Polymerizable compounds with one or more surfactant-like properties

Abstract

Some embodiments of the present disclosure relate to polymerizable compounds that comprise biocidal activity and/or the potential for increased biocidal activity and that comprise at least one hydrophobic portion and at least one hydrophilic portion. Together the hydrophobic portion and the hydrophilic portion of the compounds may provide the polymerizable compounds with one or more surfactant-like properties. The polymerizable compounds can be incorporated into polymer coating formulations. The polymer coating formulations can be used to coat one or more surfaces of a substrate. The coating formulation can provide biocidal activity and/or the potential for increased biocidal activity to the coated substrate-surface.

Claims

1. A compound which is: ##STR00031##

2. A compound of a formula selected from a group consisting of: ##STR00032## ##STR00033##

3. The compound according to claim 2, wherein the compound is of Formula 6: ##STR00034##

4. The compound according to claim 2, wherein the compound is of Formula 7: ##STR00035##

5. The compound according to claim 2, wherein the compound is of Formula 9: ##STR00036##

6. The compound according to claim 2, wherein the compound is of Formula 13: ##STR00037##

7. The compound according to claim 2, wherein the compound is of Formula 14: ##STR00038##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) These and other features of the present disclosure will become more apparent in the following detailed description in which reference is made to the appended drawings, wherein:

(2) FIG. 1 is an example of experimental data obtained from an energy dispersive X-ray spectroscopy (EDX) system that analyzed an F3 control latex-formulation that was not exposed to one or more further agents;

(3) FIG. 2 is an example of experimental data obtained from an EDX system that analyzed an F3 control latex-formulation that was exposed to one or more further agents;

(4) FIG. 3 is an example of experimental data obtained from an EDX system that analyzed an F3-C3-MMAcryl-4.6% latex-coating variant that was not chlorinated;

(5) FIG. 4 is an example of experimental data obtained from an EDX system that analyzed an F3-C3-MMAcryl-4.6% latex-coating variant that was chlorinated;

(6) FIG. 5 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(7) FIG. 6 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(8) FIG. 7 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(9) FIG. 8 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(10) FIG. 9 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(11) FIG. 10 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(12) FIG. 11 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(13) FIG. 12 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(14) FIG. 13 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(15) FIG. 14 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(16) FIG. 15 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(17) FIG. 16 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(18) FIG. 17 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(19) FIG. 18 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(20) FIG. 19 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(21) FIG. 20 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(22) FIG. 21 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(23) FIG. 22 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(24) FIG. 23 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(25) FIG. 24 is an example of a synthesis pathway for making a compound according to embodiments of the present disclosure;

(26) FIG. 25 shows photographs of a polyurethane-based coating during humidity resistance testing, wherein FIG. 25A shows the coating at day 7; FIG. 25B shows the coating at day 29; and, FIG. 25C shows the coating at day 50;

(27) FIG. 26 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 26A shows the coating at day 7; FIG. 26B shows the coating at day 14; and, FIG. 26C shows the coating at day 26;

(28) FIG. 27 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 27A shows the coating at day 7; FIG. 27B shows the coating at day 14; and, FIG. 27C shows the coating at day 26;

(29) FIG. 28 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 28A shows the coating at day 3; and, FIG. 28B shows the coating at day 13;

(30) FIG. 26 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 26A shows the coating at day 7; FIG. 26B shows the coating at day 14; and, FIG. 26C shows the coating at day 26;

(31) FIG. 29 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 29A shows the coating at day 3; and, FIG. 29B shows the coating at day 13;

(32) FIG. 30 shows a photograph of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing at day 6;

(33) FIG. 31 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 31A shows the coating at day 3; and, FIG. 31B shows the coating at day 13;

(34) FIG. 32 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 32A shows the coating at day 3; and, FIG. 32B shows the coating at day 13;

(35) FIG. 33 shows photographs of a polyurethane-based coating according to embodiments of the present disclosure during humidity resistance testing, wherein FIG. 33A shows the coating at day 3; and, FIG. 33B shows the coating at day 13;

(36) FIG. 34 shows photographs of the coating of FIG. 25 during ultraviolet resistance testing, wherein FIG. 34A shows the coating at day 7; and, FIG. 34B shows the coating at day 29;

(37) FIG. 35 shows photographs of the coating of FIG. 26 during ultraviolet resistance testing, wherein FIG. 35A shows the coating at day 7; FIG. 35B shows the coating at day 14; and, FIG. 35C shows the coating at day 26;

(38) FIG. 36 shows photographs of the coating of FIG. 27 during ultraviolet resistance testing, wherein FIG. 36A shows the coating at day 7; FIG. 35B shows the coating at day 14; and, FIG. 35C shows the coating at day 26;

(39) FIG. 37 shows photographs of the coating of FIG. 28 during ultraviolet resistance testing, wherein FIG. 36A shows the coating at day 3; and, FIG. 37B shows the coating at day 13;

(40) FIG. 38 shows photographs of the coating of FIG. 29 during ultraviolet resistance testing, wherein FIG. 36A shows the coating at day 3; and, FIG. 37B shows the coating at day 13;

(41) FIG. 39 shows photographs of the coating of FIG. 30 during ultraviolet resistance testing at day 6;

(42) FIG. 40 shows photographs of the coating of FIG. 31 during ultraviolet resistance testing, wherein FIG. 40A shows the coating at day 3; and, FIG. 40B shows the coating at day 13;

(43) FIG. 41 shows photographs of the coating of FIG. 32 during ultraviolet resistance testing, wherein FIG. 41A shows the coating at day 3; and, FIG. 41B shows the coating at day 13;

(44) FIG. 42 shows photographs of the coating of FIG. 33 during ultraviolet resistance testing, wherein FIG. 42A shows the coating at day 3; and, FIG. 42B shows the coating at day 13; and

(45) FIG. 43 shows a first vial that contains a latex emulsion (control) and a second vial that shows a latex emulsion that includes a polymerizable compound with surfactant-like properties according to an embodiment of the present disclosure.

DETAILED DESCRIPTION

(46) Embodiments of the present disclosure relate to compounds that have two or more functional groups, where the functional groups may be selected from a group consisting of at least one N-halamine precursor, at least one cationic center, at least one coating incorporation group (CIG), at least one lipophilic moiety or combinations thereof. The compounds may have biocidal activity and the compounds may subsequently be chemically modified to enhance or provide biocidal activity. The chemical modification may be performed in situ and repeated once or multiple times to extend the time-frame over which the compounds have the desired biocidal activity. The functional groups may be physically separated from one another by other atoms within the compound and this physical separation may provide a desired compound-stability and influence the compound's biocidal activity.

(47) Some embodiments of the present disclosure relate to polymerizable compounds that comprise at least one N-halamine precursor, at least one cationic center, at least one CIG and at least one lipophilic moiety. The polymerizable compounds may generally comprise at least one hydrophobic portion and at least one hydrophilic portion. The hydrophobic portion can also be referred to as a non-polar portion or a lipophilic portion. The hydrophilic portion can also be referred to as a polar portion or a lipophobic portion. Together the hydrophobic portion and the hydrophilic portion of the compounds may provide the compounds with one or more surfactant-like properties.

(48) The at least one CIG may incorporate the compound into a coating or the at least one CIG may incorporate the coating onto a surface of a substrate, or the CIG may perform both functions. For example, the CIG may link or cure or tether or polymerize the polymerizable compound. The CIG may allow the polymerizable compound to be incorporated into a polymer, including incorporation into a polymer backbone, within various different polymers by different synthesis methods. The different polymers may be synthesized through various synthesis methods, including but not limited to: condensation polymerization; addition polymerization; step-growth polymerization; radical polymerization; chain-growth polymerization; latex emulsion polymer synthesis or any combination of these or other polymerization methods through concurrent or subsequent polymer processing or polymerization processes.

Definitions

(49) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

(50) As used herein, the term “about” refers to an approximately +/− 10% variation from a given value. It is to be understood that such a variation is always included in any given value provided herein, whether or not it is specifically referred to.

(51) As used herein, the term “activity” refers to biocidal activity that kills, inhibits the growth of or otherwise renders a microbe harmless.

(52) The terms “biocide” as used herein means a chemical compound, a chemical composition or a chemical formulation, such as a disinfectant, that has biocidal activity and can kill or render harmless one or more microbes.

(53) The term “formulation” refers to the chemical components of a recipe that is used to make a polymer and/or a coating that comprises one or more polymers, such as a latex coating.

(54) The terms “halo” or “halogen” by themselves or as part of another substituent, as used herein, have the same meaning as commonly understood by one of ordinary skill in the art, and refer to chlorine, bromine or iodine.

(55) The term “latex” as used herein means an emulsion of a first liquid in which polymer particles are dispersed. The polymer particles may also be referred to as polymer colloid and/or polymer sol. The term “latex” may also be referred to herein as a polymer dispersion.

(56) The term “liquid” as used herein means an incompressible fluid that may be in the form of a bulk phase, a surface phase, a spray, a droplet, a micro droplet or a nano droplet.

(57) As used herein, the terms “microbe” and “microbes” refer to one or more single celled, or multi-cellular, microorganisms exemplified by at least one of bacterium, archaea, yeast or fungi.

(58) The term “N-halamine” as used herein refers to a compound containing one or more nitrogen-halogen covalent bonds that is normally formed by the halogenation of imide, amide or amine groups of a compound. The presence of the halogen on an N-halamine moiety may render the compound biocidal or enhance the compound's biocidal activity. N-halamines, as referred to in the present disclosure, include both cyclic, acyclic N-halamine compounds and may also be a reference to precursors of N-halamine compounds.

(59) The term “polymerizable” as used herein refers to a property of a compound to be incorporated into a polymer through one or more chemical bonds between the compound and another chemical component of the polymer or another chemical component of a pre-polymer compound, such as a monomer. The polymer may be a homopolymer, a co-polymer or a heteropolymer. In some examples of the present disclosure the polymerizable compounds can act as monomers in a polymerization process wherein the monomers are linked, cured, tethered or polymerized into the chemical structure of a polymer. In some examples of the present disclosure the polymerizable property may arise due to the compound comprising one or more CIGs.

(60) The terms “quaternary ammonium cation”, “quaternary ammonium compound”, “quaternary ammonium salt”, “QAC”, and “quat” may be used interchangeably throughout the present disclosure to refer to ammonium compounds in which four organic groups are linked to a nitrogen atom that produces a positively charged ion (cation) of the structure NR.sub.4.sup.+.

(61) Embodiments of the present disclosure will now be described by reference to the figures, FIG. 1 to FIG. 42

(62) Some embodiments of the present disclosure relate to polymerizable compounds that have surfactant-like properties, a cationic charge and biocidal activity, or the potential for increased biocidal activity. Some embodiments of the present disclosure relate to compounds with the following general-formula (Formula 1):

(63) ##STR00006##
wherein,
A is an N-halamine precursor that may be selected from a group comprising imidazolidine-2,4-dione (hydantoin); 5,5-dimethylhydantoin; 4,4-dimethyl-2-oxazalidione; tetramethyl-2-imidazolidione; 2,2,5,5-tetramethylimidazo-lidin-4-one; a uracil derivative; and piperidine, including 2,2,6,6-tetramethyl-piperidine;
M.sub.1 and M.sub.2 are each independently selected from nitrogen, phosphorous or nil, but both.sub.are not nil;
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from a group consisting of: a linear alkyl group (C.sub.nH.sub.(2n+1)) where n is an integer between 0 and 18; a branched alkyl group (C.sub.mH.sub.(2m+1)) where m is an integer between 0 and 18; a phenyl group; a cyclohexyl group; a linear alkyloyl group: (C.sub.aH.sub.2aOH) where a is an integer between 0 and 18; and a branched alkyloyl group (C.sub.bH.sub.2bOH) where b is an integer between 0 and 18, wherein in R.sub.1 and R.sub.2 n, m, a and b are 0 when M.sub.1 is nil, and wherein R.sub.3 and R.sub.4 n, m, a and b are 0 when M.sub.2 is nil;
X.sub.1 and X.sub.2 are ions each independently selected from one of Cl.sup.−, Br.sup.−, I.sup.− and PO.sub.4.sup.3−; o, p and q are each an integer independently selected between 0 and 12; and Z is selected from a group comprising at least one of vinyl, vinyl derivative, methyl methacrylate, acrylate, styrene, vinyl benzyl, acrylamide, epoxy, —COOH, —CHO, —CN, —NCO, —NH2, —CNO, —SCN, —NCS and —OH.

(64) Some of embodiments of the present disclosure relate to polymerizable compounds with the following general formula (Formula 2):

(65) ##STR00007##
wherein,
A is an N-halamine precursor that may be selected from a group comprising imidazolidine-2,4-dione (hydantoin); 5,5-dimethylhydantoin; 4,4-dimethyl-2-oxazalidione; tetramethyl-2-imidazolidione; 2,2,5,5-tetramethylimidazo-lidin-4-one; a uracil derivative; piperidine and 2,2,6,6-tetramethyl-piperidine;
M.sub.1 and M.sub.2 are each independently selected from nitrogen, phosphorous or nil, but both are not nil;
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently selected from a group consisting of: a linear alkyl group (C.sub.nH.sub.(2n+1)) where n is an integer between 0 and 18; a branched alkyl group (C.sub.mH.sub.(2m+1)) where m is an integer between 0 and 18; a phenyl group; a cyclohexyl group; a linear alkyloyl group: (C.sub.aH.sub.2aOH) where a is an integer between 0 and 18; or a branched alkyloyl group (CbH2bOH) where b is an integer between 0 and 18, wherein in R.sub.1 and R.sub.2 n, m, a and b are 0 when M.sub.1 is nil, and wherein R.sub.3 and R.sub.4 n, m, a and b are 0 when M.sub.2 is nil;
X.sub.1 and X.sub.2 are ions each independently selected from one of Cl.sup.−, Br.sup.−, I.sup.− and PO.sub.4.sup.3−;
o, p, q and r are each an integer independently selected between 0 and 12; and Z is selected from a group comprising at least one of vinyl, vinyl derivative, methyl methacrylate, acrylate, styrene, vinyl benzyl, acrylamide, epoxy, —COOH, —CHO, —CN, —NCO, —NH2, —CNO, —SCN, —NCS and —OH; and
i is an integer between 1 and 5.

(66) Some of embodiments of the present disclosure relate to polymerizable compounds with the following general-formula (Formula 3):

(67) ##STR00008##
wherein,
A is an N-halamine precursor that may be selected from a group comprising imidazolidine-2,4-dione (hydantoin); 5,5-dimethylhydantoin; 4,4-dimethyl-2-oxazalidione; tetramethyl-2-imidazolidione; 2,2,5,5-tetramethylimidazo-lidin-4-one; a uracil derivative; and piperidine, including 2,2,6,6-tetramethyl-piperidine
M.sub.1, M.sub.2 and M.sub.3 are each independently selected from nitrogen or phosphorous; R 1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sup.6, R.sup.7 and R.sup.8 are each independently selected from: a linear alkyl group (C.sub.nH.sub.2n+1) where n is an integer between 0 and 18; a phenyl group; a cyclohexane group; or an alkyloyl group (C.sub.mH.sub.2mOH) where m is an integer between 0 and 18;
X.sub.1.sup.−, X.sub.2.sup.− and X.sub.3.sup.− are ions each independently selected from but not limited to Cl.sup.−, Br.sup.−, I.sup.− or PO.sub.4.sup.3−;
o, p and q are each an integer independently selected between 0 and 12; and Z is selected from a group comprising at least one of vinyl, vinyl derivative, methyl methacrylate, acrylate, styrene, vinyl benzyl, acrylamide, epoxy, —COOH, —CHO, —CN, —NCO, —NH2, —CNO, —SCN, —NCS and —OH.

(68) Some of embodiments of the present disclosure relate to polymerizable compounds with the following general-formula (Formula 4):

(69) ##STR00009##
wherein,
A is an N-halamine precursor that may be selected from a group comprising imidazolidine-2,4-dione (hydantoin); 5,5-dimethylhydantoin; 4,4-dimethyl-2-oxazalidione; tetramethyl-2-imidazolidione; 2,2,5,5-tetramethylimidazo-lidin-4-one; a uracil derivative; piperidine and 2,2,6,6-tetramethyl-piperidine;
M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5, M.sub.6 and M.sub.7 are each independently selected from nitrogen, phosphorous or nil, wherein not all are nil;
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, Ria and Ria are each independently selected from a linear alkyl group (C.sub.nH.sub.2n+1) where n is an integer between 0 and 18; a branched alkyl group (C.sub.mH.sub.(2m+1)) where m is an integer between 0 and 18; a phenyl group; a cyclohexyl group; a linear alkyloyl group (C.sub.aH.sub.2aOH) where a is an integer between 0 and 18; and a branched alkyloyl group (C.sub.bH.sub.2bOH) where b is an integer between 0 and 18, wherein in R.sub.1, R.sub.2 and R.sub.3 n, m, a and b are 0 when M.sub.5 is nil, wherein in R.sub.4, R.sub.5 and R.sub.6 n, m, a and b are 0 when M.sub.6 is nil; wherein in R.sub.7, R.sub.8 and R.sub.9 n, m, a and b are 0 when Ma is nil, wherein in R.sub.10, R.sub.11 and R.sub.12n, m, a and b are 0 when M.sub.7 is nil, and wherein in R.sub.13 and R.sub.14 n, m, a and b are 0 when M.sub.3 is nil;
X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6 and X.sub.7 are ions each independently selected from one of Cl.sup.−, Br.sup.−, I.sup.− and PO.sub.4.sup.3−;
L.sub.1, L.sub.2, L.sub.3, L.sub.5, L.sub.6 and La are each selected from nil, linear alkylene (C.sub.dH.sub.(2d+1)) where d is an integer between 0 and 18; a branched alkylene (C.sub.eH.sub.(e+1)) where e is an integer between 0 and 18; a linear alkylol (C.sub.fH.sub.2fOH) where f is an integer between 0 and 18; or a branched alkylol (C.sub.gH.sub.2g-2OH) where g is an integer between 0 and 18;
L.sub.4 and L.sub.7 are each selected from a linear alkylene (C.sub.dH.sub.(2d+1)) where d is an integer between 0 and 18; a branched alkylene (C.sub.eH.sub.(e+1)) where e is an integer between 0 and 18; a linear alkylol (C.sub.fH.sub.2fOH) where f is an integer between 0 and 18; or a branched alkylol (C.sub.gH.sub.2g−2OH) where g is an integer between 0 and 18;
Z is selected from at least one of vinyl, vinyl derivative, methyl methacrylate, acrylate, styrene, vinyl benzyl, acrylamide, epoxy, —COOH, —CHO, —CN, —NCO, —NH2, —CNO, —SCN, —NCS or —OH.

(70) Some of embodiments of the present disclosure relate to polymerizable compounds with the following general-formula (Formula 4A):

(71) ##STR00010##
wherein,
A is an N-halamine precursor that may be selected from a group comprising imidazolidine-2,4-dione (hydantoin); 5,5-dimethylhydantoin; 4,4-dimethyl-2-oxazalidione; tetramethyl-2-imidazolidione; 2,2,5,5-tetramethylimidazo-lidin-4-one; a uracil derivative; and piperidine, including 2,2,6,6-tetramethyl-piperidine
M.sub.1, M.sub.2, M.sub.3, M.sub.4, M.sub.5, M.sub.6, M.sub.7, and M.sub.8 are each independently selected from nitrogen, phosphorous or nil;
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are each independently selected from a linear alkyl group (C.sub.nH.sub.(2n+1)); a branched alkyl group (C.sub.mH.sub.(2m+1)) where m is an integer between 0 and 18; a phenyl group; a cyclohexane group; a linear alkyloyl group (C.sub.aH.sub.2aOH) where a is an integer between 0 and 18; and a branched alkyloyl group (C.sub.bH.sub.2bOH) where b is an integer between 0 and 18;
X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and X.sub.8 are each independently selected from but not limited to Cl.sup.−, Br.sup.−, I.sup.− or PO.sub.4.sup.3−;
L1, L2, L3, L5, L6, L8, L9 and L10 are each independently selected from nil, a linear alkyl (CdH(2d+1)) where b is an integer between 0 and 18; a branched alkyl (CeH(2e-1)) where e is an integer between 0 and 18; a linear alkylol (CfH2fOH) where f is an integer between 0 and 18; or a branched alkylol (CgH2gOH) where g is an integer between 0 and 18; i is an integer selected between 1 and 5; and
Z1 and Z2 are each independently selected from at least one of vinyl, vinyl derivative, methyl methacrylate, acrylate, styrene, vinyl benzyl, acrylamide, epoxy, —COOH, —CHO, —CN, —NCO, —NH2, —CNO, —SCN, —NCS, —OH or nil.

(72) One embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C10-C3-methyl, methyl, acrylamide, or PIP-C10-C3-MMAcryl and that has the following formula (Formula 5):

(73) ##STR00011##

(74) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C10-C2-methyl, methyl, acrylamide, or PIP-C10-C2-MMA and that has the following formula (Formula 6):

(75) ##STR00012##

(76) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C12-C2-methyl, methyl, acrylamide, or PIP-C10-C2-MMA and that has the following formula (Formula 7):

(77) ##STR00013##

(78) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C4-methyl, methyl, acrylamide, or PIP-C4-MMA and that has the following formula (Formula 8):

(79) ##STR00014##

(80) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C11-methyl, methyl, acrylamide, or PIP-C11-MMA and that has the following formula (Formula 9):

(81) ##STR00015##

(82) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C11-methyl, methyl, acrylamide-phosphate, or PIP-C11-MMA-phosphate and that has the following formula (Formula 10):

(83) ##STR00016##

(84) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C4-PPh-C4-PPh-benzyl vinyl and that has the following formula (Formula 11):

(85) ##STR00017##

(86) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C4-P-C3-P-benzyl vinyl and that has the following formula (Formula 12):

(87) ##STR00018##

(88) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C4-P-C4-P-C11-MMA and that has the following formula (Formula 13):

(89) ##STR00019##

(90) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C12-C3-MMA and that has the following formula (Formula 14):

(91) ##STR00020##

(92) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-P-C4-P-C12-C3-MMA and that has the following formula (Formula 15):

(93) ##STR00021##

(94) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C4-C2-12-C2-8-2-MMA-C2-12 and that has the following formula (Formula 16):

(95) ##STR00022##

(96) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C3-OH-P-C2-MMA and that has the following formula (Formula 17):

(97) ##STR00023##

(98) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C12-C4-triphenyl phosphate or PIP-C12-C4-TPP and that has the following formula (Formula 18):

(99) ##STR00024##

(100) Another embodiment of the present disclosure relates to a polymerizable compound that

(101) ##STR00025##
may be referred to herein as PIP-C12-C3-TPP and that has the following formula (Formula 19):

(102) ##STR00026##

(103) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C1-vinyl and that has the following formula (Formula 21):

(104) ##STR00027##

(105) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C1-vinyl and that has the following formula (Formula 22):

(106) ##STR00028##

(107) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as Di-phos hydroxyl and that has the following formula (Formula 23):

(108) ##STR00029##

(109) Another embodiment of the present disclosure relates to a polymerizable compound that may be referred to herein as PIP-C2-OH-C4-TPP and that has the following formula (Formula 24):

(110) ##STR00030##

(111) Some embodiments of the present disclosure relate to polymer coatings that incorporate one or more of the polymerizable compounds of Formula 1 through Formula 24 above. The polymer coatings can be used to coat substrates that have hard surfaces and/or soft surfaces. Some examples of suitable hard surfaces include, but are not limited to: glass, ceramic, metal, wood and polymers. Some examples of suitable soft surfaces include, but are not limited to: natural textiles, synthetic textiles and combinations thereof.

(112) FIG. 5 through FIG. 24 show examples of synthetic pathways for making one or more polymerizable compounds according to the present disclosure.

EXAMPLES

Example 1—Experimental Data

(113) Compounds of Formula 5, Formula 6, Formula 7 and Formula 8 were subjected to various experiments to demonstrate the compounds have surfactant-like properties and biocidal activity and/or the potential for increased biocidal activity.

(114) Table 1 provides a summary of the compounds that were tested by the various experiments, described herein further below.

(115) TABLE-US-00001 TABLE 1 Summary of the compounds tested Molecular Weight Formula Compound Abbreviation (g/mol) Acrylic latex synthesis 5 PIP-C10- M1 654.52 C3-MMA 6 PIP-C10- M3 641.60 C2-MMA 7 PIP-C12- M6 503.59 C2-MMA 8 PIP-C4- M5 979.33 MMA 9 PIP-C11- M2 503.59 MMA 10 PIP-C11- MP MMA- Phosphate 11 PIP-C4- PB 979.33 PPh-C4- PPh-Benzyl Vinyl 12 PIP-C4-P- PV 965.3 C3-P- Benzyl Vinyl 13 PIP-C4-P- PM 1145.98 C4-P-C11- MMA 18 PIP-C12- ETI-CEM-1 944.54 C4-TTP 19 PIP-C12- ETI-CEM-2 930.91 C3-TTP 20 PIP-C12- ETI-CEM-3 1095 C4-TTP-NO hydroxyl group Polyol Synthesis 21 PIP-C1- none 305.3 Vinyl Polyurethane Formulation 22 Diol QAS- D2 1161.78 QPS 23 Di-phos D3 1075.81 hydroxyl 24 D4 597.61

Surface Tension Measurements

(116) Compounds of Formula 5, Formula 6 and Formula 9 were subjected to surface tension experiments to assess any surfactant-like properties.

(117) A KRUSS K100 Tensiometer was used to determine the surface tension of a sample of the compounds in liquid water at different concentrations. The concentrations tested were 0.5%, 1.0%, 3.0%, 5.0% and 10%. A platinum plate with dimensions of about 19.9 mm×about 0.2 mm×about 10 mm (width, thickness and height respectfully) was attached to a sensitive mass balance. The sample was raised to the fixed platinum plate at a rate of 10 mm/min with a detection sensitivity of 0.005 g until the liquid sample reached the bottom of the plate. The plate was then immersed in the liquid sample at a depth of 2 mm for 60-150 seconds and any change in mass was recorded by the equipment as a function of time. Force was determined using the equation f=ma.

(118) The surface tension (γ) of each liquid sample was calculated from the force measurement (f) using the equation outlined in Method C: Surface Tension by Wilhelmy plate, ASTM D1331-14.

(119) $\gamma =\frac{f}{2\left(l+t\right)}.Math.\cos \theta$
where (l) is the length and (t) is the thickness of the plate. The contact angle was assumed to be 0. The test results describe a trend and general indication of the surfactant properties of each compound tested.

(120) Table 2 below summarizes the experimental CMC data obtained using the compound of Formula 5 following a 60 second measurement.

(121) TABLE-US-00002 TABLE 2 A summary of Formula 5 experimental surface tension data. Concentration 0.5% 1.0% 3.0% 5.0% 10.0% Surface Mean 36.93 32.55 31.23 30.28 29.57 Tension Standard 0.271 0.802 0.697 0.201 0.856 (mN/m) Deviation

(122) Table 3 below summarizes the experimental surface tension data obtained using the compound of Formula 6 following a 150 second measurement.

(123) TABLE-US-00003 TABLE 3 A summary of Formula 6 experimental surface tension data. Concentration 0.5% 1.0% 3.0% 5.0% 10.0% Surface Mean 47.18 39.51 36.93 35.50 36.39 Tension Standard 1.69 0.45 0.30 0.17 0.15 (mN/m) Deviation

(124) Table 4 below summarizes the experimental surface tension data obtained using the compound of Formula 9 following a 150 second measurement.

(125) TABLE-US-00004 TABLE 4 A summary of Formula 9 experimental surface tension data. Concentration 0.5% 1.0% 3.0% 5.0% 10.0% Surface Mean 37.16 36.19 35.80 35.84 30.44 Tension Standard 0.21 0.08 0.04 0.05 0.45 (mN/m) Deviation

(126) Each of the compounds tested demonstrated surfactant-like properties as evidenced by the surface tension values that were measured as compared to water which is about 72 mN/m.

Example 2—Coating Formulations

(127) Each of the compounds with Formula 5-13 and Formula 18-20 were used to make a polymer coating formulation by a latex-emulsion polymerization process. All coating formulations included a mixture of n-butyl acrylate and methyl methacrylate as major constituents of the polymer backbone, with which each of the compounds of Formula 5-13 and Formula 18-20 were mixed and emulsified.

(128) Briefly, water and a non-ionic surfactant were placed in a multi-neck glass reactor equipped with a water bath, condenser, nitrogen line, an overhead stirrer, and an anchor type agitator. The temperature was raised to about 70° C. before about 2% of a pre-emulsion of monomers was added. The pre-emulsion of monomers comprises a mixture of MMA and BA monomers, non-ionic surfactant and water. This mixture was emulsified by high speed agitation to form a stable “pre-emulsion”. A cationic radical seed-2,2′-Azobis(2-methylpropionamidine)dihydrochloride added at 0.2 wt % in total was next added which immediately turned the dispersion blue, indicating the beginning of polymerization and formation of seed particles. Monomer emulsion and initiator feeding was then carried out over a period of about 3 hours, after which the temperature was raised to about 75° C. at which the latex emulsion was held for about 1 hour before cooling the latex down to about 50° C. Chasers were then added at 50° C., with tert-butyl hydrogen peroxide at 0.1 wt % added as a shot and mixed-in for 15 minutes, while BRUGGOLITE® FF6M (BRUGGOLITE is a registered trademark of L. BRUGGEMANN KG) at 0.1 wt % was fed-in gradually over 30 minutes. When the chasers were added the latex was cooled down to about 30° C. and an oil-based antifoam agent (Rhodoline 646) at 0.2 wt % was added before filtering the latex through a 150 μm filter. Final pH was recorded. Level of coagulum for all coating formulations was less than 0.1%.

(129) Tables 5, 6, 7, 8A, 8B and 9 below summarize acrylic latex coating formulations and the components of the coating formulations made according to embodiments of the present disclosure.

(130) TABLE-US-00005 TABLE 5 Summary of examples of acrylic coating formulations. Formulation Surfactant Type Compound Compound % F1-Control Cationic None 0.0% F1-M1-5% Cationic Formula 5 5.0% F1-M1-10% Cationic Formula 5 10.0% F2-Control Non-Ionic None 0.0% F2-M1-4.6% Non-Ionic Formula 5 4.6% F3-Control Non-Ionic None 0.0% F3-M1-4.6% Non-Ionic Formula 5 4.6% F3-M1-10% Non-Ionic Formula 5 10.0% F3-M2-5% Non-Ionic Formula 9 5.1% F3-M3-6% Non-Ionic Formula 6 5.7% F3-M3-11% Non-Ionic Formula 6 11.6% F3-M5-5% Non-Ionic Formula 8 4.8% F3-M6-6% Non-Ionic Formula 7 6.0% F3-MP-4.6% Non-Ionic Formula 10 4.6% F3-MP-10% Non-Ionic Formula 10 10.1% F3-PB-4.6% Non-Ionic Formula 11 4.6% F3-PB-10% Non-Ionic Formula 11 10.1% F3-PV-9% Non-Ionic Formula 12 8.7% F3-PM-4.6% Non-Ionic Formula 13 4.6% F4-Control Non-Ionic None 0.0% F4-M6-6% Non-Ionic Formula 7 6.0% F4-CEM1-13% Non-Ionic Formula 18 12.8% F4-CEM2-13% Non-Ionic Formula 19 12.5% F4-CEM3-10% Non-Ionic Formula 20 9.8%

(131) TABLE-US-00006 TABLE 6 Summary of the components of variants of Formulation F1. Formulation Component F1-Control F1-M1-5% F1-M1-10% Water 58.2 56.0 53.7 n-butyl acrylate 17.0 17.0 17.0 Methyl methacrylate 22.5 22.5 22.5 Cationic surfactant 1.7 1.7 1.7 Non-ionic surfactant 0 0 0 Polymerizable surfactant 0 2.2 4.5 Initiator 0.2 0.2 0.2 Reducing agent 0.1 0.1 0.1 Oxidizing agent 0.1 0.1 0.1 Antifoam 0.2 0.2 0.2 Total mass (grams) 100 100 100

(132) TABLE-US-00007 TABLE 7 Summary of the components of variants of Formulation F2. Formulation Component F2-Control F2-M1-4.6% Water 52.48 50.48 n-butyl acrylate 22.6 22.6 Methyl methacrylate 21.0 21.0 Cationic surfactant 0 0 Non-ionic surfactant 3.7 3.7 Polymerizable surfactant 0 2.0 Initiator 0.2 0.2 Reducing agent 0 0 Oxidizing agent 0 0 Antifoam 0.02 0.02 Total mass (grams) 100 100

(133) TABLE-US-00008 TABLE 8A Summary of the components of variants of Formulation F3. Formulation F3- F3-M1- F3-M1- F3-M2- F3-M3- F3-M3- F3-M5- Component Control 4.6% 10% 5% 6% 11% 5% Water 52.28 50.28 47.58 50.08 49.78 47.18 50.18 Acetone 0 0 0 0 0 0 0 n-butyl 22.6 22.6 22.6 22.6 22.6 22.6 22.6 acrylate Methyl methacrylate 21.0 21.0 21.0 21.0 21.0 21.0 21.0 Cationic surfactant 0 0 0 0 0 0 0 Non-ionic surfactant 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Polymerizable 0 2.0 4.7 2.2 2.5 5.1 2.1 surfactant Initiator 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Reducing agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Oxidizing agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antifoam 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Total mass (grams) 100 100 100 100 100 100 100

(134) TABLE-US-00009 TABLE 8B Summary of the components of variants of Formulation F3. Formulation F3-M6- F3-MP- F3-MP- F3-PB- F3-PB- F3-PV- F3-PM- Component 6% 4.6% 10% 4.6% 10% 9% 4.6% Water 49.68 50.28 47.88 49.58 47.08 47.78 49.98 Acetone 0 0 0 0.7 0.8 0.7 0.3 n-butyl acrylate 22.6 22.6 22.6 22.6 22.6 22.6 22.6 Methyl methacrylate 21.0 21.0 21.0 21.0 21.0 21.0 21.0 Cationic surfactant 0 0 0 0 0 0 0 Non-ionic surfactant 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Polymerizable 2.6 2.0 4.4 2.0 4.4 3.8 2.0 surfactant Initiator 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Reducing agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Oxidizing agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Antifoam 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Total mass (grams) 100 100 100 100 100 100 100

(135) TABLE-US-00010 TABLE 9 Summary of the components of variants of Formulation F4. Formulation F4-M6- F4-CEM1- F4-CEM2- F4-CEM3- Component 6% 13% 13% 10% Water 51.18 47.48 47.58 48.03 Acetone 0 0.7 0.7 0.7 n-butyl acrylate 22.6 22.6 22.6 22.6 Methyl methacrylate 21.0 21.0 21.0 21.0 Cationic surfactant 0 0 0 0 Non-ionic surfactant 2.2 2.2 2.2 2.95 Polymerizable 2.6 5.6 5.5 4.3 surfactant Initiator 0.2 0.2 0.2 0.2 Reducing agent 0.1 0.1 0.1 0.1 Oxidizing agent 0.1 0.1 0.1 0.1 Antifoam 0.02 0.02 0.02 0.02 Total mass (grams) 100 100 100 100

Active Chlorine Quantification

(136) Energy Dispersive X-ray (EDX) spectroscopy testing was performed on the following coating formulations: F3 control, unchlorinated (see FIG. 1), F3 control, chlorinated (see FIG. 2), F3-M1-4.6%, unchlorinated (see FIG. 3) and F3-M1-4.6%, chlorinated (see FIG. 4). The chlorinated samples were exposed to 200 ppm chlorine solutions for about 10 minutes.

(137) The EDX was completed using an Octane Super Detector on a FEI Quanta 650 FEG scanning electron microscope. The software package used for analysis was TEAM™ available from EDAX.

Latex Particle Size Distribution

(138) Analysis of the latex particle size distribution was conducted using a Malvern Nano ZS and size distribution report was provided by Intensity V2.1 software. Table 10 summarizes the latex particle size distribution.

(139) TABLE-US-00011 TABLE 10 Summary of Latex Particle Size Distribution Compound Z-Average nm Formulation % (Pdi) F1-M1-5%  5.0% 90.44 (.041) F2-Control  0.0% 113.1 (.014) F2-M1-4.6%  4.6% 132.0 (.127) F3-Control  0.0% 116.4 (.026) F3-M1-4.6%  4.6% 124.9 (.036) F3-PB-10% 10.0% 92.30 (.026)

Biocidal Activity Testing

(140) Coating formulations were tested for biocidal activity in accordance with ISO 22196: Measurement of antibacterial activity on plastics and other non-porous surfaces. Briefly, the sample size was scaled down to 2.5 cm×2.5 cm and the test conditions included testing in phosphate buffered saline (PBS) or 5% fetal bovine serum (FBS). The samples were challenged with E. coli (ATCC 25922). An overnight culture of E. coli was diluted to 106 colony forming units (CFU)/mL, and about 50 μL of the diluted bacterial was added onto a 2.5 cm×2.5 cm testing surface that was coated with one of the coating formulations. Per ISO 22196 protocol, a polyethylene terephthalate cover film (2 cm×2 cm) was applied overtop to ensure contact between the coating formulation and the bacteria. The test surfaces then incubated with the bacteria at room temperature for the reported contact times. At the end of each contact time 2.5 ml of neutralizer was added to allow counting of bacteria.

(141) Table 11 summarizes the biocidal activity experimental data of F1 variants of the coating formulations with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 10.7 following exposure to E. coli in PBS.

(142) TABLE-US-00012 TABLE 11 Summary of F1 coating formulation biocidal activity in PBS. Log Reduction (Log.sub.10) at Various Contact Times in PBS 30 60 Full Log Bacteria Sample ID min min Reduction Gram- E. coli Unchlorinated F1- 4.73 4.73 4.73 negative ATCC Control 25922 Unchlorinated F1- 4.73 4.73 M1-5% Unchlorinated F1- 4.73 4.73 M1-10% Chlorinated F1-Control 4.73 4.73 Chlorinated F1-M1-5% 4.73 4.73 Chlorinated F1-M1-10% 4.73 4.73

(143) Without being bound by any particular theory, it is postulated that unchlorinated killing of microbes was due to the use of the cationic surfactant (C-TAB) in the latex synthesis steps, as shown in Table 6.

(144) 12 summarizes the biocidal activity experimental data of F2 variants of the coating formulations with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 7 following exposure to E. coli in PBS.

(145) TABLE-US-00013 TABLE 12 Summary of F2 coating formulation biocidal activity in PBS. Log Reduction (Log.sub.10) at Various Contact Times in PBS 30 60 Full Log Bacteria Sample ID min min Reduction Gram- E. coli Unchlorinated F2- / 1.15 5.71 negative ATCC Control 25922 Unchlorinated F2- / 1.01 M1-4.6% Chlorinated F2-Control 1.03 2.35 Chlorinated F2-M1-4.6% 5.71 5.71

(146) Table 13 summarizes the biocidal activity experimental data of F3 variants of the coating formulations with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 7 following exposure to E. coli in PBS.

(147) TABLE-US-00014 TABLE 13 Summary of F3 coating formulation biocidal activity in PBS. Log Reduction (Log10) at Various Contact Times in PBS Full Log Bacteria Sample ID 10 min 30 min 60 min Reduction Gram- E. coli Unchlorinated F3-Control / / 0.15 4.76 negative ATCC Unchlorinated F3-M1-4.6% / / 0.33 25922 Unchlorinated F3-M1-10% / / 0.55 4.81 Unchlorinated F3-M2-5% / / −0.06 Unchlorinated F3-M3-6% 0.47 0.56 0.61 4.98 Unchlorinated F3-M3-11% 0.28 0.40 0.42 Unchlorinated F3-M5-5% 0.60 0.66 0.73 Unchlorinated F3-M6-6% 0.19 0.36 0.21 4.88 Unchlorinated F3-MP-4.6% 0.00 0.00 / 5.98 Unchlorinated F3-PB-4.6% 0.14 .07 / 4.67 Unchlorinated F3-PB-10% 0.72 0.96 / 4.93 Unchlorinated F3-PV-9% 0.47 0.58 0.58 4.97 Unchlorinated F3-PM-4.6% 0.15 0.15 / 4.67 Chlorinated F3-Control 0.26 0.65 0.60 4.76 Chlorinated F3-C3-M1-4.6% 4.76 4.76 4.76 Chlorinated F3-C3-M1-10% 4.81 4.81 4.81 4.81 Chlorinated F3-M2-5% 4.81 4.81 4.81 Chlorinated F3-M3-6% 4.98 4.98 4.98 4.98 Chlorinated F3-M3-11% 0.67 4.98 4.98 Chlorinated F3-M5-5% 4.98 4.98 4.98 Chlorinated F3-M6-6% 4.88 4.88 4.88 4.88 Chlorinated F3-MP-4.6% 5.98 5.98 / 5.98 Chlorinated F3-PB-4.6% 4.67 4.67 / 4.67 Chlorinated F3-PB-10% 4.93 4.93 / 4.93 Chlorinated F3-PV-9% 1.24 2.42 4.97 4.97 Chlorinated F3-PM-4.6% 1.46 4.67 / 4.67

(148) Table 14 summarizes the biocidal activity experimental data of F4 variants of the coating formulations with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 7 following exposure to E. coli in PBS.

(149) TABLE-US-00015 TABLE 14 Summary of F4 coating formulation biocidal activity in PBS. Log Reduction (Log10) at Various Contact Times in PBS Full Log Bacteria Sample ID 10 min 30 min 60 min Reduction Gram- E. coli Unchlorinated F4-M6-6% / / 0.29 5.85 negative ATCC Unchlorinated F4-CEM1-13% 0.55 1.99 1.04 4.54 25922 Unchlorinated F4-CEM2-13% 4.54 4.54 4.54 Unchlorinated F4-CEM3-10% / / 4.82 4.82 Chlorinated F4-M6-6% 0.53 1.50 5.85 5.85 Chlorinated F4-CEM1-13% 4.54 4.54 4.54 4.54 Chlorinated F4-CEM2-13% 4.54 4.54 4.54 Chlorinated F4-CEM3-10% 4.82 4.82 4.82 4.82

(150) Without being bound by any particular theory, it is postulated that the unchlorinated killing of microbes shown in Table 14 is evidence of the CEM monomers leaching, or otherwise dissociating, from the polymer particles after synthesis of the latex.

(151) Table 15 summarizes the biocidal activity experimental data of F2 and F3 variants of the coating formulations tested with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 7 following exposure to E. coli in 5% FBS.

(152) TABLE-US-00016 TABLE 15 Summary of F2 and F3 coating formulation biocidal activity in 5% FBS. Log Reduction (Log10) at Vari- ous Contact Times in 5% FBS Full Log Reduc- Bacteria Sample ID 10 min 30 min 60 min tion Gram- E. coli Unchlorinated / / −0.17 4.89 negative ATCC F2-M1-4.6% 25922 Unchlorinated / / −0.09 F3-M1-4.6% Unchlorinated / / −0.21 F3-M1-10% Unchlorinated / / 0.01 4.90 F3-M2-5% Unchlorinated / / 0.42 4.99 F3-M3-6% Unchlorinated / / 0.32 F3-M5-5% Unchlorinated / / 0.46 5.00 F3-M6-6% Unchlorinated / / 0.70 5.20 F3-MP-4.6% Unchlorinated 0.49 0.55 0.56 4.94 F3-PB-4.6% Unchlorinated 0.49 0.65 1.03 F3-PB-10% Unchlorinated 0.54 0.58 0.45 F3-PM-4.6% Chlorinated 0.64 1.93 4.89 4.89 F2-M1-4.6% Chlorinated 0.82 4.89 4.89 F3-C3-M1-4.6% Chlorinated 1.16 4.89 4.89 F3-C3-M1-10% Chlorinated 0.39 1.37 2.50 4.90 F3-M2-5% Chlorinated 0.20 0.67 1.72 4.99 F3-M3-6% Chlorinated 0.38 1.86 2.63 F3-M5-5% Chlorinated 0.31 0.64 2.82 5.00 F3-M6-6% Chlorinated 0.63 0.88 1.84 5.20 F3-MP-4.6% Chlorinated 0.71 0.96 2.53 4.94 F3-PB-4.6% Chlorinated 4.94 4.94 4.94 F3-PB-10% Chlorinated 0.47 0.45 0.54 F3-PM-4.6%

(153) Table 16 summarizes the biocidal activity experimental data of F4 variants of the coating formulations tested with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 7 following exposure to E. coli in 5% FBS.

(154) TABLE-US-00017 TABLE 16 Summary of F4 coating formulation biocidal activity in 5% FBS. Log Reduction (Log10) at Various Contact Times in 5% FBS Full Log Reduc- Bacteria Sample ID 10 min 30 min 60 min tion Gram- E. coli Unchlorinated 0.37 0.53 0.47 4.90 negative ATCC F4-CEM1-13% 25922 Unchlorinated 4.59 4.59 4.59 4.59 F4-CEM2-13% Unchlorinated / 0.46 0.89 4.91 F4-CEM3-10% Chlorinated 0.31 0.57 0.75 4.90 F4-CEM1-13% Chlorinated 4.59 1.29 1.17 4.59 F4-CEM2-13% Chlorinated / 0.48 0.65 4.91 F4-CEM3-10%

Protein Adsorption Testing

(155) Various of the coating formulations were tested for the relative protein adsorption into the surface of the coating formulations. These tests are based upon a Lowry/BCA assay kit to measure the concentration of eluted protein from the surface of the coating formulations. Table 17 summarizes the protein adsorption data obtained by these experiments using 5% FBS and E. coli exposure as described herein above.

(156) TABLE-US-00018 TABLE 17 Summary of protein adsorption data. Protein per cm.sup.2 Sample ID μg/cm2 F2-M1-4.6% 2.01 ± 0.17 F3-Control 1.31 ± 0.36 F3-M1-4.6% 1.76 ± 0.57 F3-M1-10% 4.90 ± 0.20 F3-M2-5% 1.84 ± 0.16 F3-PB-10% 8.64 ± 0.10 F4-M6-6% 2.04 ± 0.04

(157) Table 18 and Table 19 below summarize the formulations of polyol synthesis and the components of the polyol formulations made.

(158) TABLE-US-00019 TABLE 18 Summary of polyol synthesis formulations. Compound Compound Formulation Compound wt % mol % C2-Control None 0.0% 0.0% C1-PB-7.8% Formula 11 5.8% 1.0% C3-M1-4.5% Formula 5  4.5% 1.0% C6- PIP-C1-Vinyl-3.75% Formula 21 3.8% 2.0%

(159) TABLE-US-00020 TABLE 19 Summary of the components of variants of 5L batch of polyol synthesis of Formulation C1, C3 and C6 (in grams). C2- C1- C3-M1- C6-PIP-C1- Formulation Component Control PB-5.8% 4.5% Vinyl-3.8% Polymerizable monomer 0 206 138 154 mixture of acrylate and 2000-3000 2000-3000 2000-3000 2000-3000 styrenic monomers Initiator 100-200 100-200 100-200 100-200 Solvent 400-600 400-600 400-600 400-600 Co-Solvent 200-300 200-300 100-200 200-300

(160) Table 20, Table 21 and Table 22 below summarize the polyurethane coating formulations and the components of the coating formulations made.

(161) TABLE-US-00021 TABLE 20 Summary of polyurethane coating formulations. Compound Formulation Polyol Compound wt % C2NAP0 C2-Control None  0.0% C2D2P9 C2-Control Formula 22  5.4% C2D3P17 C2-Control Formula 23  9.6% C2D4P15 C2-Control Formula 24  8.3% C2D4P22 C2-Control Formula 24 12.4% C2M6P14 C2-Control Formula 7   8.6% C6NAP0 C6-PIP-C1-Vinyl- None  0.0% 3.75% C6D3P16 C6-PIP-C1-Vinyl- Formula 23  8.8% 3.75% C6D3P24 C6-PIP-C1-Vinyl- Formula 23 13.6% 3.75%

(162) TABLE-US-00022 TABLE 21 Summary of the components of variants of polyurethane coating formulations with C2-Control polyol. Formulation Component C2NAP0 C2D2P9 C2D3P17 C2D4P15 C2D4P22 C2M6P14 Polyol (C2) 80 75 75 72 68 72 Polymerizable 0 7.5 15 12.62 19.05 12.12 monomer Solvent 4 10 20 20 20 10.80 Co-solvent 4 0 0 0 0 0 Isocyanate 45.38 46.56 46.56 46.56 46.56 46.56 Catalyst 0.16 0.16 0.16 0.16 0.16 0.16 Total mass (grams) 133.54 139.22 156.72 151.34 153.77 141.64

(163) TABLE-US-00023 TABLE 22 Summary of the components of variants of polyurethane coating formulations with C6-PIP-C1-Vinyl-3.8% polyol. Formulation Component C6NAP0 C6D3P16 C6D3P24 Polyol (C6) 80 75 72 Polymerizable 0 14.29 22.86 monomer Solvent 26 26 26 Co-solvent 0 0 0 Isocyanate 46.56 46.56 46.56 Catalyst 0.16 0.16 0.16 Total mass 152.72 162.01 167.58 (grams)

Biocidal Activity Testing

(164) Coating formulations were tested for biocidal activity in accordance with ISO 22196: Measurement of antibacterial activity on plastics and other non-porous surfaces. Briefly, the sample size was scaled down to 2.5 cm×2.5 cm and the test conditions included testing in PBS or 5% FBS. The samples were challenged with E. coli 0157. An overnight culture of E. coli was diluted to 106 colony forming units (CFU)/mL, and about 50 μL of the diluted bacterial was added onto a 2.5 cm×2.5 cm testing surface that was coated with one of the coating formulations. Per ISO 22196 protocol, a polyethylene terephthalate cover film (2 cm×2 cm) was applied overtop to ensure contact between the coating formulation and the bacteria. The test surfaces then incubated with the bacteria at room temperature for reported contact times. At the end of each contact time 2.5 ml of neutralizer was added to allow counting of bacteria.

(165) Table 23 summarizes the biocidal activity experimental data of F1 variants of the coating formulations tested with or without exposure to 200 ppm of chlorine for 10 minutes at a pH of 7 following exposure to E. coli in 5% FBS.

(166) TABLE-US-00024 TABLE 23 Summary of all the polyurethane coating formulations biocidal activity in 5% FBS. Log Reduction (Log10) at Various Contact Times in 5% FBS Full Log 60 min 120 min 180 min Reduction / / 0.02 4.70 / / 0.70 4.70 −0.08 0.03 0.16 4.76 1.35 4.76 4.76 4.76

Humidity and UV Resistance Testing

(167) FIG. 25 through to FIG. 33 summarize the results of humidity-resistance tests of polyurethane coating formulations made according to embodiments of the present disclosure. The humidity-resistance tests were conducted in accordance with ASTM D2247 and D870: in 100% relative humidity.

(168) FIG. 34 through to FIG. 42 summarize the results of ultraviolet resistance tests results of polyurethane coating formulations made according to embodiments of the present disclosure. The ultraviolet resistance tests were conducted according to ASTM D4587 Standard Practice for Fluorescent UV/Condensation cycles: 4 hours of exposure to ultraviolet radiation (340 nm, 0.89 W/(m2.Math.nm) followed by about 4 hours of condensation at about 60° C.

(169) FIG. 43 shows a first vial 10 and a second vial 12. The first vial 10 contains a volume of fluid latex emulsion that does not contain a polmerizable compound with surfactant-like properties (F3-control). The second vial 12 contains a polmerizable compound with surfactant-like properties (F4-M6-6% as shown in Table 5 and Table 9). The two vials 10, 12 were kept closed at room temperature for about ten months. the first vial 10 clearly shows the growth of microbes and the second vial 12 does not.