and B2 was substantially the same as that for producing Comparative Latex Polymer A but for substituting Polymerizable Surfactant Bl or B2, respectively, for Phosphate ester emulsifier A.

[00217] Example 6- Making paints comprising the inventive polymer made from the mono- and di-phosphate monomer mixture and the polymerizable surfactant for testing in Direct to Metals Uses.

[00218] This example compared the properties for Direct to Metal use of the following: [00219] Comparative Paint A formulated with Comparative Latex Polymer A made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Phosphate Ester Emulsifier A;

[00220] Inventive Paint Bl formulated with Inventive Latex Polymer Bl made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A and 3 wt% MAA and 1 wt% Polymerizable Surfactant Monomer Bl;

[00221] Inventive Paint B2 formulated with Inventive Latex Polymer B2 made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A and 3 wt% MAA and 1 wt% Polymerizable Surfactant Monomer B2; [00222] The latex of the paints being the above-described styrene acrylic latex having Tg of about 36°F in the paint formulation of 18PVC/ 36 % VS / about 150 g/1 VOC.

[00223] By NMR, the average proportion of MAP : DAP in Inventive phosphate ester composition A was measured to have a MAP:DAP 74.4 : 25.6 (± 0.7) mol. %; 65.4 : 34.6 (± 0.8) wt. %. DAP was Ethylene glycol methacrylate phosphate. MAP was Bis(ethylene glycol methacrylate) phosphate.

[00224] The paints had the composition listed in TABLE 3.

[00225] The paints had the composition listed in TABLE 4.

[00226] TABLE 5 lists the Screening latex properties, except for the phosphate ester that varied among the different latexes.

TABLE 5 - Screening latex

*methyl methacrylate (MMA); 2-ethylhexyl acrylate (2EHA); methacrylic acid (MMA)

[00227] Example 7 -Metal Adhesion

[00228] The paints were tested for Metal Adhesion testing using the following test procedure.

ASTM D3359 - crosshatch adhesion

Adhesion Tape: ELCOMETER 99 ASTM D3359-09 CROSS HATCH ADHESION test tape

ASTM Rating: 0B = complete fail (no adhesion); 5B = perfect adhesion (no paint is removed)

Paints applied at a Dry Film Thickness of ~50um

Panels tested: Cold-roll steel (CRS) panels (S412 panels supplied by Q-lab); Bare Aluminum panels (A412 supplied by Q-lab); Hot-dipped galvanized unexposed (HDG panels supplied by ACT test panels)

Panels evaluated for adhesion at 1 day dry and 7 day dry (if necessary)

Dry adhesion: Panels scribed in duplicates for testing. Adhesion Tape is applied on the scribe, firmly pressed down onto film, and then pulled off at —180 degree angle from panel. Scribes are rated based on ASTM D3359 method. Wet adhesion: Panels are scribed in duplicates for testing. The scribes are then covered with a bi-fold towel and soaked with DI water for 30 minutes. After 30 minutes, the towels are removed, the panel is patted dry , and then allowed to fully dry for 30 minutes. After 30 minutes, the adhesion is tested in same manner as dry adhesion.

[00229] The paints were tested for Metal Adhesion according to ASTM D3359 - crosshatch adhesion (Adhesion Tape: ELCOMETER 99 ASTM D3359-09 CROSS HATCH ADHESION test tape). The samples were each a polished Cold-roll steel (CRS) panel of bare aluminum (hot roll A653) having a 50 um dry fdm thickness that underwent a 1 day and a 7 day cure in CT CH (72°F/50% Relative Humidity (RH). It was tested for wet adhesion after a 30 minute soak and 30 minute recovery.

[00230] FIG. 1 shows a standard classification of adhesion test results according to the ASTM D3359 Cross Hatch Method.

[00231] FIG. 2 shows the results of testing paints for Metal Adhesion according to the ASTM D3359 method. This shows that the Polymerizable surfactant monomers Bl, B2 can improve adhesion to difficult metal substrates.

[00232] FIG. 3 compares Adhesion after Weathering with either 240 hours of salt spray or 4 hours dray and 24 hours soaked in deionized water for Comparative Paint A including Comparative Latex Polymer A made with Phosphate Ester Emulsifier A vs. Inventive Paint Bl including Inventive Latex Polymer Bl made with Polymerizable Surfactant Monomer Bl on CRS (cold rolled steel) and aluminum. This shows improved adhesion under adverse conditions with Inventive Paint BL

[00233] Example 8 - Cleveland Condensation Test

[00234] Cleveland condensation is a method that uses an instrument that exposes panels to elevated temperatures and humidity. For this test, a QCT condensation chamber, also known as a humidity chamber, supplied by Q-labs was used to expose the coated metal panels to a temperature of 40°C and to a 100% condensing humidity. This method is used to measure water sensitivity by evaluating paint blistering and also for measuring gloss retention after being exposed to high humidity.

[00235] Panel preparation

1. Treated aluminum panels supplied by Q-lab were coated using the test paints at a dry film thickness of approximately 50 microns.

2. The panels were dried in a controlled temperature and humidity room for 7 days.

3. The panels were then placed in the humidity chamber and rated for blistering over the course of 120 hours (5 days).

4. Blistering was rated using ASTM method D714 following the rating system shown in TABLE 6: TABLE 6

[00236] Humidity chamber @ 40 °C with 100% humidity for 5 days [00237] Treated aluminum at paint Dry Film Thickness (DFT) 50 micron [00238] FIG. 4 shows results of tests for blistering resistance of Comparative Paint A including Comparative Latex Polymer A made from the emulsified latex blend, with 2 wt% phosphate ester composition A, 3 wt% MAA, and 1 wt% Phosphate ester emulsifier (RS710K25) vs. Inventive Paint B2 including Inventive Latex Polymer B2 made from the emulsified latex blend with 2 wt% Specialty Phosphate Ester Monomer Mixture A, 3 wt% MAA, and 1 wt% Polymerizable Surfactant Monomer B2. FIG. 4 shows improved blistering resistance under adverse conditions for Inventive Paint B2 including Latex B2 made with Polymerizable Surfactant Monomer B2. Increased blistering occurred for Comparative Paint A including Latex A made with Phosphate Ester Emulsifier A.

[00239] TABLE 7 shows ASTM D-714 Ratings. Comparative Paint A had an ASTM D-714 rating of 6F.

TABLE 7

[00240] Example 9 - Water Soak Test for Water Resistance

[00241] Paint Dry Film Thickness (DFT) 50 micron on Cold-roll steel (CRS)

[00242] Cure in CTCH (72°F/50%RH) for 1 day

[00243] Submersed in deionized water (DI) water for 14 days

[00244] Rated for blistering and adhesion

[00245] FIG. 5 shows results of tests for water resistance of Comparative Paint A including Latex A made with Specialty Phosphate Ester Monomer Mixture A and Phosphate Ester Emulsifier A vs. Inventive Paint Bl including Latex Bl made with Specialty Phosphate Ester Monomer Mixture A and Polymerizable Surfactant Monomer Bl. This shows improved water resistance under adverse conditions for Inventive Paint Bl. Increased blistering occurred for Comparative Paint A.

[00246] CERAMICS COATINGS MATERIALS AND TESTING

[00247] Example 10 - Comparative Latex Polymer C Production with Phosphate Ester Emulsifier A and no Specialty Phosphate Ester Monomer Mixture A

[00248] Comparative Latex Polymer C was made similarly to Comparative Latex Polymer A but did not include the Specialty Phosphate Ester Monomer Mixture A. The procedure for emulsion polymerization to produce Comparative Latex Polymer C was substantially the same as that for producing Comparative Latex Polymer A but for substituting additional Butyl methacrylate (BMA) for the Specialty Phosphate Ester Monomer Mixture A.

[00249] The resulting composition was Sty 25 / MMA 22 / 2EHA 32 / MAA 5.0 / BMA 16, with all amounts wt% BOTM (based on total monomers), and the Phosphate Ester Emulsifier A in an amount of 2.0 wt% BOTM).

[00250] Example 11 - Inventive Latex Polymer D Production - For Ceramic Tests

[00251] Inventive Latex Polymer D was made from a mixture of Specialty Phosphate Ester

Monomer Mixture A, Polymerizable Surfactant Monomer B2, and a monomer composition.

[00252] The resulting composition was Sty 25 / MMA 22 / 2EHA 32 / MAA 5.0 / BMA 14 / Specialty monomer mixture 2.0, with all amounts wt% BOTM (based on total monomers), and the Polymerizable Surfactant Monomer B2 was included in an amount of 2.0 wt% BOTM (based on total monomers).

[00253] The procedure for emulsion polymerization to produce Inventive Latex Polymer D was substantially the same as that for producing Inventive Latex Polymer B2 but for introducing BMA as monomer in the polymerization. TABLE 8 summarizes this procedure to produce Inventive Latex Polymer D.

TABLE 8 - procedure to produce Inventive Latex Polymer D

[00254] Procedure:

[00255] Ensure that the reactor and all supporting equipment are clean.

[00256] Charge 1-2 to the reactor and start the agitation.

[00257] Start a nitrogen-purge, head spray and condenser-water.

[00258] Heat to 60°C.

[00259] Charge 14, 15 into initiator feed tank after a homogeneous liquid has been obtained.

[00260] Charge 5-12 to monomer feed tank and start agitation.

[00261] At 60°C charge 10% of the monomer feed to the reactor in +- 3 minutes.

[00262] After 5 minutes of mixing, add solution 3 and 4 (initiator shot) in 2-3 min into the reactor.

[00263] The reaction will be exothermic, wait for the exotherm.

[00264] 5 minutes after the initiator shot, put the temperature set point to 85 °C.

[00265] At 85 °C (approximately 10 minutes after the initiator shot), start both feeds, both feeds should take 90°C minutes at 85 °C.

[00266] When the feeds has been completed, rinse the feed tank with 16.

[00267] Rinse the initiator tank with 17.

[00268] Maintain reaction temperature for 60 minutes.

[00269] Then cool the batch to 30°C.

[00270] At < 50°C add a mixture of 18-19 to the reactor in +- 30 minutes.

[00271] After charged ammonia solution continue mix for 60 minutes

[00272] Add 20 to the reactor and mix for 5 minutes.

[00273] Filter the batch using 50 micron AMA filter cartridges

[00274] This example demonstrates that the Phosphate Ester Composition A with the Polymerizable Surfactant B2 stabilizes a pre-emulsion of monomers such as styrene, methyl methacrylate (MMA), 2-Ethylhexyl Acrylate (2HEA), methacrylic acid (MAA), and BMA. Inventive Latex Polymer D had a glass transition temperature of about 29 °C, average particle size of 90 to about 110 nm, solids content of about 45.0 wt.%, a pH of about 7.0 to about 8.0.

[00275] Example 12 (ceramic) - Making coatings comprising the inventive polymer made from the mono- and di-phosphate monomer mixture and the polymerizable surfactant for testing in Ceramic Uses.

[00276] This following coatings were prepared for Direct to Ceramic application:

[00277] Comparative Coating Formulation C formulated with Comparative Latex Polymer C, and Inventive Coating Formulation D formulated with Inventive Latex Polymer D.

[00278] The coating formulations had the compositions shown in TABLE 9.

TABLE 9

[00279] TABLE 10 lists the Screening latex properties, except for the phosphate ester that varied among the different latexes.

TABLE 10 - Screening latex

* methyl methacrylate (MMA); 2-ethylhexyl acrylate (2EHA); methacrylic acid (MMA); n-Butyl methacrylate (BMA)

[00280] Example 13 - Ceramic Adhesion

[00281] The Comparative Coating Formulation C and Inventive Coating Formulation D were tested for Ceramic Adhesion testing using the following test procedure. [00282] 1. Use water wash the surface of the ceramic and then make the surface dry;

[00283] 2. Coat the resin (wet fdm 80um) into the ceramic substrate by wire-wound rod;

[00284] 3. Put the coated ceramic into the 50C oven for 2 hours;

[00285] 4. Leave the ceramic overnight (around 16 hours) at room temperature;

[00286] 5. check the adhesion according to ASTM D3359 method B (spacing 1 mm).

[00287] FIG. 6 shows results of tests for ceramic adhesion of Sample #005 of Comparative

Coating Formulation C including Comparative Polymer C made with Phosphate Ester Emulsifier A and no Specialty Phosphate Ester Monomer Mixture A vs. Sample 001# of Inventive Coating Formulation D including Inventive Polymer D made with Polymerizable Surfactant Monomer B2 and Specialty Phosphate Ester Monomer Mixture A.

[00288] TABLE 11 summarizes the results of tests for ceramic adhesion of Comparative Coating Formulation C vs. Inventive Coating Formulation D. This shows improved ceramic adhesion under adverse conditions with Inventive Coating Formulation D. A rating of 0B is the worst adhesion and a rating of 5B is the best adhesion according to the testing standard ASTM D3359-23 method B. This shows improved ceramic adhesion under adverse conditions with Inventive Coating Formulation D due to Polymerizable Surfactant Monomer B2.

[00289] CLAUSES OF THE INVENTION

[00290] The following clauses describe various aspect of the invention:

[00291] Clause 1. A polymerizable composition comprising a mixture of:

(A) a phosphate ester composition comprising at least one polymerizable phosphate mono-ester compound or salt thereof and at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition comprising:

R’-C(O)- R² -X¹ (I) wherein:

X¹ is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and (b) at least one polymerizable phosphate di-ester compound or a salt thereof having the formula (II): R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4- 2.1:1, 1.5-2 1:1, 1.5-2.0T, 1.6-1 9:1, 1.7-1 9:1, or 1.8-1.9T;

(B) at least one polymerizable surfactant of formula (III):

wherein Ri is a Cs-Ci4 alkyl group or a bicyclic group; wherein “x” is an integer from 1-20, wherein “y” is an integer from 1-30; wherein M⁺ is H⁺, Na⁺, NH4⁺, K⁺ or Li⁺; and

(C) at least one other polymerizable monomer, preferably one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers, vinyl ester monomers, butadiene, ethylene, or vinyl chloride.

[00292] Clause 2. The polymerizable composition of clause 1, wherein the polymerizable phosphate mono-ester compound is 30-60, wt. %, typically 40-50 wt%, more typically 43-47 wt.% of the phosphate ester composition on a dry (water free) basis.

[00293] Clause 3. The polymerizable composition of clause 1 or 2, wherein M⁺ is Na⁺ or NH4+.

[00294] Clause 4. The polymerizable composition of any of the preceding clauses, wherein R¹ is selected from the group consisting of CH2=CH-, CH2=C(CHs)-, or cis-CH(COOH)=CH.

[00295] Clause 5. The polymerizable composition of any of the preceding clauses, wherein R² has one to five, preferably one to three oxy ethylene units. [00296] Clause 6. The polymerizable composition of any of the preceding clauses, wherein R² has at least one oxyethylene unit.

[00297] Clause 7. The polymerizable composition of any of the preceding clauses, wherein R² has an absence of oxypropylene units.

[00298] Clause 8. The polymerizable composition of any of the preceding clauses, wherein R³ is selected from the group consisting of CH2=CH-, CH2=C(CHs)-, or cis-CH(COOH)=CH-.

[00299] Clause 9. The polymerizable composition of any of the preceding clauses, wherein R⁴ is a divalent polyoxyalkylene radical having at least one oxyethylene unit.

[00300] Clause 10. The polymerizable composition of any of the preceding clauses, wherein R⁴ is a divalent poly oxy alkylene radical having one to three oxy ethylene units.

[00301] Clause 11. The polymerizable composition of any of the preceding clauses, wherein ((2- methyl-1 -oxopropane- 1, 3 -diyl)bis(oxy))bis(ethane-2,l-diyl)bis(2-methacrylate) is 10 to 20 wt.%, more typically 15-20 wt%, for example 16-18 wt% of the phosphate ester composition.

[00302] Clause 12. The polymerizable composition of any of the preceding clauses, wherein ethylene glycol dimethacrylate is 1 to 10 wt.%, typically 2-8 wt%, more typically 3-7 wt%, for example 4- 6 wt% of the phosphate ester composition.

[00303] Clause 13. The polymerizable composition of any of the preceding clauses, further comprising phosphoric acid, preferably the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) is 10:90 to 25:75, typically 10:90 to 20:80, more typically 10:90 to 18:82, for example 11:89- 16:84.

[00304] Clause 14. The polymerizable composition of any of the preceding clauses, wherein the at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I) and the at least one polymerizable phosphate di-ester compound or a salt thereof having the formula (II) have been neutralized with one or more of sodium hydroxide, potassium hydroxide or ammonium hydroxide, preferably ammonium hydroxide.

[00305] Clause 15. The polymerizable composition of any of the preceding clauses, wherein Ri is a bicyclo[d _e qheptyl or bicyclo[d _e qheptenyl 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-Ce)alkyl groups.

[00306] Clause 16. The polymerizable composition of any of the preceding clauses, wherein “x” is an integer from 1-40, and wherein “y” is an integer from 1-50.

[00307] Clause 17. The polymerizable composition of any of the preceding clauses, wherein “x” is an integer from 1-5.

[00308] Clause 18. The polymerizable composition of any of the preceding clauses, wherein “y” is an integer from 5-15.

[00309] Clause 19. The polymerizable composition of any of the preceding clauses, wherein the mixture further comprises a secondary surfactant. [00310] Clause 20. The polymerizable composition of any of the preceding clauses, further comprising a surfactant, wherein the composition comprises 0.5 to 3 wt.% said surfactant based on total monomer including the polymerizable phosphate mono-ester compound, polymerizable phosphate di-ester compound, and other polymerizable monomer; wherein the surfactant is preferably anionic surfactant, more preferably a phosphate ester anionic surfactant; wherein the polymer composition is an emulsion polymer composition.

[00311] Clause 21. The polymerizable composition of any of the preceding clauses, further comprising a surfactant, wherein the surfactant comprises any of 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.

[00312] Clause 22. The polymerizable composition of any of clauses 1-21, wherein the at least one other monomer is selected from acrylate monomers, styrene monomers, vinyl ester monomers, or combinations thereof.

[00313] Clause 23. The polymerizable composition of any clauses 1-21, 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 mixtures thereof.

[00314] Clause 24. The polymerizable composition of any of the preceding clauses, further comprising at least one ingredient selected from chain transfer agents, additives to adjust pH, compounds utilized as protective colloids, and combinations thereof.

[00315] Clause 25. A polymer composition comprising monomeric units from the polymerizable composition of any of the preceding clauses comprising:

(A) the at least one polymerizable phosphate mono-ester compound or salt thereof and the at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition comprising:

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

(B) a polymerizable surf actant of formula (III):

(C) at least one other polymerizable monomer, preferably one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers, vinyl ester monomers, butadiene, ethylene, or vinyl chloride; and

(D) optionally, at least one secondary surfactant.

[00316] Clause 26. A waterborne coating comprising the polymer composition of clause 25.

[00317] Clause 27. A coating composition comprising a polymer formed from:

(A) a phosphate ester composition comprising at least one polymerizable phosphate mono-ester compound or salt thereof and at least one polymerizable phosphate di-ester compound or salt thereof of the phosphate ester composition comprising: (a) at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I):

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4- 2.1:1, 1.5-2.1:1, 1.5-2.0:!, 1.6-1 9:1, 1.7-1 9:1, or 1.8-1 9:1;

(B) at least one polymerizable surfactant, wherein the polymerizable surf actant has formula (III):

wherein:

M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof; and

(C) at least one other polymerizable monomer.

[00318] Clause 28. The coating composition of clause 27, wherein M⁺ is Na⁺,NH4+, or combinations thereof.

[00319] Clause 29. The coating composition of clause 27 or 28, wherein x is 2 to 4 and y is 14 to 18.

[00320] Clause 30. The coating composition of any of clauses 27-29, wherein the coating composition is an industrial coating, elastomeric coating, architectural coating, or both.

[00321] Clause 31. The coating composition of any of clauses 27-30, wherein the coating composition is a latex coating.

[00322] Clause 32. A method of improving the corrosion resistance of a metal or ceramic substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition of clause 25, compared to coating the substrate with a coating composition which is the same but does not include monomeric units from the polymerizable surfactant.

[00323] Clause 33. A method of improving the water resistance of a coating composition to a substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition of clause 25, compared to coating the substrate with a coating composition which is the same but does not include monomeric units from said polymerizable phosphate mono-ester compound or a salt thereof and said polymerizable phosphate di-ester compound or a salt thereof.

[00324] Clause 34. A method of improving the adhesion of a coating composition to a metal substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition of clause 25.

[00325] Clause 35. A method of improving the adhesion of a coating composition intended to be coated to a metal substrate comprising contacting at least a portion of the surface of the substrate with a coating composition, called conversion coating, wherein the conversion coating comprises the polymer composition of clause 25.

[00326] Clause 36. A method of treating a first metal surface SI of a first substrate intended to be bonded to a second surface S2 of a second substrate by adhesive bonding, and of imparting a resistance to the adhesive failure to the bonding, said method comprising contacting at least a portion of the first metal surface SI with a coating composition, wherein the coating composition comprises the polymer composition of clause 25.

[00327] Clause 37. The method of any of clauses 32-36, wherein the substrate is ceramic, aluminum, steel or galvanized steel.

[00328] Clause 38. A method of making a polymer composition of any of clauses 1-24 comprising: combining (A) the phosphate ester composition, (B) the polymerizable surfactant, and (C) the at least one other polymerizable monomer, and optionally secondary surfactant; and polymerizing (A) the phosphate ester composition, (B) the polymerizable surfactant, and (C) the at least one other polymerizable monomer.

[00329] Clause 39. The method of clause 38, wherein the mixture further comprises the secondary surfactant, wherein the mixture comprises 0.5 to 3 wt.% said secondary surfactant based on total monomer including the polymerizable phosphate monoester compound, polymerizable phosphate di-ester compound, and other polymerizable monomer; wherein the secondary surfactant is preferably anionic surfactant, more preferably a phosphate ester anionic surfactant; and the composition is an emulsion polymer composition, and the polymerization is by emulsion polymerization of the mixture.

[00330] Clause 40. The method of clause 38 or 39, wherein the mixture further comprises phosphoric acid, preferably wherein the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) 10:90 to 25:75, preferably 12:88 to 20:80.

[00331] Clause 41. A method of making a coating composition comprising emulsion polymerizing the at least one polymerizable composition of any of clauses 1-24 with the at least one other monomer.

[00332] Having described the invention in detail by reference to the preferred embodiments and specific examples thereof, it will be apparent that modifications and variations are possible without departing from the spirit and scope of the disclosure and claims.

Claims

1. A polymerizable composition comprising a mixture of:

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4-2.1:1, 1.5-2.1:1, 1.5-2.0:1, 1.6-1 9:1, 1.7-1 9:1, or 1.8-1 9:1;

(B) at least one polymerizable surfactant of formula (III):

2. The polymerizable composition of claim 1, wherein the polymerizable phosphate mono-ester compound is 30-60, wt. %, typically 40-50 wt%, more typically 43-47 wt.% of the phosphate ester composition on a dry (water free) basis.

3. The polymerizable composition of claim 1 or 2, wherein M⁺ is Na⁺ or NH4+.

4. The polymerizable composition of any of the preceding claims, wherein R¹ is selected from the group consisting of CH2=CH-, CH2=C(CHs)-, or cis-CH(COOH)=CH.

5. The polymerizable composition of any of the preceding claims, wherein R² has one to five, preferably one to three oxyethylene units.

6. The polymerizable composition of any of the preceding claims, wherein R² has at least one oxyethylene unit.

7. The polymerizable composition of any of the preceding claims, wherein R² has an absence of oxypropylene units.

8. The polymerizable composition of any of the preceding claims, wherein R³ is selected from the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH-.

9. The polymerizable composition of any of the preceding claims, wherein R⁴ is a divalent polyoxyalkylene radical having at least one oxyethylene unit.

10. The polymerizable composition of any of the preceding claims, wherein R⁴ is a divalent polyoxyalkylene radical having one to three oxy ethylene units.

11. The polymerizable composition of any of the preceding claims, wherein ((2 -methyl- 1 -oxopropane- 1,3- diyl)bis(oxy))bis(ethane-2,l-diyl)bis(2 -methacrylate) is 10 to 20 wt.%, more typically 15-20 wt%, typically 16-18 wt% of the phosphate ester composition.

12. The polymerizable composition of any of the preceding claims, wherein ethylene glycol dimethacrylate is 1 to 10 wt.%, typically 2-8 wt%, more typically 3-7 wt%, typically 4-6 wt% of the phosphate ester composition.

13. The polymerizable composition of any of the preceding claims, further comprising phosphoric acid, preferably the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) is 10:90 to 25:75, typically 10:90 to 20:80, more typically 10:90 to 18:82, typically 11:89-16:84.

14. The polymerizable composition of any of the preceding claims, wherein the at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I) and the at least one polymerizable phosphate di-ester compound or a salt thereof having the formula (II) have been neutralized with one or more of sodium hydroxide, potassium hydroxide or ammonium hydroxide, preferably ammonium hydroxide.

15. The polymerizable composition of any of the preceding claims, wherein Ri is a bicyclo[d _e qheptyl or bicyclo[d _e qheptenyl 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-Ce)alkyl groups.

16. The polymerizable composition of any of the preceding claims, wherein “x” is an integer from 1-40, and wherein “y” is an integer from 1-50.

17. The polymerizable composition of any of the preceding claims, wherein “x” is an integer from 1-5.

18. The polymerizable composition of any of the preceding claims, wherein “y” is an integer from 5-15.

19. The polymerizable composition of any of the preceding claims, wherein the mixture further comprises a secondary surfactant.

20. The polymerizable composition of any of the preceding claims, further comprising a surfactant, wherein the composition comprises 0.5 to 3 wt.% said surfactant based on total monomer including the polymerizable phosphate mono-ester compound, polymerizable phosphate di-ester compound, and other polymerizable monomer; wherein the surfactant is preferably anionic surfactant, more preferably a phosphate ester anionic surfactant; wherein the polymer composition is an emulsion polymer composition.

21. The polymerizable composition of any of the preceding claims, further comprising a surfactant, wherein the surfactant comprises any of 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.

22. The polymerizable composition of any of claims 1-21, wherein the at least one other monomer is selected from acrylate monomers, styrene monomers, vinyl ester monomers, or combinations thereof.

23. The polymerizable composition of any claims 1-21, 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 mixtures thereof.

24. The polymerizable composition of any of the preceding claims, further comprising at least one ingredient selected from chain transfer agents, additives to adjust pH, compounds utilized as protective colloids, and combinations thereof.

25. A polymer composition comprising monomeric units from the polymerizable composition of any of the preceding claims comprising:

(a) the at least one polymerizable phosphate mono-ester compound or a salt thereof having the formula (I): R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

(B) a polymerizable surf actant of formula (III):

wherein Ri is a Cs-Ci4 alkyl group or a bicyclic group; wherein “x” is an integer from 1-20, wherein “y” is an integer from 1-30; wherein M⁺ is H⁺, Na⁺, NH4⁺, K⁺ or Li⁺; and (C) at least one other polymerizable monomer, preferably one or more (co)polymerizable monomers comprising acrylate monomers, styrene monomers, vinyl ester monomers, butadiene, ethylene, or vinyl chloride; and

(D) optionally, at least one secondary surfactant.

26. A waterborne coating comprising the polymer composition of claim 25.

27. A coating composition comprising a polymer formed from:

R’-C(O)- R² -X¹ (I) wherein:

R³-C(O)- R⁴ -X²- R⁴-C(O)-R³ (II) wherein:

X² is a phosphate group, wherein the salt, if present, is preferably sodium, potassium or ammonium salt; and wherein the weight ratio of the polymerizable phosphate mono-ester compound of formula (I) to the polymerizable phosphate di-ester compound of formula (II) ranges from 1.2-2.1 : 1 , or typically 1.4- 2.1:1, 1.5-2.1:!, 1.5-2.0:!, 1.6-1 9:1, 1.7-1 9:1, or 1.8-1 9:1;

(B) at least one polymerizable surfactant, wherein the polymerizable surfactant has formula (III):

wherein:

M⁺ is H⁺, Na⁺, NH4⁺, K⁺, Li⁺, or combinations thereof; and

(C) at least one other polymerizable monomer.

28. The coating composition of claim 27, wherein M⁺ is Na⁺, NH4+, or combinations thereof.

29. The coating composition of claim 27 or 28, wherein x is 2 to 4 and y is 14 to 18.

30. The coating composition of any of claims 27-29, wherein the coating composition is an industrial coating, elastomeric coating, architectural coating, or both.

31. The coating composition of any of claims 27-30, wherein the coating composition is a latex coating.

32. A method of improving the corrosion resistance of a metal or ceramic substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition of claim 25, compared to coating the substrate with a coating composition which is the same but does not include monomeric units from the polymerizable surfactant.

33. A method of improving the water resistance of a coating composition to a substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition of claim 25, compared to coating the substrate with a coating composition which is the same but does not include monomeric units from said polymerizable phosphate mono-ester compound or a salt thereof and said polymerizable phosphate di-ester compound or a salt thereof.

34. A method of improving the adhesion of a coating composition to a metal substrate comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition of claim 25.

35. A method of improving the adhesion of a coating composition intended to be coated to a metal substrate comprising contacting at least a portion of the surface of the substrate with a coating composition, called conversion coating, wherein the conversion coating comprises the polymer composition of claim 25.

36. A method of treating a first metal surface S 1 of a first substrate intended to be bonded to a second surface S2 of a second substrate by adhesive bonding, and of imparting a resistance to the adhesive failure to the bonding, said method comprising contacting at least a portion of the first metal surface SI with a coating composition, wherein the coating composition comprises the polymer composition of claim 25.

37. The method of any of claims 32-36, wherein the substrate is ceramic, aluminum, steel or galvanized steel.

38. A method of making a polymer composition of any of claims 1-24 comprising: combining (A) the phosphate ester composition, (B) the polymerizable surfactant, and (C) the at least one other polymerizable monomer, and optionally secondary surfactant; and polymerizing (A) the phosphate ester composition, (B) the polymerizable surfactant, and (C) the at least one other polymerizable monomer.

39. The method of claim 38, wherein the mixture further comprises the secondary surfactant, wherein the mixture comprises 0.5 to 3 wt.% said secondary surfactant based on total monomer including the polymerizable phosphate monoester compound, polymerizable phosphate di-ester compound, and other polymerizable monomer; wherein the secondary surfactant is preferably anionic surfactant, more preferably a phosphate ester anionic surfactant; and the composition is an emulsion polymer composition, and the polymerization is by emulsion polymerization of the mixture.

40. The method of claim 38 or 39, wherein the mixture further comprises phosphoric acid, preferably wherein the weight ratio of the phosphoric acid to total polymerizable phosphate mono-ester compound of formula (I) and polymerizable phosphate di-ester compound of formula (II) 10:90 to 25:75, preferably 12:88 to 20:80.

41. A method of making a coating composition comprising emulsion polymerizing the at least one polymerizable composition of any of claims 1-24 with the at least one other monomer.