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Title:
FLUORINATED ANIONIC POLYMERS AND COMPOSITIONS INCLUDING THEM
Document Type and Number:
WIPO Patent Application WO/2018/118962
Kind Code:
A1
Abstract:
The fluorinated polymer includes a first divalent unit represented by formula: (Formula (I)) a second divalent unit comprising a poly(alkyleneoxy) group, and at least one of a pendant phosphate group or a pendant phosphonate group. In the formula, Rf represents a fluoroalkyl group having from 1 to 8 carbon atoms, R1 is hydrogen or methyl, Q is a bond or -SO2-N(R)-, wherein R is alkyl having from 1 to 6 carbon atoms, and m is an integer from 1 to 20. The fluorinated polymer may be useful, for example, for improving the soil and stain resistance in a paint or coating composition. Compositions that include the fluorinated polymer may be aqueous compositions that further include a film-forming polymer.

Inventors:
FAN, Wayne W. (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
RINK, Kevin J. (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
AUDENAERT, Frans A. (Hermeslaan 7, Diegem, Diegem, BE)
DAMS, Rudolf J. (Hermeslaan 7, Diegem, Diegem, BE)
YANG, Yu (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
SAVU, Patricia M. (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
SMITH, Sean M. (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
Application Number:
US2017/067374
Publication Date:
June 28, 2018
Filing Date:
December 19, 2017
Export Citation:
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Assignee:
3M INNOVATIVE PROPERTIES COMPANY (3M Center, Post Office Box 33427Saint Paul, Minnesota, 55133-3427, US)
International Classes:
C08F214/18; C08F14/18; C08F22/24; C08F220/22; C08F230/02; C08L27/12; C08L43/02; C09D127/12; C09D143/02
Domestic Patent References:
WO2016099952A12016-06-23
WO2016028499A12016-02-25
Foreign References:
US20140228450A12014-08-14
US20130012615A12013-01-10
Attorney, Agent or Firm:
GROSS, Kathleen B. et al. (3M Center, Office of Intellectual Property CounselPost Office Box 3342, Saint Paul Minnesota, 55133-3427, US)
Download PDF:
Claims:
What is claimed is:

1. A fluorinated polymer comprising:

a first divalent unit represented by formula:

wherein

Rf represents a fluoroalkyl group having from 1 to 8 carbon atoms;

R1 is hydrogen or methyl;

Q is a bond or -S02-N(R)-, wherein R is alkyl having from 1 to 6 carbon atoms; and m is an integer from 1 to 20,

a second divalent unit comprising a poly (alky leneoxy) group; and

at least one of a pendant phosphate group or a pendant phosphonate group.

2. The fluorinated polymer of claim 1, wherein the phosphate group is represented by formula -0-P(0)(OY)2, wherein the phosphonate group is represented by formula -P(0)(OY)2, and wherein each Y is independently hydrogen or a counter cation.

3. The fluorinated polymer of claim 1 or 2, wherein the second divalent unit is present in an amount of at least 30 percent by weight, based on the total weight of the fluorinated polymer.

4. The fluorinated polymer of any one of claims 1 to 3, wherein at least one of the second divalent units is represented by formula:

wherein

R2 is hydrogen or methyl; R3 is alkyl having up to 4 carbon atoms, -0-P(0)(OY)2, or hydrogen;

each Y is independently selected from the group consisting of hydrogen and a counter cation;

EO represents -CH2CH20-;

each R40 is independently selected from the group consisting of -CH(CH3)CH20-, -CH2CH2CH2O-, -CH2CH(CH3)0-, -CH2CH2CH2CH2O-, -CH(CH2CH3)CH20-, -CH2CH(CH2CH3)0-, and -CH2C(CH3)20-;

each p is independently a value from 0 to 150; and

each q is independently a value from 0 to 150 , wherein p+q is at least 5;

with the proviso that when R3 is alkyl having up to 4 carbon atoms or hydrogen, the fluorinated polymer further comprises at least one third divalent unit represented by formula:

YO— P=0

I

OY ; or

wherein

Q1 is selected from the group consisting of -0-, -S-, and -N(R7)-;

each R7 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;

each R' is independently hydrogen or methyl;

V is alkylene that is optionally interrupted by at least one ether linkage, thioether linkage, or amine linkage;

Z is selected from the group consisting of -P(0)(OY)2 and -0-P(0)(OY)2; and each Y is independently selected from the group consisting of hydrogen and a counter cation.

5. The fluorinated polymer of claim 4, wherein the fluorinated polymer comprises the third divalent unit, and wherein the third divalent unit is present in an amount up to 20 percent by weight, based on the total weight of the fluorinated polymer.

6. The fluorinated polymer of claim 4 or 5, wherein the third divalent unit is represented by formula:

wherein

Q1 is selected from the group consisting of -0-, -S-, and -N(R7)-;

R7 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;

R' is hydrogen or methyl;

V is alkylene that is optionally interrupted by at least one ether linkage, thioether linkage, or amine linkage; and

each Y is independently hydrogen or a counter cation.

7. The fluorinated polymer of any one of claims 1 to 6, wherein at least one of the second divalent units is represented by formula:

wherein

R2 is independently hydrogen or methyl;

EO represents -CH2CH20-;

each R40 is independently selected from the group consisting of -CH(CH3)CH20-, -CH2CH2CH2O-, -CH2CH(CH3)0-, -CH2CH2CH2CH2O-, -CH(CH2CH3)CH20-, -CH2CH(CH2CH3)0-, and -CH2C(CH3)20-;

each p is independently a value from 0 to 150;

each q is independently a value from 0 to 150, wherein p+q is at least 5;

each Y is independently hydrogen or a counter cation.

8. The fluorinated polymer of any one of claims 1 to 7, wherein Q is -S02N(R)- and R is methyl, ethyl, or hexyl, and wherein Rf represents a fluoroalkyl group having up to 4 carbon atoms.

9. The fluorinated polymer of any one of claims 1 to 8, wherein at least one of the second divalent units is represented by formula:

wherein

R2 is hydrogen or methyl;

R3a is alkyl having up to 4 carbon atoms or hydrogen;

EO represents -CH2CH20-;

each R40 is independently selected from the group consisting of -CH(CH3)CH20-, -CH2CH2CH2O-, -CH2CH(CH3)0-, -CH2CH2CH2CH2O-, -CH(CH2CH3)CH20-, -CH2CH(CH2CH3)0-, and -CH2C(CH3)20-;

each p is independently a value from 0 to 150; and

each q is independently a value from 0 to 150 , wherein p+q is at least 5.

10. The fluorinated polymer of any one of claims 1 to 9, wherein at least one of the second divalent units is represented by formula:

wherein R2 is hydrogen or methyl;

EO represents -CH2CH20-;

each R40 is independently selected from the group consisting of -CH(CH3)CH20- -CH2CH2CH2O- -CH2CH(CH3)0- -CH2CH2CH2CH2O-, -CH(CH2CH3)CH20- -CH2CH(CH2CH3)0- and -CH2C(CH3)20-;

each p is independently a value from 0 to 150; and

each q is independently a value from 0 tol50 , wherein p+q is at least 150.

11. The fluorinated polymer of any one of claims 1 to 10, wherein the fluorinated polymer is substantially free of divalent unit represe

wherein

each R5 is independently alkyl having from 1 to 30 carbon atoms; and

each R6 is independently hydrogen or methyl.

12. The fluorinated polymer of any one of claims 1 to 11, wherein the fluorinated polymer is substantially free of volatile organic solvent.

13. A composition comprising the fluorinated polymer of any one of claims 1 to 12 and a film-forming polymer.

14. The composition of claim 13, further comprising at least one of a pigment, a thickener, or an inorganic filler. 15. The composition of claim 13 or 14, wherein the composition further comprises water and has a pH of at least 7.

Description:
FLUORINATED ANIONIC POLYMERS AND COMPOSITIONS INCLUDING THEM Cross-Reference to Related Application

This application claims priority to U.S. Provisional Application No. 62/436,829, filed December 20, 2016, the disclosure of which is incorporated by reference in its entirety herein.

Background

Fluorochemicals have been used in a variety of applications for many years. For example, fluorinated surfactants have been added to a variety of formulations (e.g., coatings and foams). The addition of a fluorinated surfactant to a formulation (e.g., a coating formulation) may enhance the properties of the formulation by improving, for example, wetting behavior, leveling properties, stability (e.g., with respect to phase separation or foam half-life), easy-cleanability, and stain resistance. In other applications, fluorochemicals have been used to provide properties such as hydrophobicity and oleophobicity to various materials (e.g., ceramics, fibrous substrates and porous stones).

Certain polymers including fluorinated groups and phosphate groups have been reported. See, for example, U.S. Pat. No. 8,945,712 (Dams et al.), which describes treating surfaces with certain polymers to make the surfaces stain-resistant, hydrophobic, and oleophobic.

Certain polymers including fluorinated groups and hydrophilic groups have been described as useful additives in paint compositions in U.S. Pat. No. 7,041,727 (Kubicek et al.).

Summary

In one aspect, the present disclosure provides a fluorinated polymer that includes a first divalent unit represented by formula:

a second divalent unit comprising a poly(alkyleneoxy) group, and at least one of a phosphate group or a phosphonate group. In this formula, Rf represents a fluoroalkyl group having from 1 to 8 carbon atoms, R 1 is hydrogen or methyl, Q is a bond or -S0 2 -N(R)-, wherein R is alkyl having from 1 to 6 carbon atoms, and m is an integer from 1 to 20.

In another aspect, the present disclosure provides this fluorinated polymer for use in an aqueous composition. The aqueous composition may be a paint or coating composition. The fluorinated polymer may be useful, for example, for making the resulting paint or coating easier to clean or more stain- resistant.

In another aspect, the present disclosure provides a composition including the aforementioned fluorinated polymer and a film-forming polymer. The composition can also include at least one of a pigment, a thickener, or an inorganic filler. The composition may be an aqueous composition with a pH of at least 7.

The fluorinated polymer described herein has several repeating units and therefore a higher molecular weight than monomeric fluoroalkyl surfactants, e.g., perfluoroalkyl diester and mono-ester phosphate surfactants. The fluorinated polymer described herein poses less health and safety concerns such as inhalation toxicity in compositions that are applied by spraying. When used in paint and coating compositions, the fluorinated polymers disclosed herein typically provide excellent surface properties and stain and soil resistant performance.

In this application:

Terms such as "a", "an" and "the" are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terms "a", "an", and "the" are used interchangeably with the term "at least one".

The phrase "comprises at least one of followed by a list refers to comprising any one of the items in the list and any combination of two or more items in the list. The phrase "at least one of followed by a list refers to any one of the items in the list or any combination of two or more items in the list.

The term "solvent" refers to a homogeneous liquid material (inclusive of any water with which it may be combined) that is capable of at least partially dissolving the fluorinated polymer disclosed herein at 25 °C.

"Alkyl group" and the prefix "alk-" are inclusive of both straight chain and branched chain groups and of cyclic groups. Unless otherwise specified, alkyl groups herein have up to 20 carbon atoms. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have from 3 to 10 ring carbon atoms.

The phrase "interrupted by at least one functional group", for example, with regard to an alkyl (which may or may not be fluorinated), alkylene, or arylalkylene refers to having part of the alkyl, alkylene, or arylalkylene on both sides of the functional group.

The term "polymer" refers to a composition having a structure which essentially includes the multiple repetition of units derived, actually or conceptually, from monomers of low relative molecular mass. The term "polymer" encompasses oligomers. Polymers are usually a mixture of molecules having a distribution of molecular weights.

The term "fluoroalkyl group" includes linear, branched, and/or cyclic alkyl groups in which all C- H bonds are replaced by C-F bonds as well as groups in which hydrogen or chlorine atoms are present instead of fluorine atoms. In some embodiments, up to one atom of either hydrogen or chlorine is present for every two carbon atoms. In some embodiments of fluoroalkyl groups, when at least one hydrogen or chlorine is present, the fluoroalkyl group includes at least one trifluoromethyl group. The term "phosphate group" refers to groups having the structure

, where one or more of the oxygen atoms is bonded to a pendant group of the polymer. In some embodiments, one oxygen atom is bonded to a pendant group of the polymer, and the other oxygen atoms are bonded to hydrogen, a counter cation, an alkyl group, or a combination thereof. In some embodiments, two oxygen atoms are bonded to pendant groups of the polymer, and the other oxygen atom is bonded to hydrogen, a counter cation, or an alkyl group. In some embodiments, a phosphate group is represented by formula -0-P(0)(OY)2, wherein each Y is independently hydrogen or a counter cation, that is bonded to a pendant group of the polymer.

The term "phosphonate group" refers to groups having the structure

, where the phosphorous atom is bonded to a carbon atom on a pendant group of the polymer. One or more of the oxygen atoms may also be bonded to a pendant group of the polymer. In some embodiments, each oxygen is independently bonded to hydrogen, a counter cation, or an alkyl group. In some embodiments, a phosphonate group is represented by formula -P(0)(OY)2, wherein each Y is independently hydrogen or a counter cation, that is bonded to a pendant group of the polymer.

All numerical ranges are inclusive of their endpoints and nonintegral values between the endpoints unless otherwise stated (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.).

Detailed Description

The fluorinated polymer according to and useful for practicing the present disclosure comprises (e.g., at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or at least 20 up to 30, 35, 40, 45, 50, 100, or up to 200) first divalent units independently represented by formula:

Rf-Q-C m H 2m -0-C=0

X

For divalent units having this formula, Q is a bond or -S02N(R)-, wherein R is alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl). In some embodiments, Q is a bond. In some embodiments, Q is -S0 2 N(R)-. In some of these embodiments, R is methyl or ethyl, m is an integer from 1 to 11 (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11). In some of these embodiments, m is 1; in other of these embodiments, m is 2. In some embodiments wherein Q is -S02N(R)-, m is an integer from 2 to 11, 2 to 6, or 2 to 4. In some embodiments wherein Q is a bond, m is an integer from 1 to 6, 1 to 4, or 1 to 2. In embodiments wherein Q is a bond, it should be understood that the first divalent units may also be represented by formula:

p-c m H 2m -0-c-o

XIa

In some embodiments, fluorinated polymers according to the present disclosure comprise (e.g., at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or at least 20 up to 30, 35, 40, 45, 50, 100, or up to 200) first divalent units independently represented by formula:

Xlb

For divalent units of this formula, n is an integer from 2 to 20 (i.e., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20). In some embodiments, n is an integer from 2 to 6 or 2 to 4. R is alkyl having 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, or n-hexyl). In some embodiments, R is methyl, ethyl, or n-hexyl.

For any of the embodiments of the first divalent units having Rf groups, each Rf independently represents a fluorinated alkyl group having from 1 to 8 (in some embodiments, 1 to 6, 2 to 6 or 2 to 4) carbon atoms (e.g., trifluoromethyl, perfluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chlorotetrafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, 1,1,2,3,3,3-hexafluoropropyl, perfluoroisobutyl, perfluoro-seobutyl, or perfluoro-/er -butyl, perfluoro-n-pentyl, pefluoroisopentyl, or perfluorohexyl). In some embodiments, Rf is perfluorobutyl (e.g., perfluoro-n-butyl, perfluoroisobutyl, or perfluoro-seobutyl). In some embodiments, Rf is perfluoropropyl (e.g., perfluoro-n-propyl or perfluoroisopropyl). Rf may contain a mixture of fluoroalkyl groups (e.g., with an average of up to 8, 6, or 4 carbon atoms).

For any of the embodiments of the first divalent units having Rf 2 groups, each Rf 2 independently represents a fluorinated alkyl group having from 1 to 8 (in some embodiments, 1 to 8, 1 to 6, or 2 to 4) carbon atoms (e.g., trifluoromethyl, perfluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chlorotetrafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-n-butyl, 1, 1,2,3, 3,3-hexafluoropropyl,

perfluoroisobutyl, perfluoro-seobutyl, or perfluoro-iert-butyl, perfluoro-n-pentyl, pefluoroisopentyl, perfluorohexyl, perfluoroheptyl, or perfluorooctyl). In some embodiments, Rf 2 is perfluorobutyl (e.g., perfluoro-n-butyl, perfluoroisobutyl, or perfluoro-seobutyl). In some embodiments, Rf 2 is

perfluoropropyl (e.g., perfluoro-n-propyl or perfluoroisopropyl). Rf 2 may contain a mixture of fluoroalkyl groups (e.g., with an average of up to 8, 6, or 4 carbon atoms).

In some embodiments of fluorinated polymers according to and useful for practicing the present disclosure, the first divalent units have up to 6 fluorinated carbon atoms.

For any of the embodiments of the first divalent units, R 1 is hydrogen or methyl. In some embodiments, R 1 is hydrogen. In some embodiments, R 1 is methyl.

When there is more than one first divalent unit, each R 1 , Rf, Q, and m and Rf 2 , R, and n can be independently selected.

The second divalent unit in the fluoropolymer according to the present disclosure comprises a poly(alkyleneoxy) group. The poly (alky leneoxy) group in fluorinated polymers according to and useful for practicing the present disclosure can comprise a plurality (i.e., multiple) of repeating alkyleneoxy groups having from 2 to 4 or 2 to 3 carbon atoms (e.g., -CH 2 CH 2 0- -CH(CH 3 )CH 2 0-,

-CH 2 CH(CH 3 )0- -CH 2 CH 2 CH 2 0- -CH(CH 2 CH 3 )CH 2 0- -CH 2 CH(CH 2 CH 3 )0- or -CH 2 C(CH 3 ) 2 0-). In some embodiments, the poly(alkyleneoxy) group comprises a plurality of ethoxy groups, propoxy groups, butoxy groups, or combinations thereof. In some embodiments, the poly(alkyleneoxy) group comprises a plurality of ethoxy groups, propoxy groups, or combinations thereof. The poly(alkyleneoxy) group may have a number average molecular weight of at least 200, 300, 500, 700, or even at least 1000 grams per mole up to 2000, 4000, 5000, 8000, 10000, 15,000, or even up to 20000 grams per mole. Two or more differing alkyleneoxy groups may be distributed randomly in the series or may be present in alternating blocks. The poly(alkyleneoxy) group may be pendant from the polymer chain, or it may be a segment incorporated into the polymer backbone. The fluoropolymer according to the present disclosure may also have both a poly(alkyleneoxy) group pendant from the polymer chain and a poly (alkyleneoxy) segment incorporated into the polymer backbone.

In some embodiments, the fluorinated polymer comprises at least one (e.g., at least 1, 2, 5, 10, 15, 20, or at least 25) second divalent unit represented by formula:

XII

XIII

In formulas XII and XIII, each R 2 is independently hydrogen or methyl (in some embodiments, hydrogen and in some embodiments, methyl). Each R 3 is independently alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl), -P(0)(OY)2, wherein each Y is independently as described below in connection with formula XVIII, or hydrogen. In some embodiments, R 3 is R 3a , and each R 3a is independently alkyl having up to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl) or hydrogen. EO represents -CH 2 CH 2 0-. Each R 4 0 is

independently selected from the group consisting of -CH(CH 3 )CH 2 0-, -CH 2 CH 2 CH 2 0- -CH 2 CH(CH 3 )0- -CH 2 CH 2 CH 2 CH 2 0-, -CH(CH 2 CH 3 )CH 2 0- -CH 2 CH(CH 2 CH 3 )0- and

-CH 2 C(CH 3 ) 2 0- In some embodiments, each R 4 0 independently represents -CH(CH 3 )CH 2 0- or -CH 2 CH(CH 3 )0-). Each p is independently a value from 0 to 150 (in some embodiments, from 7 to about 130, or from 14 to about 130, or from 10 to 20); and each q is independently a value from 0 to 150 (in some embodiments, from about 20 to about 100, 1 to 55, or from about 9 to about 25, or from 15 to 25). The sum p + q is at least 5 (in some embodiments, at least 10 or at least 20.) In some embodiments, the ratio p/q has a value from at least 0.5, 0.75, 1 or 1.5 to 2.5, 2.7, 3, 4, 5, or more.

In some embodiments, at least one of the second divalent units is represented by formula XVI:

XVI.

wherein R 2 is hydrogen or methyl (in some embodiments, hydrogen, and in some embodiments, methyl). R 4 is independently alkyl having from 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl, or isobutyl). In some embodiments, R 4 is methyl or ethyl. Also formula XVI, r is in a range from 1 to 50 (in some embodiments, 1 to 25, 5 to 25, or 5 to 20). The fluorinated polymer may include at least one (e.g., at least 1, 2, 5, 10, 15, 20, or at least 25) and up to 200, 100, or 50 of these second divalent units.

In some embodiments, the second divalent unit is represented by formula:

XV

wherein p, q, R 2 , EO, and R 4 0 are as defined above for formulas XII and XIII in any of their embodiments.

In some embodiments the second divalent unit may be a sulfur-terminated segment (e.g., -S(0)o-2-C 3 H 2s -C(0)-0-(EO)p-C(0)-CsH 2s -S(0)o-2-,

-S(0)o-2-C 3 H 2s -C(0)-0-(EO)p-(R 4 0) q -(EO)p-C(0)-C 3 H 2s -S(0)o-2-, or

-S(0)o-2-CsH2s-C(0)-0-(PO) q -(EO)p-(PO) q -C(0)-C 3 H2s-S(0)o-2-, wherein p, q, EO, and R 4 0 are as defined above for formulas XII and XIII in any of their embodiments and s is an integer from 1 to 5, or in some embodiments, 2 to 3).

In some embodiments, the second divalent unit comprising the poly(alkyleneoxy) group also comprises a phosphate group. In some of these embodiments, at least one of the second divalent units is represented by formula:

XIX or

XX,

wherein p, q, R 2 , EO, and R 4 0 are as defined above for formulas XII and XIII in any of their embodiments, and Y is independently hydrogen or a counter cation. The counter cation may be any of those described below in connection with formula XVIII.

A combination of any of the second divalent units described above may be useful for the fluorinated polymer of the present disclosure. When there is more than one second divalent unit, each p, q, r, Y, R 2 , R 3 , R 3a , R 4 , and R 4 0 can be independently selected.

In some embodiments, fluorinated polymers according to and useful for practicing the present disclosure further comprise at least one (e.g., at least 1, 2, 5, 10, 15, 20, or at least 25) third divalent unit represented by formula:

YO— P=0

I

OY ; or

XVII

XVIIIb

The third divalent units are optional in the fluorinated polymer of the present disclosure. For example, if the second divalent unit includes a phosphate or phosphonate group, the third divalent unit need not be present. If the second divalent unit does not include a phosphate or phosphonate groups, the fluorinated polymer includes a third divalent unit. In formulas XVIII and XVIIIb, Q 1 is -0-, -S-, or -N(R 7 )- (in some embodiments, -0-). Each R 7 is independently hydrogen or alkyl having from 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl). V is alkylene that is optionally interrupted by at least one ether linkage (i.e., -0-) or amine linkage (i.e., -N(R 7 )-). In some embodiments, V is not a poly(alkyleneoxy) group. In some embodiments, V is alkylene that is optionally interrupted by one ether linkage (i.e., -0-), thioether (i.e., -S-) linkage, or amine linkage (i.e., -N(R 7 )-). In some embodiments, V is alkylene having from 2 to 4 (in some embodiments, 2) carbon atoms. In formula XVIII, each Z is independently selected from the group consisting of -P(0)(OY)2 and -0-P(0)(OY)2. In formulas XVII, XVIII, and XVIIIb, each R' is independently hydrogen or methyl (in some embodiments, hydrogen, and in some embodiments, methyl), and each Y is independently selected from the group consisting of hydrogen, a counter cation, and an alkyl group. In some embodiments, each Y is independently selected from hydrogen and a counter cation. In some embodiments, each Y is hydrogen. In some embodiments, each Y is a counter cation. Examples of suitable Y counter cations include alkali metal (e.g., sodium, potassium, and lithium), ammonium, mono-, di-, tri- or tetraalkyl ammonium (e.g., tetraalkylammonium), and five to seven membered heterocyclic groups having a positively charged nitrogen atom (e.g, a pyrrolium ion, pyrazolium ion, pyrrolidinium ion, imidazolium ion, triazolium ion, isoxazolium ion, oxazolium ion, thiazolium ion, isothiazolium ion, oxadiazolium ion, oxatriazolium ion, dioxazolium ion, oxathiazolium ion, pyridinium ion, pyridazinium ion, pyrimidinium ion, pyrazinium ion, piperazinium ion, triazinium ion, oxazinium ion, piperidinium ion, oxathiazinium ion, oxadiazinium ion, and morpholinium ion). In some embodiments, Y is alkyl having from 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, or t-butyl). A combination of different third divalent units may be useful. When there is more than one third divalent unit, each R', Z, Y, Q 1 , and V can be independently selected.

In some embodiments, the first divalent units independently represented by Formula X, XIa, or Xlb are present in a range from 10 to 60 (in some embodiments, from 10 to 55, from 15 to 50, from 20 to 50, from 20 to 45, or from 25 to 45) weight percent, based on the total weight of the fluorinated polymer.

In some embodiments, the second divalent unit is present in an amount of at least 30 percent by weight, based on the total weight of the fluorinated polymer. In some embodiments, the second divalent units are present in a range from 30 to 90 (in some embodiments, from 30 to 75, from 30 to 65, or from 35 to 65) weight percent, based on the total weight of the fluorinated polymer. This is advantageous because lower amounts of fluorinated monomers may be used; therefore, the fluorinated polymer may be lower in cost. Even with a relatively low amount of fluorinated carbons in the fluorinated polymer, useful soil resistance can be achieved, as shown in the Examples, below.

In some embodiments, the fluorinated polymer comprises the optional third divalent unit, and the third divalent unit is present in an amount up to 20 percent by weight, based on the total weight of the fluorinated polymer. In some embodiments, the third divalent units are present in a range from 1 to 20 (in some embodiments, from 1 to 15, from 1 to 10, or from 1 to 5) weight percent, based on the total weight of the fluorinated polymer. The combination of the poly(alkyleneoxy) group and the phosphate group aids in the solubility of the fluorinated polymer in aqueous compositions. The presence of the poly(alkyleneoxy) groups in the second divalent unit allows for fewer phosphate groups to be present in the fluorinated polymer to achieve good solubility in aqueous compositions. While the phosphate groups are beneficial for promoting solubility in the aqueous compositions and imparting soil and stain resistance to the composition, phosphate groups can be sensitive to certain cations (e.g., magnesium and calcium) found in the aqueous compositions. For compositions that contain magnesium and calcium ions, for example, the presence of too many phosphate groups can cause precipitation in the aqueous composition.

In some embodiments of fluorinated polymers according to the present disclosure, the first and second divalent groups and optionally third divalent units or any other divalent units present are randomly connected. In some embodiments, the fluorinated polymer according to the present disclosure and/or useful in the compositions according to the present disclosure is represented by formula:

In this formula, Rf, Q, m, EO, R 4 0, p, q, Q 1 , V, Y, R', R 1 , R 2 , and R 3 are as defined above in any of their embodiments, x is in a range from 1 to 100 or more, y is in a range from 1 to 150 or more, and z is in a range from 1 to 50 or more, or x, y, and z are any of the ranges described above for the number of divalent units. It should be understood that the representation of the order of the divalent units in this formula is for convenience only and not meant to specify that the copolymers are block copolymers. Random copolymers having first, second, and third divalent units are also included in the representation. Also, in this formula divalent units of formula XIII, XIV, XV, and XVI may also be used instead of the divalent unit of formula XII. Also, in this formula, divalent units of formula XVII and XVIII may be used instead of the divalent unit of formula XVIIIb.

In some embodiments, the fluorinated polymer according to the present disclosure and/or useful in the compositions according to the present disclosure is represented by formula:

In this formula, Rf, Q, m, EO, R 4 0, p, q, Y, R 1 and R 2 are as defined above in any of their embodiments, x is in a range from 1 to 100 or more and y is in a range from 1 to 150 or more, or x and y are any of the ranges described above for the number of divalent units. It should be understood that the representation of the order of the divalent units in this formula is for convenience only and not meant to specify that the copolymers are block copolymers. Random copolymers having first and second divalent units are also included in the representation. Also, in this formula divalent units of formula XX may also be used instead of the divalent unit of formula XIX.

In some embodiments, fluorinated polymers useful for practicing the present disclosure further comprise at least one (e.g., at least 1, 2, 5, 10, 15, 20, 25, or at least 50) divalent unit represented by Formula XXI:

XXI

wherein each R 6 is independently hydrogen or methyl (in some embodiments, hydrogen, in some embodiments, methyl), and wherein each R 5 is independently alkyl having from 1 to 30 (in some embodiments, 1 to 25, 1 to 20, 1 to 10, 4 to 25, 8 to 25, or 12 to 25) carbon atoms. In some embodiments, each R 5 is independently alkyl having up to 8 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl, iso-butyl, n-pentyl, neopentyl, hexyl, heptyl, or octyl). In some embodiments, R 5 is hexadecyl or octadecyl. In some of these embodiments, the fluorinated polymer is made by including at least one compound represented by formula R 5 -0-C(0)-C(R 6 )=CH 2 in the components to be polymerized.

Compounds of formula R 5 -0-C(0)-C(R 6 )=CH 2 , (e.g., methyl methacrylate, butyl aery late, hexadecyl methacrylate, octadecyl methacrylate, stearyl acrylate, behenyl methacrylate) are available, for example, from several chemical suppliers (e.g., Sigma-Aldrich Company, St. Louis, MO; VWR International, West Chester, PA; Monomer-Polymer & Dajac Labs, Festerville, PA; Avocado Organics, Ward Hill, MA; and Ciba Specialty Chemicals, Basel, Switzerland) or may be synthesized by conventional methods. Some compounds of formula R 5 -0-C(0)-C(R 6 )=CH 2 are available as single isomers (e.g., straight-chain isomer) of single compounds. Other compounds of formula R 5 -0-C(0)-C(R 6 )=CH 2 are available, for example, as mixtures of isomers (e.g., straight-chain and branched isomers), mixtures of compounds (e.g., hexadecyl acrylate and octadecylacrylate), and combinations thereof. In some embodiments, fluorinated polymers useful for practicing the present disclosure are substantially free divalent units represented by formula XXI. "Substantially free" of units of formula XXI can mean free of these divalent unit or having up to 5, 4, 3, 2, 1, or less than 1 percent by weight of these divalent units, based on the total weight of the fluorinated polymer. Units of formula XXI are typically hydrophobic and may compromise the solubility of the fluorinated polymer in water. Fluorinated polymers according to the present disclosure are generally considered to be anionic polymers. In some embodiments, including any of the aforementioned embodiments, fluorinated polymers according to and useful for practicing the present disclosure can be essentially free of cationic and amphoteric divalent units such as those described in U.S. Pat. Appl. Pub. No. 2015/0329766 (Dams et al.). "Essentially free" of cationic and amphoteric divalent units can mean free of these divalent unit or having up to 1, 0.5, 0.1, 0.05, 0.01, or less than 0.01 percent by weight of these divalent units, based on the total weight of the fluorinated polymer.

Fluorinated polymers disclosed herein can be prepared, for example, by polymerizing a mixture of components typically in the presence of an initiator. By the term "polymerizing" it is meant forming a polymer or oligomer that includes at least one identifiable structural element due to each of the components. Typically the polymer that is formed has a distribution of molecular weights and compositions. The polymer may have one of many structures (e.g., a random or graft copolymer or a block copolymer). The components that are useful for preparing the polymers disclosed herein include a fluorinated free-radically polymerizable monomer independently represented by formula

Rf-Q-(C m H 2m )-0-C(0)-C(R 1 )=CH 2 or Rf-S0 2 -N(R)-(CnH2n)-0-C(0)-C(R 1 )=CH 2 , wherein Rf, R 1 , m, and n are as defined above.

Some compounds of Formula Rf-Q-(C m H2m)-0-C(0)-C(R 1 )=CH 2 , are available, for example, from commercial sources (e.g., 3, 3,4,4,5, 5,6,6,6-nonafluorohexyl aery late from Daikin Chemical Sales, Osaka, Japan, 3,3,4,4,5, 5,6,6,6-nonafluorohexyl 2-methylacrylate from Indofine Chemical Co.,

Hillsborough, NJ, lH,lH,2H,2H-perfluorooctylacrylate from ABCR, Karlsruhe, Germany, and

2,2,3,3,4,4,5, 5-octafluoropentyl aery late and methacrylate and 3,3,4,4,5, 6,6,6-octafluoro-5- (trifluoromethyl)hexyl methacrylate from Sigma-Aldrich, St. Louis, MO). Others can be made by known methods (see, e.g., EP1311637 Bl, published April 5, 2006, for the preparation of 2,2,3,3,4,4,4- heptafluorobutyl 2-methylacrylate). Compounds wherein Q is -S0 2 N(R)- can be made according to methods described in, e.g., U.S. Pat. Nos. 2,803,615 (Albrecht et al.) and 6,664,354 (Savu et al.), the disclosures of which, relating to free-radically polymerizable monomers and methods of their preparation, are incorporated herein by reference.

In some embodiments, the components that are useful for preparing the polymers disclosed herein include a poly(alkyleneoxy) acrylate (e.g., monoacrylate, diacrylate, or a mixture thereof). Some alky leneoxy -containing polymerizable compounds are commercially available (e.g., polyoxyalkylene glycol acrylates and diacrylates (e.g., diethylene glycol diacrylate, tri(ethylene glycol) dimethacrylate, tri(ethylene glycol) divinyl ether, and available, for example, from Nippon Oil & Fats Company, Tokyo, Japan under the trade designation "BLEMMER"). Other useful alky leneoxy -containing polymerizable compounds can be prepared by known methods, for example, combining one or two equivalents of acryloyl chloride or acrylic acid with a polyethylene glycol or a monoalkyl ether thereof having a molecular weight of about 200 to 10,000 grams per mole (e.g., those available from Dow Chemical Company, Midland, MI, under the trade designation "CARBOWAX") or a block copolymer of ethylene oxide and propylene oxide having a molecular weight of about 500 to 15000 grams per mole (e.g., those available from BASF Corporation, Ludwigshafen, Germany, under the trade designation "PLURONIC"). The reaction of acrylic acid with a poly(alkylene oxide) is typically carried out in the presence of an acid catalyst and a polymerization inhibitor at an elevated temperature in a suitable solvent; (see, e.g., Example 1 of U. S. Pat. No. 3,787,351 (Olson), the disclosure of which is incorporated herein by reference). In embodiments wherein the fluorinated polymer includes divalent units represented by formula XII or XIII, the alkyleneoxy -containing polymerizable compound can be at least one of HO-(EO) p -(R 4 0) q -(EO) p -C(0)-C(R 2 )=CH 2 or R 3 0-(R 4 0) q -(EO) p -(R 4 0) q -C(0)-C(R 2 )=CH 2 , wherein R 2 , R 3 , R 4 0, EO, p, and q are as defined above In embodiments wherein the fluorinated polymer includes divalent units represented by formula XIV or XV, the alkyleneoxy -containing polymerizable compound can be CH 2 =C(R 2 )-C(0)0-(EO)p-(R 4 0) q -(EO)p-C(0)-C(R 2 )=CH 2 or

CH 2 =C(R 2 )-C(0)0-(R 4 0) q -(EO) p -(R 4 0) q -C(0)-C(R 2 )=CH 2 , wherein R 2 , R 3 , R 4 0, EO, p, and q are as defined above.

Sulfur-terminated polyalkyleneoxy segments can be incorporated into the fluorinated polymers by copolymerization of a difimctional mercaptan, which can react with fluorinated acrylates (e.g.,

Rf-Q-(C m H 2m )-0-C(0)-C(R 1 )=CH 2 or Rf-N(R)-S0 2 -(C I1 H 2n )-0-C(0)-C(R 1 )=CH 2 ) under free-radical polymerization conditions to provide block copolymers. Examples of difimctional mercaptans include HS-C 3 H 2s -C(0)-0-(EO) p -C(0)-C 3 H 2s -SH, HS- C s H 2s -C(0)-0-(EO) p -(R 4 0) q -(EO) p -C(0)-C 3 H 2s -SH, or HS-C 3 H 2s -C(0)-0-(PO) q -(EO) p -(PO) q -C(0)-C 3 H 2s -SH, wherein p, q, EO, and R 4 0 are as defined above for formulas XII and XIII in any of their embodiments and s is an integer from 1 to 5, or in some embodiments, 2 to 3. The resulting polymer or oligomer can then optionally be oxidized using conventional techniques. Difimctional mercaptans can be prepared, for example, by reaction of a diol-functional polyethylene glycol or a block copolymer of ethylene oxide and propylene oxide with, for example, mercaptoacetic acid or mercaptopropionic acid. In other embodiments, polyalkyleneoxy -containing diacrylates can be treated with H 2 S or other sulfhydryl-containing compounds according to the methods of U.S. Pat. No. 3,278,352 (Erickson), incorporated herein by reference, to provide mercaptan-terminated polyalkyleneoxy compounds.

Third divalent units of Formula XVIII and XVIIIb can be incorporated into the fluorinated polymers disclosed herein by copolymerization of a compound of formula

Rf 2 -Q-(C m H 2m )-0-C(0)-C(R 1 )=CH 2 or Rf-S0 2 -N(R)-(C I1 H 2n )-0-C(0)-C(R 1 )=CH 2 with a compound of formula (YO) 2 (0)P-0-V-Q 1 C(0)-C(R')=CH 2 . Useful compounds of these formulas include ethylene glycol methacrylate phosphate and polyethylene glycol methacrylate phosphate. Mono (or di) acryloxyethyl acid phosphate, dimethacryloxyethyl acid phosphate, mono (or di) aery loxy propyl acid phosphate, mono (or di) methacryloxypropyl acid phosphate, and 2-methacryloxyethyl acid phosphate monoethanolamine mono salt may also be useful for incorporating a pendant phosphate group into a polymer. Third divalent units of Formula XVIII can also be incorporated into the fluorinated polymers disclosed herein by copolymerization of a compound of formula Rf 2 -Q-(C m H2m)-0-C(0)-C(R 1 )=CH 2 or Rf-S0 2 -N(R)-(CnH2n)-0-C(0)-C(R 1 )=CH 2 with a compound of formula Z-V-Q 1 C(0)-C(R')=CH 2 , in which Z is -P(0)(OY) 2 . Compounds of formula Z-V-Q^^-CCR^CH,, in which Z is -P(0)(OY) 2 , can be made, for example, from a compound formula HO-V-0-C(0)-C(R')=CH 2 , wherein R' and V are as defined above may be used. A compound formula HO-V-0-C(0)-C(R')=CH 2 can be converted to a thiol- terminated monomer of formula HS-V-0-C(0)-C(R')=CH 2 using conventional functional group transformation. The thiol-terminated monomer can be reacted with allyl phosphonic acid or a salt thereof under free-radical conditions.

Divalent units of Formulas XVII can be incorporated into the fluorinated polymers disclosed herein by copolymerization of a compound of formula Rf 2 -Q-(C m H 2m )-0-C(0)-C(R 1 )=CH 2 or

Rf-S0 2 -N(R)-(C n H 2n )-0-C(0)-C(R 1 )=CH 2 with a compound of formula (YO) 2 (0)P-C(R')=CH 2 , vinyl phosphonic acid.

In some embodiments, when the -0-P(0)(OY) 2 group is on the second divalent unit, a polymer made by copolymerization of a compound of formula Rf 2 -Q-(C m H 2m )-0-C(0)-C(R 1 )=CH 2 or

Rf-S0 2 -N(R)-(C n H 2n )-0-C(0)-C(R 1 )=CH 2 with a poly(alkyleneoxy) acrylate (e.g., monoacrylate, diacrylate, or a mixture thereof) as described in any of the above embodiments can be treated with P 2 0¾, POCI3, or pyrophosphoric acid at elevated temperature using conventional techniques. Alternatively, any of the hydroxyl-terminated monomers useful for making the second divalent units described above in any of their embodiments can be treated with P 2 0¾, POCI3, or pyrophosphoric acid at elevated temperature using conventional techniques to make acrylates and methacrylates including phosphate groups.

Similarly, in some embodiments, when the -P(0)(OY) 2 group is on the second divalent unit, in a polymer made by copolymerization of a compound of formula Rf 2 -Q-(C m H 2m )-0-C(0)-C(R 1 )=CH 2 or Rf-S0 2 -N(R)-(C n H 2n )-0-C(0)-C(R 1 )=CH 2 with a poly(alkyleneoxy) acrylate (e.g., monoacrylate, diacrylate, or a mixture thereof) as described in any of the above embodiments, a terminal hydroxyl group can be converted to a thiol using conventional functional group transformation. The thiol terminated polymer can be reacted with allyl phosphonic acid or a salt thereof under free-radical conditions.

Alternatively, any of the hydroxyl-terminated monomers useful for making the second divalent units described above in any of their embodiments can be converted to thiol-terminated monomers using conventional functional group transformation. The thiol-terminated monomer can be reacted with allyl phosphonic acid or a salt thereof under free-radical conditions.

Fluorinated polymers useful for practicing the present disclosure may also be preparable by adding additional monomers to the polymerization reaction. For example, a compound formula

HO-V-0-C(0)-C(R')=CH 2 , wherein R' and V are as defined above may be used. Examples of these monomers include hydroxyethyl methacrylate. Other examples include vinylidene chloride, vinyl chloride, silicone acrylates available, for example, from Shin-Etsu Silicones of America, Inc., Akron, OH, under the trade designation "X22-2426", and urethane acrylates available, for example, from Sartomer Company, Exton, PA under the trade designation "CN966J75. These units may be incorporated into the compound by selecting additional components for the free-radical reaction such as allyl esters (e.g., allyl acetate and allyl heptanoate); vinyl ethers or allyl ethers (e.g., cetyl vinyl ether, dodecylvinyl ether, 2- chloroethylvinyl ether, or ethylvinyl ether); alpha-beta unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, or alkyl cyanoacrylates); alpha-beta- unsaturated carboxylic acid derivatives (e.g., allyl alcohol, allyl glycolate, acrylamide, methacrylamide, n- diisopropyl acrylamide, or diacetoneacrylamide), styrene and its derivatives (e.g., vinyltoluene, alpha- methylstyrene, or alpha-cyanomethyl styrene); olefinic hydrocarbons which may contain at least one halogen (e.g., ethylene, propylene, isobutene, 3-chloro-l-isobutene, butadiene, isoprene, chloro and dichlorobutadiene, 2,5-dimethyl-l,5-hexadiene, and vinyl and vinylidene chloride); and hydroxyalkyl- substituted polymerizable compounds (e.g., 2-hydroxyethyl methacrylate).

In some embodiments, fluorinated polymers useful for practicing the present disclosure are free of divalent units comprising a pendant silane group and free of silane terminal groups.

The polymerization reaction can be carried out in the presence of an added free-radical initiator. Free radical initiators such as those widely known and used in the art may be used to initiate

polymerization of the components. Exemplary free-radical initiators are described in U. S. Pat. No. 6,664,354 (Savu et al.), the disclosure of which, relating to free-radical initiators, is incorporated herein by reference. In some embodiments, the polymer or oligomer that is formed is a random graft copolymer. In some embodiments, the polymer or oligomer that is formed is a block copolymer.

In some embodiments, the polymerization reaction is carried out in solvent. The components may be present in the reaction medium at any suitable concentration, (e.g., from about 5 percent to about 80 percent by weight based on the total weight of the reaction mixture). Illustrative examples of suitable solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane, cyclohexane), aromatic solvents (e.g., benzene, toluene, xylene), ethers (e.g., diethyl ether, glyme, diglyme, and diisopropyl ether), esters (e.g., ethyl acetate and butyl acetate), alcohols (e.g., ethanol and isopropyl alcohol), ketones (e.g., acetone, methyl ethyl ketone and methyl isobutyl ketone), halogenated solvents (e.g.,

methylchloroform, l,l,2-trichloro-l,2,2-trifluoroethane, trichloroethylene, trifluoro toluene, and hydrofluoroethers available, for example, from 3M Company, St. Paul, MN under the trade designations "HFE-7100" and "HFE-7200"), and mixtures thereof.

Polymerization can be carried out at any temperature suitable for conducting an organic free- radical reaction. Temperature and solvent for a particular use can be selected by those skilled in the art based on considerations such as the solubility of reagents, temperature required for the use of a particular initiator, and desired molecular weight. While it is not practical to enumerate a particular temperature suitable for all initiators and all solvents, generally suitable temperatures are in a range from about 30 °C to about 200 °C (in some embodiments, from about 40 °C to about 100 °C, or from about 50 °C to about 80 °C). Free-radical polymerizations may be carried out in the presence of chain transfer agents. Typical chain transfer agents that may be used in the preparation compositions according to the present invention include hydroxyl-substituted mercaptans (e.g., 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2- propanol, 3-mercapto-l-propanol, and 3-mercapto-l,2-propanediol (i.e., thioglycerol)); poly(ethylene glycol)-substituted mercaptans; carboxy-substituted mercaptans (e.g., mercaptopropionic acid or mercaptoacetic acid): amino-substituted mercaptans (e.g., 2-mercaptoethylamine); difunctional mercaptans (e.g., di(2-mercaptoethyl)sulfide); and aliphatic mercaptans (e.g., octylmercaptan, dodecylmercaptan, and octadecylmercaptan).

Adjusting, for example, the concentration and activity of the initiator, the concentration of each of the reactive monomers, the temperature, the concentration of the chain transfer agent, and the solvent using techniques known in the art can control the molecular weight of a polyacrylate polymer or copolymer.

In some embodiments, fluorinated polymers disclosed herein have weight average molecular weights in a range from 1000 grams per mole to 100,000 grams per mole. In some embodiments, the weight average molecular weight is at least 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or 10000 grams per mole up to 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, or up to 90,000 grams per mole. Fluorinated polymers disclosed herein typically have a distribution of molecular weights and compositions. Weight average molecular weights can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using techniques known to one of skill in the art.

In some embodiments, the fluorinated polymer according to the present disclosure is substantially free of volatile organic solvent. "Substantially free of volatile organic solvent" can mean that volatile organic solvent may be present (e.g., from synthesis of the fluorinated polymer, a previous synthetic step, or in a commercially available monomer) in an amount of up to 2.5 (in some embodiments, up to 2, 1, 0.5, 0.1, 0.05, or 0.01) percent by weight, based on the total weight of the composition. "Substantially free of volatile organic solvent can also mean free of volatile organic solvent. Volatile organic solvents are typically those have a boiling point of up to 150 °C at atmospheric pressure. A volatile organic solvent can be a volatile organic compound (VOC) as defined in the California Consumer Products Regulations, Subchapter 8.5, Article 2, 94508, last amended September 17, 2014 (Register 2014, No. 38). A person skilled in the art may understand a volatile organic solvent as a solvent not listed as "exempt" or otherwise excluded in the California Consumer Products Regulations, Subchapter 8.5, Article 2, 94508, last amended September 17, 2014 (Register 2014, No. 38). VOCs (e.g., those not listed as exempt or otherwise excluded) include hydrocarbon solvents (e.g., benzene, toluene, xylenes, and d-limonene); acyclic and cyclic ketones (e.g., pentanone, hexanone, cyclopentanone, and cyclohexanone); acyclic or cyclic acetals, ketals or ortho esters (e.g., diethoxy methane, dimethoxy methane, dipropoxy methane, dimethoxy ethane, diethoxy ethane, dipropoxy ethane, 2,2-dimethoxy propane, 2,2-diethoxy propane, 2,2- dipropoxy propane, 2,2-dimethyl-l,3-dioxalane, trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthobenzoate, and triethyl orthobenzoate); and alcoholic solvents (e.g., methanol, ethanol, or propanol such as isopropanol). If volatile organic solvent is used in the preparation of the fluorinated polymer or a starting monomer for the fluorinated polymer, it can typically be removed by vacuum distillation .

Compositions according to the present disclosure that include the fluorinated polymer disclosed herein according to any of the above embodiments can also include at least one polymeric material, typically a film-forming polymer. Examples of suitable polymers include acrylic polymers, (e.g., poly(methyl methacry late-co-ethyl acrylate) or poly(methyl aery late-co-acrylic acid)); polyurethane s, (e.g., reaction products of aliphatic, cycloaliphatic or aromatic diisocyanates with polyester glycols or polyether glycols); polyolefins, (e.g., polystyrene); copolymers of styrene with acrylate(s) (e.g., poly(styrene-co-butyl acrylate); polyesters, (e.g, polyethylene terephthalate, polyethylene terephthalate isophthalate, or polycaprolactone); polyamides, (e.g., polyhexamethylene adipamide); vinyl polymers, (e.g., poly(vinyl acetate/methyl acrylate), poly(vinylidene chloride/vinyl acetate); polydienes, (e.g., poly(butadiene/styrene)); poly(vinylidene fluoride); epoxies; polyester-epoxies; cellulosic derivatives including cellulose ethers and cellulose esters, (e.g., ethyl cellulose, or cellulose acetate/butyrate), urethane-acrylate copolymers, and combinations thereof. In some embodiments, the non-fluorinated polymer is at least one of an acrylic polymer, a polyurethane, a polystyrene, or a styrene-acrylate copolymer. In some embodiments, the film-forming polymer comprises at least one of an acrylate, methacrylate, vinyl, styrene, methyl styrene, or acrylonitrile. In some embodiments, the film-forming polymer comprises at least one of an acrylate, methacrylate, or acrylonitrile.

Compositions including such film-forming polymers may be useful, for example, as paints and coatings.

In some embodiments, compositions according to the present disclosure that include a film- forming polymer further include water. Methods and materials for preparing aqueous emulsions or latexes of any of the film-forming polymers described above are known, and many of such waterborne formulations are available from commercial sources. In some embodiments, in the composition that includes the fluorinated polymer according to present disclosure and a film-forming polymer, the film- forming polymer is selected from the group consisting of an acrylic polymer, a polyurethane, polystyrene, and a copolymer of styrene and at least one acrylate.

Waterborne compositions according to the present disclosure may also contain one or more cosolvents (e.g., coalescing solvents) including ethers of polyhydric alcohols (e.g., ethylene glycol monomethyl (or monoethyl) ether, diethylene glycol methyl (or ethyl or butyl) ether, triethylene glycol monomethyl (or monoethyl) ether, 2-butoxyethanol (i.e., butyl cellusolve), or di(propylene glycol) methyl ether (DPM)); alkylene glycols and polyalkylene glycols (e.g., ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, diethylene glycol, polyethylene glycol,

polypropylene glycol); 2-phenoxyethanol, dibutylphthalate, and 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate (an ester alcohol available from Eastman Chemical Company, Kingsport, TN, under the trade designation "TEXANOL"). Other water-miscible organic solvents that may be added to the composition include alcohols having 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol, or isobutanol); amides and lactams, (e.g., Ν,Ν-dimethylformamide, N,N-dimethylacetamide, or N- methylpyrrolidone); ketones and ketoalcohols (e.g., acetone, cyclohexanone, methyl isobutyl ketone, diacetone alcohol); ethers (e.g., tetrahydrofuran, dimethoxyethane, and dioxane); esters (e.g., methyl acetate); propylene carbonate; dimethylsulfoxide; sulfolane; l,3-dimethyl-2-imidazolidinone; and combinations thereof.

Coalescing solvent is preferably utilized at a level between about 12 to 60 grams (e.g., about 40 grams) of coalescing solvent per liter of the aqueous composition or at about 20 to 30 weight percent based on the weight of the polymer solids in the aqueous composition. However, in some embodiments, the composition is substantially free of VOCs as described above, and/or no coalescing solvent is used in the formulation.

In some embodiments, the composition according to the present disclosure further comprises at least one pigment, including either natural or synthetic pigments. Examples of useful pigments include various clays (e.g., natural or calcined clays), calcium carbonate (e.g., natural or precipitated calcium carbonate), mica, silicas (e.g., natural or synthetic pyrogenic silicas), talcs, engineered molecules, blanc fixe, lithopone, zinc sulfide, lead titanate, antimony oxide, zirconium oxide, leaded zinc oxide, titanium dioxide (e.g., rutile or anatase), carbon black, phthalo blue, hansa yellow, red iron oxide, brown oxide, ochres, umbers, and combinations of any of these.

In some embodiments, the composition according to the present disclosure further comprises at least one inorganic filler. Examples of useful inorganic fillers include diatomaceous earth, talc, lime, barytes, clay, sand, nepheline syenite, and ceramic microspheres (e.g., solid beads or glass bubbles). In some embodiments, the inorganic filler includes titanium dioxide, carbon black, calcium carbonate, nepheline syenite, ceramic microspheres, and combinations thereof. Examples of commercially available ceramic microspheres include glass bubbles marketed by 3M Company, Saint Paul, Minnesota, as "3M

GLASS BUBBLES" in grades Kl, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S60, and S60HS; ceramic microspheres marketed by 3M Company under the trade designation "3M CERAMIC MICROSPHERES" (e.g., grades W-610 and W-410); silica-alumina ceramic hollow spheres with thick walls marketed by Valentine Chemicals of Lockport, Louisiana, as "ZEEOSPHERES CERAMIC MICROSPHERES" in grades G-200, G200-PC, G-400, G600, G-800, G-850,N-200, N-200PC, N-400, N-600, N-800, N1000, and N1200; solid glass spheres available from Cospheric LLC, Santa Barbara, California as "SODA LIME SOLID GLASS MICROSPHERES", "BOROSILICATE SOLID GLASS MICROSPHERES", "BARIUM TITANATE GLASS SPHERES", and "E GLASS SPHERES".

In compositions according to the present disclosure, including paints and coatings, inorganic fillers and pigment particles may be present in a variety of useful amounts. For example, the filler and pigment particles combined may provide in a range from 20 percent to 80 percent by weight of the paint or coating composition, based on the total weight of the composition. In some embodiments, the filler and pigment particles combined may provide in a range from 25 percent to 55 percent or 30 percent to 50 percent by weight of the paint or coating composition.

Depending on the application, compositions according to the present disclosure may also include biocides (e.g., fungicides or mildewcides), surfactants (e.g., for improved wetting or leveling), emulsifiers, defoamers, pH adjuster, anticorrosive agents, dispersants, rust inhibitors, thickeners (i.e., that may be polymeric or inorganic), UV absorbers, fireproofing agents, or any combination of these. Other additives may also be useful. 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). In some embodiments, compositions according to the present disclosure are neutral to alkaline. In some embodiments, a pH adjuster is added to provide the composition with a pH of at least 7, in some embodiments, a pH of 7 to 9.

It can be useful for latex paints and other coating compositions to contain thickeners to modify the rheological properties of the composition to ensure good spreading, handling, and application characteristics. The thickener may be an associative thickener. Examples of useful associative thickeners include hydrophobically modified alkali swellable acrylic copolymers and hydrophobically modified urethane copolymers. Representative examples of commercially available associative thickeners include polyacrylic acids (available, for example, from Rohm & Haas Co., Philadelphia, Pa., under the trade designations "ACRYSOL RM-825" and "QR-708 Rheology Modifier") and activated attapulgite (available from Engelhard, Iselin, N.J., under the trade designation "ATTAGEL 40"). A thickener such as magnesium aluminum silicate, sold by R.T. Vanderbilt Co., Norwalk, CT, under the trade designation "VEEGUM T" is another suitable thickening agent that may be used at 0.3 to about 0.6 % by weight, based on the total weight of the composition. Other representative commercially available water thickeners include xanthan gums (e.g., available from CP Kelco, Houston, TX, under the trade designation "KELZAN" and from R. T. Vanderbilt Co. under the trade designation "VANZAN"); diutan gums (e.g., available from CP Kelco under the trade designation "GEOVIS XT"); gellan gums (e.g., available from CP Kelco under the trade designation "KELCOGEL"); carrageenan gums (e.g., available from CP Kelco under the trade designation "GENUVISCO X-906-02") and hydrocolloids (e.g., available from Noveon, Inc. under the trade designation "NOVEGUM C865").

Typically, in compositions according to the present disclosure, the fluorinated polymer is present in the composition at at least 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.075, 0.08, 0.085, 0.09, 0.095, 0.1, 0.15, 0.2, 0.25, 0.5, 1, 1.5, 2, 3, 4, or 5 percent by weight, up to 5, 6, 7, 8, 9, or 10 percent by weight, based on the total weight of the treatment composition. For example, the amount of the fluorinated polymer in the compositions may be in a range of from 0.01 to 10, 0.1 to 10, 0.1 to 5, 1 to 10, 0.5 to 2, 1 to 5, 0.001 to 1, 0.001 to 0.5, or 0.01 to 0.3 percent by weight, based on the total weight of the composition. Lower and higher amounts of the fluorinated polymer in the compositions may also be used, and may be desirable for some applications.

The components of the compositions described herein including fluorinated polymers can be combined using techniques known in the art for combining these types of materials, including using conventional magnetic stir bars or mechanical mixer (e.g., in-line static mixer and recirculating pump).

Latex paint compositions can be prepared using conventional techniques. For example, some of the paint ingredients are generally blended together under high shear to form a mixture commonly referred to as "the grind" by paint formulators. The consistency of this mixture is comparable to that of mud, which is desirable in order to efficiently disperse the ingredients with a high shear stirrer. During the preparation of the grind, high shear energy is used to break apart agglomerated pigment particles.

The ingredients not included in the grind are commonly referred to as "the letdown". The letdown is usually much less viscous than the grind, and is usually used to dilute the grind to obtain a final paint with the proper consistency. The final mixing of the grind with the letdown is typically carried out with low shear mixing. Paints are generally prepared by adding the latex polymer in the letdown.

When a waterborne composition is applied to a substrate, water and any solvent present evaporate, and the polymer particles coalesce to form a continuous film. Waterborne compositions according to the present disclosure are typically applied, dried, and optionally heated, leaving the finished product with a solid coating. They may be applied by a variety of useful methods (e.g., brushing, mopping, bar coating, spraying, dip coating, gravure coating, or roll coating).

In some embodiments, the composition is allowed to dry on the substrate surface at a temperature in a range from about 10 °C (50 °F) to about 40 °C (100 °F) and a humidity in a range from about 20% to about 90% relative humidity. Drying conditions may be selected such that at least some of the fluorinated polymer can migrate to the surface of the coating as it dries so that the resulting dried coating has a fluorine-enriched surface.

Compositions that may be improved by the addition of the fluorinated polymer according to the present disclosure include architectural paint (e.g., for indoor or outdoor applications), floor polishes and finishes, varnishes for a variety of substrates (e.g., wood floors), waterborne gels applied in the manufacture of photographic film, automotive or marine coatings (e.g., primers, base coats, or topcoats), sealers for porous substrates (e.g., wood, concrete, or natural stone), hard coats for plastic lenses, coatings for metallic substrates (e.g., cans, coils, electronic components, or signage), inks (e.g, for pens or gravure, screen, or thermal printing), and coatings used in the manufacture of electronic devices (e.g., photoresist inks). In some embodiments, the composition according to the present disclosure is an architectural paint composition.

As shown in the Examples, below, the fluorinated polymers according to the present disclosure provide excellent soil and stain resistance. In some embodiments, cleanability of a paint composition including the fluorinated polymer of the present disclosure is better than the cleanability of a paint composition including a fluorinated polymer having the first and second divalent units but having no pendant phosphate group. Furthermore, fluorinated polymers including first and third divalent units but having no second divalent units did not mix well into the paint composition.

Some Embodiments of the Disclosure

In a first embodiment, the present disclosure provides a fluorinated polymer comprising:

a first divalent unit represented by formula:

wherein

Rf represents a fluoroalkyl group having from 1 to 8 carbon atoms;

R 1 is hydrogen or methyl;

Q is a bond or -S02-N(R)-, wherein R is alkyl having from 1 to 4 carbon atoms; and m is an integer from 1 to 11,

a second divalent unit comprising a poly (alky leneoxy) group; and

at least one of a pendant phosphate group or a pendant phosphonate group.

In a second embodiment, the present disclosure provides the fluorinated polymer of the first embodiment, wherein the phosphate group is represented by formula -0-P(0)(OY)2, wherein the phosphonate group is represented by formula -P(0)(OY)2, and wherein each Y is independently hydrogen or a counter cation.

In a third embodiment, the present disclosure provides the fluorinated polymer of the first or second embodiment, wherein the second divalent unit is present in an amount of at least 30 by weight, based on the total weight of the fluorinated polymer.

In a fourth embodiment, the present disclosure provides the fluorinated polymer of any one of the first to third embodiments, wherein at least one of the second divalent units is represented by formula:

wherein R 2 is hydrogen or methyl;

R 3 is alkyl having up to 4 carbon atoms, -0-P(0)(OY)2, or hydrogen;

each Y is independently selected from the group consisting of hydrogen and a counter cation;

EO represents -CH 2 CH 2 0-;

each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0-, -CH2CH2CH2O-, -CH 2 CH(CH 3 )0-, -CH2CH2CH2CH2O-, -CH(CH2CH 3 )CH 2 0-, -CH2CH(CH 2 CH 3 )0-, and -CH 2 C(CH 3 ) 2 0-;

each p is independently a value from 0 to 150; and

each q is independently a value from 0 to 150 , wherein p+q is at least 5;

and wherein the fluorinated polymer may further comprise at least one third divalent unit represented by formula:

YO— P=0

I

OY ; or

wherein

Q 1 is selected from the group consisting of -0-, -S-, and -N(R 7 )-;

each R 7 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;

each R' is independently hydrogen or methyl;

V is alkylene that is optionally interrupted by at least one ether linkage, thioether linkage, or amine linkage;

Z is -P(0)(OY) 2 or -0-P(0)(OY) 2 ; and

each Y is independently selected from the group consisting of hydrogen and a counter cation,

with the proviso that when R 3 is -0-P(0)(OY)2, the third divalent unit may be present or may be not present, and with the further proviso that when R 3 is alkyl having up to 4 carbon atoms or hydrogen, the third divalent unit is present. In a fifth embodiment, the present disclosure provides the fluorinated polymer according to the fourth embodiment, wherein the fluorinated polymer comprises the third divalent unit, and wherein the third divalent unit is present in an amount up to 20 percent by weight, based on the total weight of the fluorinated polymer.

In a sixth embodiment, the present disclosure provides the fluorinated polymer of any one of the first to fifth embodiments, wherein the first divalent unit is present in an amount up to 60 percent by weight, based on the total weight of the fluorinated polymer.

In a seventh embodiment, the present disclosure provides the fluorinated polymer of any one of the first to sixth embodiments, further comprising a third divalent unit represented by formula:

YO— P=0

I

OY ; or

wherein

Q 1 is selected from the group consisting of -0-, -S-, and -N(R 7 )-;

R 7 is selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;

R' is hydrogen or methyl;

V is alkylene that is optionally interrupted by at least one ether linkage, thioether linkage, or amine linkage;

Z is -P(0)(OY) 2 or -0-P(0)(OY) 2 ; and

each Y is independently hydrogen or a counter cation.

In an eighth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to seventh embodiments, wherein at least one of the second divalent units or third divalent units is represented by formula:

wherein

R 2 is independently hydrogen or methyl;

EO represents -CH 2 CH 2 0-;

each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0- -CH2CH2CH2O- -CH 2 CH(CH 3 )0-, -CH2CH2CH2CH2O-, -CH(CH 2 CH3)CH 2 0- -CH 2 CH(CH 2 CH3)0- and -CH 2 C(CH 3 )20-;

each p is independently a value from 0 to 150;

each q is independently a value from 0 to 150, wherein p+q is at least 5; and each Y is independently hydrogen or a counter cation.

In a ninth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to eighth embodiments, wherein Q is -S0 2 N(R)- and R is methyl or ethyl.

In a tenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to ninth embodiments, wherein Rf represents a fluoroalkyl group having up to 4 carbon atoms.

In an eleventh embodiment, the present disclosure provides the method according to any one of the first to tenth embodiments, wherein at least one of the second divalent units is represented by formula:

wherein

each R 2 is independently hydrogen or methyl; each R 3 is independently alkyl having up to 4 carbon atoms or hydrogen;

EO represents -CH 2 CH 2 0-;

each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0- -CH2CH2CH2O- -CH 2 CH(CH 3 )0- -CH2CH2CH2CH2O-, -CH(CH 2 CH3)CH 2 0- -CH 2 CH(CH 2 CH3)0- and -CH 2 C(CH 3 )20-;

each p is independently a value from 0 to 150; and

each q is independently a value from 0 to 150 , wherein p+q is at least 5.

In a twelfth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to eleventh embodiments, wherein at least one of the second divalent unit is represented by formula:

wherein

each R 2 is independently hydrogen or methyl;

EO represents -CH 2 CH 2 0-;

each R 4 0 is independently selected from the group consisting of -CH(CH 3 )CH 2 0-, -CH2CH2CH2O-, -CH 2 CH(CH 3 )0- -CH2CH2CH2CH20-,-CH(CH2CH 3 )CH 2 0-, -CH 2 CH(CH 2 CH 3 )0-, and

-CH 2 C(CH 3 ) 2 0-;

each r is independently a value from 0 to 150; and

each q is independently a value from 0 tol50 , wherein p+q is at least 150.

In a thirteenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to eleventh embodiments, wherein the second divalent unit comprises a pendant poly(alkyleneoxy) group.

In a fourteenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to thirteenth embodiments, wherein the fluorinated polymer further comprises at least one divalent unit represented by formula:

wherein

each R 5 is independently alkyl having from 1 to 30 carbon atoms; and

each R 6 is independently hydrogen or methyl.

In a fifteenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to thirteenth embodiments, wherein the fluorinated polymer is substantially free of divalent units represented by formula:

wherein

each R 5 is independently alkyl having from 1 to 30 carbon atoms; and

each R 6 is independently hydrogen or methyl.

In a sixteenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to fifteenth embodiments, wherein the fluorinated polymer is substantially free of divalent units represented by formula:

wherein

Q 1 is selected from the group consisting of -0-, -S-, and -N(R 7 )-;

each R 7 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 4 carbon atoms;

each R' is independently hydrogen or methyl;

V is alkylene that is optionally interrupted by at least one ether linkage or amine linkage; and

Z 1 is selected from the group consisting of -[N(R 8 ) 3 ] + M ~ , -N + (R 8 )2-(CH 2 )g-S0 3 Y 1 , and -N + (R 8 )2-(CH 2 )g-C0 2 Y 1 ,wherein each R 8 is independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms;

each g is independently an integer from 2 to 6;

M " is a counter anion; and

Y 1 is selected from the group consisting of hydrogen and a free anion.

In a seventeenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to sixteenth embodiments, wherein the fluorinated polymer is free of divalent units comprising a pendant silane group and free of silane terminal groups.

In an eighteenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to seventeenth embodiments, wherein the fluorinated polymer is free of pendent amino groups.

In a nineteenth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to eighteenth embodiments, wherein the fluorinated polymer is substantially free of volatile organic solvent.

In a twentieth embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to nineteenth embodiments, wherein the fluorinated polymer is a polymer having a weight average molecular weight in a range from 1,000 grams per mole to 100,000 grams per mole.

In a twenty -first embodiment, the present disclosure provides the fluorinated polymer according to any one of the first to twentieth embodiments, used in a paint composition.

In a twenty-second embodiment, the present disclosure provides a composition comprising a film- forming polymer and the fluorinated polymer according to any one of the first to twenty -first embodiments.

In a twenty -third embodiment, the present disclosure provides the composition according to the twenty -second embodiment, further comprising a pigment.

In a twenty -fourth embodiment, the present disclosure provides the composition according to the twenty -second or twenty -third embodiment, further comprising an inorganic filler.

In a twenty -fifth embodiment, the present disclosure provides the composition according to any one of the twenty-second to twenty -fourth embodiments, further comprising a thickener.

In a twenty-sixth embodiment, the present disclosure provides the composition according to any one of the twenty-second to twenty -fifth embodiments, further comprising water.

In a twenty -seventh embodiment, the present disclosure provides the composition according to any one of the twenty-second to twenty-sixth embodiments, having a pH of at least 7.

In a twenty-eighth embodiment, the present disclosure provides the composition according to the twenty -seventh embodiment, having a pH of 7 to 9.

Embodiments of the methods disclosed herein are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight. EXAMPLES

In the following Examples, MeFBSEA was prepared according to the method of U.S. Pat. No. 6,664,354 (Savu), Example 2, Parts A and B, incorporated herein by reference, except using 4270 kilograms (kg) of N-methylperfluorobutanesulfonamidoethanol, 1.6 kg of phenothiazine, 2.7 kg of methoxyhydroquinone, 1590 kg of heptane, 1030 kg of acrylic acid, 89 kg of methanesulfonic acid (instead of triflic acid), and 7590 kg of water in Part B.

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, h = hours, d = days, °C = degrees Celsius, μιη = micrometers, mm = millimeters, mil = thousandths of an inch, cm = centimeters, in = inches, mL = milliLiters, kg = kilograms, lbs = pounds, Pa = pascal, rpm = revolutions per minute.

Materials

3-mercapto-l,2-propanediol Thioglycerol, available from Evans Chemetics

LP, Waterloo, NY, USA

VAZO 67 2,2'-azobis(2-methylbutyronitrile), available under the trade designation "VAZO-67" from E. I. DuPont de Nemours & Co., Wilmington, DE

Phosphorous pentoxide Available from Sigma- Aldrich Company

Water De-ionized water

IPA 2-propanol, 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

ΜΓΝΕΧ 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 4 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 preparing paint formulation

The paint formulation used to evaluate dirt pick up resistance and washability performance was prepared by first mixing the components listed in Table 2, below, in the order shown, through

DURAMITE, in a vessel, and mixing them under high speed agitation using a Dispermat D-51580 and a 1.5" (38.1 mm) cowles blade for 20 min at 4000 rpm. The grind was checked using a Hegman gauge, and the considered complete when a minimum 4 rating was obtained. The paste was then added to the pre- mixed letdown (Acronal Plus 4130 and water). After thorough mixing, the last ingredient was added slowly, with agitation of the mixture.

Table 2: Paint formulation

Method for determining Dirt Pick-up Resistance (DPUR)

Examples were dissolved in the paint formulation described above at a concentration of 0.2% active material based on total paint weight, with the Exception of Comparative Example 3 (CE-3), for which no additive was added to the paint formulation. 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, Inc., Mahwah, NJ, USA were coated on one side using a 7 mil (0.18 mm) U-shaped 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 Rimt- The painted sides of the samples were covered with SPS-2001 for 24 h. After 24 h, the samples were tapped to displace SPS-2001 and reflectance of the painted sides was again recorded as Rfmai- The ratio Rfmai / Rimt was calculated for each sample. The results, presented in Table 5, below, represent means for triplicate measurements.

Method for determining Washability

Examples were dissolved in the paint formulation described above at a concentration of 0.2% active material based on total paint weight, with the Exception of Comparative Example 3 (CE-3), for which no additive was added to the paint formulation. 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 and applied with a foam brush

· 25 cycles were used

• 2.5 g water was placed on the sponge path

• 750 g total weight used

• Reported values in Table 6, below, are means for triplicate determinations Comparative Example 1 (CE-1)

To prepare CE-1, 38 g of N-MeFBSEA and 124 g of PLURONIC L-44 acrylate (50% in toluene) were copolymerized with 5.0 g 3-mercapto-l,2-propanediol, with 4.0 g "VAZO 67" in a three-necked flask. The mixture was degassed three times using vacuum and nitrogen pressure and then heated to 65 °C for 6 h. After polymerization, toluene was removed using an aspirator vacuum at 65-70 °C at approximately 20 mmHg (2.7 kPa).

Comparative Example 2 (CE-2)

To prepare CE-2, 19 g of N-MeFBSEA and 62 g of PLURONIC L-44 acrylate (50% in toluene) were copolymerized with 2.5 g 3-mercapto-l,2-propanediol and 2.0 g "VAZO 67" in a three necked flask. The mixture was degassed three times using vacuum and nitrogen pressure and then heated to 65 °C for 6 h. After polymerization, toluene was removed using an aspirator vacuum at 60 - 70 °C at approximately 40 mmHg (5.3 kPa) . The polymer was then neutralized with NH 4 OH, however, the neutralized polymer was barely soluble in water. The un-neutralized polymer was not soluble in water.

Examples 1 - 12 (EX-1 through EX- 12)

EX-1 through EX-12 were prepared according to the process described for CE-1, except that in place of 3-mercapto-l,2-propanediol, PAM-200, Ethylene glycol phosphate methacrylate, or a combination of PAM-200 and Ethylene glycol phosphate methacrylate was used. The amounts of N- MeFBSEA, PLURONIC L-44 acrylate, PAM-200 and Ethylene glycol phosphate methacrylate used for each Example 1 - 12 are provided in Table 3.

Table 3

Examples 13 - 15 (EX- 13 through EX- 15)

For EX-13 through EX-15, the procedure described for CE-1 was followed, except that Poly (ethylene glycol) methyl ether MA, PAM-200 and IPA were used in place of PLURONIC L-44 acrylate. The amounts of N-MeFBSEA, Poly (ethylene glycol) methyl ether MA, PAM-200, 3-mercapto- 1,2-propanediol, and IPA used for each Example 13 - 15 are provided in Table 4.

Table 4

Example 16 (EX- 16)

For EX- 16, in a flask equipped with stirring, to 25 g of the above described CE-1 was added 0.6 g of phosphorus pentoxide at 100 °C in two portions over 30 min. After the addition, the mixture was stirred at 100 °C for an additional 2 h. Then, 1.0 g NH40H (30% solution) and 75 g DI water was added to the reaction with stirring, resulting in a clear solution. The % active solid was measured as 26%.

Table 5. Surface Tension Results of Sam les in DI water d ne/cm

NM = Not Measured

Table 6. Oily stain washability and DPUR results.

NM = Not Measured Various modifications and alterations of this disclosure may be made by those skilled the art without departing from the scope and spirit of the disclosure, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth herein.