WO2018119028A1

WO2018119028A1 - Fluoroalkyl containing phosphate surfactants

Info

Publication number: WO2018119028A1
Application number: PCT/US2017/067501
Authority: WO
Inventors: Wayne Wei-Qiang FAN; Kevin J. Rink; Yu Yang
Original assignee: 3M Innovative Properties Company
Priority date: 2016-12-23
Filing date: 2017-12-20
Publication date: 2018-06-28

Abstract

Compounds of formula (I) wherein R¹ is -(CH₂)_m, -(CH₂CHMeO)_mCH₂CHMe-, -(CH₂CH₂O)_mCH₂CH₂-, -(CH₂CH₂CH₂0)_mCH₂CH₂CH₂-, -R_mO(CO)R_m-, -R_mNHC(0)OR_m-, or -R_mN(SO₂C_pF_2p+1)R_m-, where p is an integer from 1 to 6; each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; m is an integer from 1 to 6; each R2 is independently a C₁ to Ce alkyl, a -SO₂C_pF_2P+1 group where p is an integer from 1 to 8, or a combination thereof; each Rf is independently a C₁ to C₂ perfluoroalkyl-or fluoroalkyl; each y is independently an integer from 1 to 12; and n is an integer from 1 to 15.

Description

FLUOROALKYL CONTAINING PHOSPHATE SURFACTANTS

FIELD

The present disclosure relates to fiuoroaklyl containing phosphate surfactants, methods of making the same, compositions containing the same and applications thereof.

BACKGROUND

Latex paints are often preferred over solvent-based paints because of their improved safety, lower toxicity, and lower volatile -organic contents. Generally, however, latex paints, particularly flat latex paints, have poor stain and soil resistance. Because of their highly porous nature and rough surface texture, flat latex paints tend to absorb stains. Penetrating type stains, such as ink, soft drinks, wine, and other colored liquids, have easy access to the interior of a flat paint film through numerous pores and microchannels, and surface dirt, such as handprints, smudges, dust, and other particulate matter, can become entrapped in the bumpy, rough texture of the paint surface.

In recent years, flat latex paints having improved stain and soil resistance with resulting improved cleanability have been formulated. Consumers, however, desire flat latex paints that can provide still better stain and soil resistance with resulting improved cleanability.

SUMMARY

wherein R¹ is -(CH₂)_m, -(CH₂CHMeO)_mCH₂CHMe-, -(CH2CH₂0)_mCH₂CH2-,

-(CH₂CH₂CH₂0)_mCH₂CH₂CH₂-, -R_mO(CO)R_m-, -R_mNHC(0)OR_m-, or -R_mN(S0₂C_pF_2p+1)R_m-, where p is an integer from 1 to 6; each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; m is an integer from 1 to 6; each R² is independently a Ci to Ce alkyl, a -S0₂C_pF_2p+i group where p is an integer from 1 to 8, or a combination thereof; each R^f is independently a Ci to Cs perfluoroalkyl-or fluoroalkyl; each y is independently an integer from 1 to 12; and n is an integer from 1 to 15.

Also disclosed are compositions that include a polymer having interpolymerized units that include units derived from styrene, methyl styrene, vinyl, or combinations thereof and one or more units derived from acrylates, methacrylates, acrylonitrile, or combinations thereof; and one or more compounds of formula I

wherein R¹ is -(CH₂)_m, -(CH₂CHMeO)_mCH₂CHMe-, -(CH2CH₂0)_mCH₂CH2-,

-(CH₂CH2CH20)_mCH2CH₂CH2-, -R_mO(CO)R_m-, -R_mNHC(0)OR_m-, or -R_mN(S0₂C_pF_2p+i)R_m-, where p is an integer from 1 to 6; each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; m is an integer from 1 to 6; each R² is independently a Ci to Οβ alkyl, a -S0₂C_pF2_P+i group where p is an integer from 1 to 8, or a combination thereof; each R^f is independently a Ci to Cs perfluoroalkyl-or fluoroalkyl; each y is independently an integer from 1 to 12; and n is an integer from 1 to 15.

Also disclosed are articles that include a coating formed from disclosed compositions.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.

DETAILED DESCRIPTION

All scientific and technical terms used herein have meanings commonly used in the art unless otherwise specified. The definitions provided herein are to facilitate understanding of certain terms used frequently herein and are not meant to limit the scope of the present disclosure.

As used in this specification and the appended claims, the singular forms "a", "an", and "the" encompass embodiments having plural referents, unless the content clearly dictates otherwise.

As used in this specification and the appended claims, the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise. The term "and/or" means one or all of the listed elements or a combination of any two or more of the listed elements.

As used herein, "have", "having", "include", "including", "comprise", "comprising" or the like are used in their open ended sense, and generally mean "including, but not limited to". It will be understood that "consisting essentially of, "consisting of, and the like are subsumed in "comprising" and the like. For example, a conductive trace that "comprises" silver may be a conductive trace that "consists of silver or that "consists essentially of silver.

As used herein, "consisting essentially of," as it relates to a composition, apparatus, system, method or the like, means that the components of the composition, apparatus, system, method or the like are limited to the enumerated components and any other components that do not materially affect the basic and novel characteristic(s) of the composition, apparatus, system, method or the like.

The words "preferred" and "preferably" refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure, including the claims.

Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. or 10 or less includes 10, 9.4, 7.6, 5, 4.3, 2.9, 1.62, 0.3, etc.). Where a range of values is "up to" a particular value, that value is included within the range. All upper and lower limits can be combined in any combination to form ranges for the particular component or property for example.

Also herein, all numbers are assumed to be modified by the term "about" and preferably by the term "exactly." As used herein in connection with a measured quantity, the term "about" refers to that variation in the measured quantity as would be expected by the skilled artisan making the measurement and exercising a level of care commensurate with the objective of the measurement and the precision of the measuring equipment used.

Use of "first," "second," etc. in the description above and the claims that follow is not intended to necessarily indicate that the enumerated number of steps are present. For example, a "second" step is merely intended to differentiate from another step (such as a "first" step). Use of "first," "second," etc. in the description above and the claims that follow is also not necessarily intended to indicate that one comes earlier in time than the other.

When a group is present more than once in a formula described herein, each group is

"independently" selected, whether specifically stated or not. For example, when more than one Rl group is present in a formula, each Rl group is independently selected. Furthermore, subgroups contained within these groups are also independently selected.

As used herein, the term "room temperature" refers to a temperature of about 20 °C to about 25 °C or about 22 °C to about 25 °C.

Fluorochemical phosphates are widely used as surfactants in paints and the coating industry. Fluorochemical phosphates are known to have good surface properties and provide good stain resistant performance as coating additives, however, the materials can present concerns based on environmental health and safety. Because of these concerns, they cannot be used for spray applications and are only utilized in limited to very low concentration in coating formulations. It is therefore desirable to develop new fluorochemical phosphate surfactants that can offer both reduced environmental or toxicity concerns and the same or improved surfactant performance

Disclosed herein are compounds that can be utilized as surfactants. The compounds can be those of formula I:

Compounds of formula I may be advantageous as surfactants for a number of reasons, including for example the extreme stability of the R^f-S bond. The compounds of formula I also contain lower fluorine contents and higher molecular weights than previously utilized fluoroalkyl surfactants, e.g.,

perfluoroalkyl diester and mono-ester phosphate surfactants, and therefore pose less concern of inhalation but still offer excellent surface properties and stain resistant performance.

In formula I, R¹ can include alkyl groups, ether containing groups, ester containing groups, urethane containing groups, sulfonamide containing groups, or combinations thereof. In some embodiments, R¹ can include alkyl groups such as -(CH₂)_m-, where m is an integer from 1 to 12, 1 to 8, or 1 to 6 for example. In some embodiments, R¹ can include ether containing groups such as - (CH2CH₂0)_mCH₂CH2-, -(CH₂CHMeO)_mCH₂CHMe-, or

(CH₂CH₂CH₂0)_mCH₂CH₂CH₂- where m is an integer from 1 to 12, 1 to 8, or 1 to 6 for example. In some embodiments, R¹ can include ester containing groups such as -R_mO(CO)R_m- where each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group and where m is an integer from 1 to 12, 1 to 8, or 1 to 6 for example. In some embodiments, R¹ can include a urethane containing group such as -R_mNHC(0)OR_m- where each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group and where m is an integer from 1 to 12, 1 to 8, or 1 to 6 for example. In some embodiments, R¹ can include sulfonamide containing groups such as - R_mN(S0₂CpF₂p+i)R_m- where each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group and where m and p are each independently integers from 1 to 8, 1 to 4, or 1 to 2 for example.

In Formula I, R² can each independently be substituted or unsubstituted alkyl groups. For example, R² can each independently be substituted or unsubstituted Ci to Cn groups, Ci to Cs groups or Ci to Ce groups, for example. R² can also include a S0₂C_pF_2p+i group where p is an integer from 1 to 8, or 1 to 6.

In Formula I, R^f can each independently be a substituted or unsubstituted fluoroalkyl or perfluoroalkyl containing group. For example, R^f can each independently be a substituted or unsubstituted Ci to Cn fluoroalkyl or perfluoroalkyl containing group, a substituted or unsubstituted Ci to Cs fluoroalkyl or perfluoroalkyl containing group or a substituted or unsubstituted Ci to Ce fluoroalkyl or perfluoroalkyl containing group, for example. In some embodiments, R^f can each independently be a Ci to Ci2 perfluoroalkyl containing group, a Ci to Cs perfluoroalkyl containing group, a C₂ to Cs perfluoroalkyl containing group or a Ci to e perfluoroalkyl containing group, for example. In Formula I, y can each independently be an integer from 1 to 12, 1 to 8, 1 to 6, 1 to 4, or even 1 to 2, for example.

In Formula I, n can be an integer from 1 to 15, from 1 to 12, from 1 to 4, or even 1 to 2, for example.

Methods of making disclosed compounds can include a step of reacting a diol with phosphoryl chloride (POCb) or diphosphorus pentoxide (P2O5) for example. In instances where the diol does not include a perfluoroalkyl or fluoroaklyl containing group the reaction product can then be reacted with a compound containing a perfluoroalkyl or fluoroaklyl containing group. In some embodiments, a diol containing a sulfonamide group and a perfluoroalkyl or fluoroalkyl containing group can be reacted with phosphoryl chloride (POCI3) or diphosphorus pentoxide (P2O5) in a single step to form disclosed compounds.

Illustrative diols can include substituted or unsubstituted alkyl diols or polyols for example. More specifically, alkyl diols can include Ci to C12 diols, Ci to Cs diols or Ci to e diols that may or may not contain other substitutions or functionalities including for example sulfonamide groups, fluoroalkyl groups or perfluoroalkyl groups or combinations thereof, or combinations thereof for example. In some embodiments, alkyl diols without additional functionalities can include, for example, 1,4-butanediol, 1,3- butanediol, 1,3 -propanediol, 1,2 -propanediol (propylene glycol), 1,6-hexanediol and ethylene glycol. In some embodiments alkyl diols that can include both sulfonamides and a fluoroalkyl or perfluoroalkyl group can include for example C₄F9S02 (C₄H₈OH)2, C₄F₉S02 (C2H40H)2, C₄F₉S02N(C₃H₆OH)2. In some embodiments, polyols can include poly (ether glycol), poly (tetramethylene glycol), poly (propylene glycol), polycaprolcatone and dimer diols for example. Useful molecular weights of polyols can vary depending on the particular polyol, the particular ultimate application of the compounds being produced, etc. but can include, for example molecular weights from 200 to 750, from 250 to 650, or form 300 to 400 for example.

In some methods, a second step of the process includes reacting a compound containing both a sulfonamide group and a fluoroalkyl or perfluoroalkyl group with the reaction product of the diol and phosphoryl chloride or diphosphorus pentoxide. Such compounds can include monoalcohol compounds for example. Specific examples of such compounds can include C₄F₉S02N(C4HsOH)2,

C₄F₉S02N(C2H40H)2, and C4F₉S02N(C₃H₆OH)2, for example.

Disclosed compounds can be utilized as surfactants in a number of compositions. Illustrative types of compositions can include coating compositions, paint compositions, etc.

In some embodiments, disclosed compounds can be utilized in latex paint compositions. In some embodiments, latex paint compositions and coatings (as used herein, the term "coating" refers to the latex paint composition after it has been applied to a substrate and has dried) that may have improved stain and soil resistance with resulting improved cleanability . The compositions can include a latex paint that includes a polymer having interpolymerized units that comprise units derived from styrene, methyl styrene, vinyl, or combinations thereof and one or more units derived from acrylates, methacrylates, acrylonitrile, or combinations thereof. In some embodiments co-monomers can include at least 40 mole percent of monomers selected from styrene, methyl styrene, or combinations thereof and at least 10 mole percent of one or more monomers selected from acrylates, methacrylates, and acrylonitrile. The acrylates and methacrylates may contain from 4 to 16 carbon atoms such as, for example, 2-ethylhexyl acrylate and methyl methacrylates. In some embodiments the monomers can be used in a proportion such that the final polymer has a glass-transition temperature (Tg) greater than 21° C and less than 95° C. The polymers may have a weight-average molecular weight of at least 100,000.

In some embodiments, the polymer can include interpolymerized units derived from 2-ethylhexyl acrylate. More specifically, the binding polymer may include polymerized units comprising from 50 to 70 mole percent of units derived from styrene, methyl styrene, or combinations thereof; from 10 to 30 mole percent of units derived from 2-ethylhexyl acrylate; and from 10 to 30 mole percent of units derived from methyl acrylate, acrylonitrile, or combinations thereof.

Illustrative specific examples of suitable polymers include a copolymer whose interpolymerized units are derived from about 49 mole percent styrene, 1 1 mole percent a-methylstyrene, 22 mole percent 2-ethylhexyl acrylate, and 18 mole percent methyl methacrylates with a Tg of approximately 45° C (available as NEOCRYL™ XA-6037 polymer emulsion from ICI Americas, Inc., Bridgewater, N.J.); a copolymer whose interpolymerized units are derived from about 51 mole percent styrene, 12 mole percent a-methylstyrene, 17 mole percent 2-ethylhexyl acrylate, and 1 mole percent methyl methacrylates with a Tg of approximately 44° C (available as JONCRYL™ 537 polymer emulsion from S. C. Johnson & Sons, Racine, Wis.); and a terpolymer whose interpolymerized units are derived from about 54 mole percent styrene, 23 mole percent 2-ethylhexyl acrylate, and 23 mole percent acrylonitrile with a Tg of approximately 44° C. (available from B. F. Goodrich Co. as CARBOSET™ XPD- 1468 polymer emulsion). Alternatively, an acrylic latex available under the trade designation ACRONAL® Plus 4130 from BASF Corporation can be utilized.

Compositions useful as latex paint compositions can also include pigments. In some

embodiments, the pigments can be "hiding pigments". A hiding pigment can function to give the paints better "hiding power" or coverage. In some embodiments, a hiding pigment has a refractive index above 1.8.

Suitable hiding pigments include white opacifying hiding pigments and colored organic and inorganic pigments. Representative examples of suitable white opacifying hiding pigments include rutile and anatase titanium dioxides, lithopone, zinc sulfide, lead titanate, antimony oxide, zirconium oxide, barium sulfide, white lead, zinc oxide, leaded zinc oxide, and the like, and mixtures thereof. In some embodiments, a white organic hiding pigment such as rutile titanium dioxide can be utilized. In some other embodiments, rutile titanium dioxide having an average particle size between about 0.2 to 0.4 microns can be utilized. Examples of colored organic pigments can include phthalo blue and hansa yellow. Examples of colored inorganic pigments can include red iron oxide, brown oxide, ochres, and umbers.

Compositions useful as latex paint compositions can also include thickeners. Thickeners can serve to modify the rheological properties of the paint to ensure good spreading, handling, and application characteristics. In some embodiments, latex paint compositions disclosed herein can include a non- cellulosic thickener (for example, an associative thickener; or more specifically, a urethane associative thickener).

Associative thickeners such as, for example, hydrophobically modified alkali swellable acrylic copolymers and hydrophobically modified urethane copolymers generally impart more Newtonian rheology to emulsion paints compared to conventional thickeners such as, for example, cellulosic thickeners. Representative examples of suitable associative thickeners include polyacrylic acids (available, for example, from Rohm & Haas Co., Philadelphia, Pa., as ACRYSOL™ RM-825 and QR- 708 Rheology Modifier) and activated attapulgite (available from Engelhard, Iselin, N.J. as ATTAGEL™ 40).

Disclosed compositions can also include other ingredients. Latex-paint films are formed by coalescence of the polymer to form a binding matrix at the ambient paint application temperature to form a hard, tack-free film. Coalescing solvents aid the coalescence of the film-forming binder by lowering the film-forming temperature. Disclosed latex paint compositions can include a coalescing solvent(s).

Representative examples of suitable coalescing solvents include 2-phenoxyethanol, diethylene glycol butyl ether, dibutyl phthalate, diethylene glycol, 2,2,4-trimethyl-l, l,3-pentanediol monoisobutyrate, and combinations thereof. Preferably, the coalescing solvent is diethylene glycol butyl ether (butyl carbitol) (available from Sigma-Aldrich, Milwaukee, Wis.) or 2,2,4-trimethyl-l,l,3-pentanediol monoisobutyrate (available from Eastman Chemical Co., Kingsport, Tenn., as Texanol™), or combinations thereof.

Coalescing solvents can be utilized at a level between about 12 to 60 grams (preferably about 40 grams) of coalescing solvent per liter of latex paint or at about 20 to 30 weight percent based on the weight of the polymer solids in the paint.

Compositions disclosed herein can be utilized to provide any type of coating, e.g., gloss, semi- gloss, satin, eggshell or flat matte. In some embodiments, the compositions can be utilized to provide or be classified as eggshell or flat paints.

Flatter paints can be produced using various approaches. One approach is to increase the pigment volume concentration (that is, the ratio by volume of all pigments in the paint to total nonvolatiles) (PVC) of the paint above its critical pigment volume concentration (CPVC). At the CPVC, many physical and optical properties of paint change abruptly and the paint changes from a semi-gloss paint to a flat paint. Typically, though, high PVC flat paints exhibit less durability than lower PVC flat paints, all else being equal, because these flat paints have less binder available per unit of pigment.

Alternatively, a flat paint can be produced by adding a flatting agent (that is, a material which reduces the gloss of a paint film). Flatting agents introduce micro-roughness to the surface causing the light to be reflected in a diffuse manner, which reduces the apparent gloss. This latter approach generally produces a better paint film. Suitable flatting agents can include silicas of various types such as, for example, NOVACITE™ Silica (available from Malvern Minerals, Hot Springs National Park, Ark.).

Conventional materials typically used in paints such as, for example, plasticizer, anti-foam agent, pigment extender, pH adjuster, tinting color, and biocide can also be utilized in disclosed paint compositions. Such typical ingredients are listed, for example, in TECHNOLOGY OF PAINTS, VARNISHES AND LACQUERS, edited by C. R. Martens, R. E. Kreiger Publishing Co., p 515 ( 1974).

Paints are commonly formulated with "functional extenders" to increase coverage, reduce cost, achieve durability, alter appearance, control rheology, and influence other desirable properties. Examples of functional extenders include, for example, barium sulphate, calcium carbonate, clay, gypsum, silica, and talc. The most common functional extenders for interior flat paints are clays. Clays have a number of properties that make them desirable. Inexpensive calcined clays, for example, are useful in controlling low-shear viscosity and have a large internal surface area, which contributes to "dry hide". But, this surface area is also available to trap stains.

Because of their tendency to absorb stains, it is preferable that calcined clays are used in disclosed paints only in the small amounts required for rheology control, for example, typically as less than about half of the total extender pigment, or are not used at all. In some embodiments, extenders for use in disclosed paint compositions are calcium carbonate, or even more specifically ultra-fine ground calcium carbonates such as, for example, OPACIMITE™ (available from ECC International, Sylacauga, Ala.), SUPERMITE™ (available from Imerys, Roswell, Ga.), or others having particle size of approximately 1.0 to 1.2 microns. Ultra-fine calcium carbonate help to space titanium dioxide optimally for hide (see, for example, K. A. Haagenson, "The effect of extender particle size on the hiding properties of an interior latex flat paint," American Paint & Coatings Journal, Apr. 4, 1988, pp. 89-94).

Typically utilized methods of formulating latex paint compositions can be utilized herein to form disclosed compositions.

Disclosed latex paint compositions can be applied to various substrate surfaces, such as, for example architectural surfaces such as walls and ceilings, articles such as furniture and boxes, or any other surface that is normally painted.

Illustrative disclosed embodiments are provided below.

wherein R¹ is -(CH₂)_m, -(CH₂CHMeO)_mCH₂CHMe-, -(CH2CH₂0)_mCH₂CH2-,

-(CH₂CH₂CH₂0)_mCH₂CH₂CH₂-, -R_mO(CO)R_m-, -R_mNHC(0)OR_m-, or -R_mN(S0₂C_pF_2p+i)R_m-; where p is an integer from 1 to 6; each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; m is an integer from 1 to 6; each R² is independently a Ci to Ce alkyl, a -S0₂C_pF_2p+i group where p is an integer from 1 to 8, or a combination thereof; each R^f is independently a Ci to Cs perfluoroalkyl-or fluoroalkyl; each y is independently an integer from 1 to 12; and n is an integer from 1 to 15. Such compounds, wherein R¹ is selected from -(CH₂)_m, -(CH₂CHMeO)_mCH₂CHMe-,

(CH2CH₂0)_mCH₂CH2-, or -(CH₂CH2CH20)_mCH₂CH2CH2-. Such compounds, wherein p is an integer from 1 to 6. Such compounds, wherein m is an integer from 1 to 4. Such compounds, wherein m is an integer from 1 to 2. Such compounds, wherein each R² is independently a Ci to alkyl. Such compounds, wherein each R^f is independently a Ci to perfluoroalkyl-or fluoroalkyl. Such compounds, wherein y is an integer from 1 to 4. Such compounds, wherein y is an integer from 1 to 2. Such compounds, wherein n is an integer from 1 to 10

Some illustrative embodiments can include compositions comprising: a polymer having interpolymerized units that comprise units derived from styrene, methyl styrene, vinyl, or combinations thereof and one or more units derived from acrylates, methacrylates, acrylonitrile, or combinations there

wherein R¹ is -(CH₂)_m, -(CH2CHMeO)_mCH₂CHMe-, -(CH2CH₂0)_mCH₂CH2-,

-(CH2CH₂CH20)_mCH2CH₂CH2-, -R_mO(CO)R_m-, -R_mNHC(0)OR_m-, or -R_mN(S02CpF_2p+i)Rm-, where p is an integer from 1 to 6;each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group; m is an integer from 1 to 6; each R² is independently a Ci to Ce alkyl, a -S0₂CpF₂p+i group where p is an integer from 1 to 8, or a combination thereof; each R^f is independently a Ci to Cs perfluoroalkyl-or fluoroalkyl; each y is independently an integer from 1 to 12; and n is an integer from 1 to 15.

Such compositions, wherein R¹ is selected from -(0¾)πι, -(CH2CHMeO)_mCH₂CHMe-, -

(CH₂CH₂0)mCH2CH2-, or -(CH2CH2CH20)_mCH₂CH₂CH2-. Such compositions, wherein p is an integer from 1 to 6. Such compositions, wherein m is an integer from 1 to 4. Such compositions, wherein each R² is independently a Ci to alkyl. Such compositions, wherein each R^f is independently a C₂ to perfluoroalkyl-or fluoroalkyl. Such compositions, wherein y is an integer from 1 to 4. Such compositions, wherein n is an integer from 1 to 10. Such compositions, further comprising one or more pigments. Such compositions, wherein at least one of the one or more pigments has a refractive index above 1.8. Such compositions further comprising one or more thickeners. Such compositions, wherein at least one of the one or more thickeners is an associative thickener. Such compositions further comprising one or more coalescing solvents. Such compositions, further comprising one or more flattening agents. Such compositions further comprising one or more plasticizers, one or more anti-foam agents, one or more pigment extenders, one or more pH adjusters, one or more tinting colors, one or more biocides, or any combination thereof. Some illustrative embodiments include an article comprising a coating formed from any of the illustrated compositions

Objects and advantages of this disclosure may be further illustrated by the following non-limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details should not be construed to limit this disclosure in any way.

EXAMPLES

Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained, or are available, from general chemical suppliers such as, for example, Sigma- Aldrich Company, Saint Louis, Missouri, or may be synthesized by conventional methods. These abbreviations are used in the following examples: g = grams, sec = seconds, min = minutes, h = hours, d = days, °C = degrees Celsius, Mw = weight average molecular weight, Mn = number average molecular weight, Mz = z average molecular weight, μιη = micrometers, mm = millimeters, mil = thousandths of an inch, cm = centimeters, in = inches, mL = milliLiters, kG = kilograms, lbs = pounds, mol = moles.

Materials

Polyethylene glycol 300 Polyethylene glycol with a Mw of

approximately 300, available from Sigma- Aldrich

Polyethylene glycol 250 Polyethylene glycol with a Mw of

approximately 250, available from Sigma- Aldnch

0=P(OPh)₂H Diphenylphosphine oxide, 99%, available from

Sigma-Aldrich

Potassium tripolyphosphate Available from Spectrum Chemical Mfg. Corp.,

New Brunswick, NJ, USA

NATROSOL PLUS 330 Hydroxyethylcellulose, available under the trade designation NATROSOL from Ashland, Lexington, KY, USA

VANTEX - T A tertiary amine additive available under the trade designation "VANTEX-T" from Eastman Chemical Company, Kingsport, TN, USA.

FOAMSTAR ST 2438 A defoamer available under the trade

designation "FOAMSTAR ST 2438" from BASF Corporation, Florham Park, NJ, USA

TAMOL 1124 A hydrophilic copolymer pigment dispersant available from Dow Chemical Company, Midland, MI, USA

TRITON CF- 10 A nonionic surfactant available from Dow

Chemical Company

TI-PURE R-706 Titanium dioxide pigment available from

Chemours, Wilmington, DE, USA

3M W-410 Alkali alumino silicate ceramic microspheres, available under the trade designation, "3M™ Ceramic Microspheres White Grade W-410," from 3M Company, St Paul, MN, USA

MINEX 4 A micronized functional filler and/or extender produced from nepheline syenite with a median particle size of 6.8 μιη, available under the trade designation, "ΜΓΝΕΧ 4," from Unimin Corporation, New Canaan, CT, USA

DURAMITE A coarse, medium particle size marble,

available under the trade designation,

"DURAMITE," from Imerys Carbonates, Roswell, GA, USA ACRONAL PLUS 4130 All acrylic latex, available under the trade

designation, "ACRONAL PLUS 4130," from

BASF Corporation, Florham Park, NJ, USA

ACRYSOL TT-935 A hydrophobically modified anionic thickener,

available under the trade designation,

"ACRYSOL TT-935," from Dow Chemical

Company

CAPSTONE FS-61 Anionic fluoro surfactant, available in a water- based dispersion under the trade designation, "CAPSTONE FLUOROSURFACTANT FS- 61," From Chemours

SPS-2001 A standard carpet dry soil, formerly available

under the trade designation, "SPS-2001," from 3M Company

Method for determining Surface Tension

Surface tension measurements were made using a K12 Tensiometer (available from KRUSS USA, Matthews, NC, USA) empolying a Pt plate cleaned between samples by rinsing with DI water and firing with a propane torch. The results provided in Table 3 for the materials at various concentrations represent means of at least five determinations, collected until the relative standard deviation (calculated as standard deviation / mean) was at most 0.07.

Method for determining Dirt Pick-up Resistance (DPUR)

Paint samples were deposited on one side of Leneta 10 mil (0.25 mm) PVC Black plastic cards, available under the trade designation, "P121-10N Leneta Scrub Test Panels," available from Leneta Company, Mahwah, NJ, USA were coated on one side using a 7 mil (0.18 mm) bird blade applicator. Paint was allowed to age under ambient temperature and humidity for 7 d. After aging, 3 in (7.62 cm) x 6 in (15.24 cm) samples were cut from the coated card. The temperature and humidity in the test room was recorded. The initial reflectance of the painted side of the test cards was measured using a ColorFlex EZ spectrophotometer, operated in Illuminant/Observer C/2 Read Y value mode (available under the trade designation ColorFlex EZ 45/0 LAV from Hunter Associates Laboratory, Inc., Reston, VA, USA) and recorded as Rmit. The painted sides of the samples were covered with SPS-2100 for 24 h. After 24 h, the samples were tapped to displace SPS-2100 and reflectance of the painted sides was again recorded as Rfinai. The ratio Rfmai / mit was calculated for each sample. The results, presented in Table 4, below, represent means for triplicate measurements.

Method for determining Washability

Washability was measured as described for testing with the nonabrasive medium as described in ASTM D3450-15, with the following modifications: The nonabrasive medium used on each test panel was prepared as 5 g of a 10% Dawn dish soap solution in water; 25 cycles were used; 2.5 g water was placed on the sponge path; and Reported values are means for triplicate determinations of both R and DE. For R, the initial reflectance of the painted side of the test cards was measured using a ColorFlex EZ spectrophotometer, operated in Illuminant/Observer C/2 Read Y value mode and recorded as Rjmt. A foam brush was used to apply Leneta ST-1 oily staining media (available from Leneta Company) to the painted sides of the test cards. After 24 h, the samples were cleaned as described above and reflectance of the painted sides was again recorded as Rfmai. The ratio Rfmai / Rmt was calculated for each sample as the R value. For DE, the color change value was calculated by the ColorFlex EZ specrtrophotomer for samples measured before and after the soiling/cleaning process.

The paint formulation used to evaluate the performance was prepared by mixing the components listed in Table 2, below, in the order shown, through the second charge of water. After thorough mixing, the last ingredient was added slowly, with agitation of the mixture.

Table 2: Paint formulation

Comparative Example 1 (CE-1)

25 g of N-MeFBSE were added to a 100 mL flask equipped with mechanic agitator and thermometer. The flask was heated to melt the alcohol. 2.5 g of P2O5 was added in 4 portions over 90 min. After the addition, the reaction was continued at 125 °C for an additional 1.5 h. The mixture was then allowed to cool. When the mixture had cooled to below 100 °C, 4.0 g NH₄OH and 120 g DI water were added, resulting in a high-viscosity phosphate ester ammonium salt determined to be approximately 15% solids.

Comparative Example 2 (CE-2)

Capstone FS-61 was diluted in water for surface tension measurements.

Example 1 (EX-1) 18.75 g N-MeFBSE and 7.74 g FBSEE were added to a three neck flask. The flask was heated to 80 °C to melt the alcohol. To the alcohol mixture was added, in portions, 2.81 g of P2O5. After addition, the mixture was heated at 120 °C for 4 h. The product was neutralized with diethanolamine and water to make a 15% solids aqueous solution

Example 2 (EX-2)

For EX-2, the procedure described for EX- 1 was followed, except that the product was dissolved in IPA before being neutralized with diethanolamine and water to make a 30% solids solution in IPA/Water. Example 3 (EX-3)

To 3.9 g of FBSEE (MW 387, 0.01 mol) (melt at 70 °C) was added slowly 3.0 g POCI3 (0.02 mol). After the addition, the reaction was heated at 70 °C for 1 h. Next, 7.1 g N-MeFBSE (0.02 mol) was added and the reaction continued at 70 °C for 3 h. The HCl generated from the reaction was removed by nitrogen bubbling. 4 g of NH4OH and 75 g of DI water was added to neutralize the product to form a viscous, approximately 15% solids solution.

Example 4 (EX-4)

To a two neck, 250 niL flask with 15.3 g of POCI3 (0.1 mol) was slowly added 9.6 g of tripropylene glycol (0.05 mol) at room temperature. After the addition, the reaction was continued for 2 h at 50 °C. Then 35.7 g N-MeFBSE (0.1 mol) was added at once, and reacted at 50 °C overnight. The HCl generated from the reaction was removed by nitrogen bubbling. The mixture was neutralized with NH₄OH in water to pH = 8-9, resulting in a viscous, 27% solids liquid.

Example 5 (EX-5)

The sample was prepared as described for PE-5, but using 4.5 g butanediol (0.05 mol.) in place of the tripropylene glycol. The product was a viscous, 25% solids solution in water.

Example 6 (EX-6)

The sample was prepared as described for PE-5, but using 0 05 mol of Polyethylene Glycol 300. The product was a viscous, 13% solids solution in water.

Example 7 (EX-7)

The sample was prepared as described for PE-5, but using 0.05 mol of Polyethylene Glycol 250. The product was a viscous, 10% solids solution in water.

Example 8 (EX-8)

77.4 g FBSEE and 47.3 g 0=P(OPh)2H were added to a 250 mL flask with mechanical stirring. The pressure inside the flask was maintained at 25 torr while the reaction temperature was slowly raised to 160 °C over 2 h. Distillate (phenol) was collected in a dry ice trap. 78 g of product in the flask was collected.

8.66 g of the obtained product, 1.72 g of tirchloroisocyanuric acid and 40 g of acetone were charged into a flask with stirring overnight at room temperature. The white solid was filtered off. The clear solution was rotavaporated and 8.8 g of solid product was obtained. 1 g of the solid product was mixed with 1 g of 28-30% ammonium hydroxide and different amount of water to prepared different concentrations. The surface tensions of the resulting solutions were measured according to the procedure described above and are provided in Table 3.

Molecular weight measurement of EX-4

The molecular weight of EX-4 before NH4OH neutralization was measured by GPC calibrating the system against narrow molecular weight polystyrene standards. Presented in Table 2, below, are the relative molecular weight and polydispersity values. Each result is the average of duplicate injections. Based on these results, the final MW after NH4OH neutralization was estimated to be approximately 1300.

Table 2: Molecular Weight

Table 3. Surface Tension Results (dynes / cm) in DI Water

NM = Not Measured

Comparative Example 3 (CE-3)

Composition prepared as described in Table 2 above

Comparative Example 4 (CE4)

Composition prepared as described in Table 2 above, with the addition of CAPSTONE FS-61 to a concentration of 0.2% solids.

Example 9 (EX-9) Composition prepared as described in Table 2 above, with the addition of EX-4 to a concentration of 0.2% solids.

Table 4: Dirt pick-up resistance and washability results

Foreseeable modifications and alterations of this disclosure will be apparent to those skilled in the art without departing from the scope and spirit of the disclosure. This disclosure should not be restricted to the embodiments that are set forth in this application for illustrative purposes. To the extent that there is any conflict or discrepancy between this specification as written and the disclosure in any document mentioned or incorporated by reference herein, this specification as written will prevail.

Claims

1. A compound of formula I

wherein R¹ is -(CH₂)m, -(CH2CHMeO)mCH₂CHMe-, -(CH₂CH₂0)mCH2CH2-,

-(CH2CH2CH₂0)mCH2CH₂CH2-, -RmO(CO)R_m-, -RmNHC(0)OR_m-, or -RmN(S02C_PF2_P+i)Rm-, where p is an integer from 1 to 6;

each R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted aryl group;

m is an integer from 1 to 6;

each R² is independently a Ci to C6 alkyl, a -S02C_PF2p+i group where p is an integer from

1 to 8, or a combination thereof;

each R^f is independently a C i to Cs perfluoroalkyl-or fluoroalkyl;

each y is independently an integer from 1 to 12; and

n is an integer from 1 to 15.

The compound according to claim 1, wherein R¹ is selected from -(CH2)m,

-(CH2CHMeO)mCH₂CHMe-, -(CFkCKO CFkCFk-, or

-(CH2CH2CH20)mCH2CH₂CH2-.

The compound according to any of claims 1 to 2, wherein p is an integer from 1 to 6. The compound according to any of claims 1 to 3, wherein m is an integer from 1 to 4.

The compound according to any of claims 1 to 3, wherein m is an integer from 1 to 2.

The compound according to any of claims 1 to 5, wherein each R² is independently a Ci to Ce alkyl.

7. The compound according to any of claims 1 to 6, wherein each R^f is independently a C2 to Ce perfluoroalkyl-or fluoroalkyl.

8. The compound according to any of claims 1 to 7, wherein y is an integer from 1 to 4.

9. The compound according to any of claims 1 to 7, wherein y is an integer from 1 to 2.

10. The compound according to any of claims 1 to 9, wherein n is an integer from 1 to 10.

1 1. A composition comprising:

a polymer having interpolymerized units that comprise units derived from styrene, methyl styrene, vinyl, or combinations thereof and one or more units derived from acrylates, methacrylates, acrylonitrile, or combinations thereof; and

the compound of formula I according to any one of claims 1 to 10.

12. The composition according to claim 1 1 , further comprising one or more pigments.

13. The composition according to claim 12, wherein at least one of the one or more pigments has a refractive index above 1.8.

14. The composition according to any of claims 1 1 to 13 further comprising one or more thickeners.

15. The composition according to claim 14, wherein at least one of the one or more

thickeners is an associative thickener.

16. The composition according to any of claims 1 1 to 15 further comprising one or more coalescing solvents.

17. The composition according to any of claims 1 1 to 16 further comprising one or more flattening agents.

18. The composition according to any of claims 1 1 to 17 further comprising one or more plasticizers, one or more anti-foam agents, one or more pigment extenders, one or more pH adjusters, one or more tinting colors, one or more biocides, or any combination thereof.

19. An article comprising a coating formed from a composition according to any of claims 11 to 18.