Dye complexing agents

Abstract

This disclosure relates to dye complexing polymers that are useful in the chemical arts, such as in the manufacture of products, such as laundry detergents and fabric softeners. In particular, the present disclosure pertains to novel compositions and processes for preparing certain water soluble dye complexing polymers.

Description

[0001] DYE COMPLEXING AGENTS

[0002] RELATED APPLICATIONS

[0003] This application claims the benefit of U.S. Provisional Application No. 63 / 625,633, filed January 26. 2024, the entire disclosure of which is incorporated herein by reference.

[0004] TECHNICAL FIELD

[0005] This disclosure relates to dye complexing polymers that are useful in the chemical arts, such as in the manufacture of products, such as laundry detergents and fabric softeners. In particular, the present disclosure relates to compositions and processes for preparing certain dye complexing polymers.

[0006] BACKGROUND

[0007] Consumers want products that simplify the way they do their laundry and help reduce the amount of time they spend dealing with laundry while still achieving high levels of benefits. As a result, products that enable the consumer to customize the amount of product they use are popular.

[0008] Typically, the product composition contains an appreciable quantity of surfactants, other cleaning ingredients and additives including dye transfer inhibitors. Such products are often provided in soluble unit dose pouches that contain a known quantity of active ingredients. Such products are also provided in liquid or powder form with a measuring cup to deliver a known quantity of product.

[0009] Dye complexing polymers have been / are being used in laundry detergent and fabric softener compositions. During washing, some dyes may bleed from colored fabric under washing conditions. The extent of bleeding is influenced by the structure of the dye, type of cloth, pH, and temperature and mechanical efficiency of the agitation process. The dye in the wash liquor can be innocuous and exit the system, however, more likely, the fugitive dye will redeposit either onto the same fabnc or onto another fabric leading to patches and changed appearance of the washed material. This redeposition of the dye can be inhibited in several ways. The most common being the introduction of a dye transfer inhibitor (DTI) compound that complexes with the fugitive dye to remove it from the wash liquor during the rinse cycle, thus preventing redeposition. A secondary mode is the deposition of the DTI polymer on the fabric where it repels any rogue (uncomplexed) dye trying to deposit.

[0010] Polyvinylpyrrolidone (PVP) has been used to inhibit dye deposition during washing of colored fabrics under standard laundry conditions. However, the performance of PVP is adversely affected by the presence of anionic surfactants in detergent compositions. Other polymers used in detergent compositions may include polyvinylimidazole, poly vinylpyridine-JV- oxide, and poly vinylpyridine-.V-carboxymethylbelaine.

[0011] Accordingly, there remains a need for improved dye complexing for use in the preparation of laundry products including detergents and fabric softeners.

[0012] SUMMARY

[0013] In one aspect, the present disclosure provides a polymer comprising formula I, formula II, and formula III:

[0014] HI, or salts thereof, wherein

[0015] A is O, NH, or alkylene;

[0016] B is alkylene or N. provided that if A is O or NH. then B is alkylene; each of L1, L2, and L3is independently a bond, alkylene, amino, amido, ester, carbonyl, alkylene-ester, alkylene-amido. or alkylamino;

[0017] R1is hetaryl, and comprises a quaternary' amine;

[0018] R2is H, OH, or alkyl;

[0019] R3is hetar l. and does not include a quaternary amine; m is an integer greater than 0; n is 0 or an integer greater than 0; and o is 0 or an integer greater than 0; wherein “ » denote points of attachment of each formula, when present, to the rest of the polymer.

[0020] In another aspect, the present disclosure provides a polymer having a backbone, the polymer comprising: a first monomer comprising a het ary I group comprising a quaternary amine, wherein the hetaryl group is conjugated to the backbone through alkylene, ester, carbonyl, amino, amido, alkylene-ester, alkylene-amido, or alkylamino; a second monomer comprising a hetaryl group, wherein the hetaryl group is conjugated to the backbone through alkylene, ester, carbonyl, amino, amido, alkylene-ester, alkylene-amido, or alkylamino; a third monomer comprising H, OH, ester, carbonyl, amino, or amido conjugated to the backbone.

[0021] In another aspect, the disclosure relates to a composition comprising the polymer according to the present disclosure.

[0022] In further aspects, the disclosure relates to an article of the polymer according to the present disclosure conjugated to a solid support.

[0023] In further aspects, the disclosure relates to a process for preparing the polymer according to the present disclosure.

[0024] In further aspects, the disclosure relates to a polymer according to the present disclosure for use in a method of inhibiting a transfer of a dye in an aqueous solution.

[0025] Additional embodiments, features, and advantages of the disclosure will be apparent from the following detailed description and through practice of the disclosure. The compounds of the present disclosure can be described as embodiments in any of the following enumerated clauses. It will be understood that any of the embodiments described herein can be used in connection with any other embodiments described herein to the extent that the embodiments do not contradict one another.

[0026] DETAILED DESCRIPTION

[0027] The object of present disclosure is to provide dye complexing agents capable of use in laundry detergent and fabric softening compositions.

[0028] In certain aspects of the present disclosure, a water-soluble dye complexing agent containing quaternary nitrogen is particularly effective in the presence of anionic surfactants. Another feature of certain embodiments of the present disclosure is the provision that the dye complexing agent is biodegradable under standard conditions.

[0029] Among the other objects and features of the present disclosure is to provide polymers having dye complexing properties useful in fabric softener and textile dye treatment compositions. DEFINITIONS

[0030] As used herein, the terms “alkyl” and “alkylene” include a chain of carbon atoms, which is optionally branched and contains from 1 to 20 carbon atoms. The term “alkyl” refers to a straight- or branched-chain monovalent hydrocarbon group. The term “alkylene” refers to a straight- or branched-chain divalent hydrocarbon group. In some embodiments, it can be advantageous to limit the number of atoms in an “alkyl” or “alkydene” to a specific range of atoms, such as C1-C20 alky 1 or C1-C20 alkylene, C1-C12 alkyl or C1-C12 alkylene, or Ci-Ce alkyl or Ci-Ce alkylene. Examples of alkyl groups include methyl (Me), ethyl (Et), n-propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl (tBu), pentyl, isopentyl, tert-pentyl, hexyl, isohexyl, and groups that in light of the ordinary skill in the art and the teachings provided herein would be considered equivalent to any one of the foregoing examples. Examples of alkylene groups include methylene (-CH2-). ethylene ((-CH2-)2). n-propylene ((-CH2-)3), iso-propylene ((-C(H)(CH?)CH2-)), n-butylene ((-CH2-)4), and the like. It will be appreciated that an alkyd or alkylene group can be unsubstituted or substituted as described herein.

[0031] An alkyd or alkylene group can be substituted with any of the substituents in the various embodiments described herein, including one or more of such substituents. It will be understood that “alkyl” or “alkylene” may be combined with other groups, such as those provided above, to form a functionalized alkyl. By way of example, the combination of an “alkyl” group, as described herein, with a “carboxylate” group may be referred to as an “alkylene-carboxylate” O group as illustratively represented by the structure: . Other non-limiting examples of an “alkylene” group, as described herein, with an “ester” group or “amido” group include “alkylene-ester” and “alkylene-amido,” respectively. Illustrative “alkylene-ester” groups, for

[0032] O example methylene-ester, can be represented by the structures: and

[0033] O . Similarly, “alkylene-amido” groups, for example methylene-amido groups, can be represented by the structures: H and 0

[0034] It will be appreciated that any hydrogen atom on “alkyl” or “alkylene” can be replaced with a substituent. For example, an alkylene group such as ethylene, shown as “B” substituted by an -L'-R1, in a structure depicted can include the following structures: Similarly, propylene, shown as “B” substituted by an -L1-

[0035] R1, in a structure depicted by can include the following structures:

[0036] As used herein, the term “alkenyl” includes a chain of carbon atoms, which is optionally branched, and contains from 2 to 20 carbon atoms, and also includes at least one carbon-carbon double bond (i.e., C=C). It will be understood that in certain embodiments, alkenyl may be advantageously of limited length, including C2-C12, C2-C9. C2-C8. C2-C7, C2-C6, and C2-C4. Illustratively, such particularly limited length alkenyl groups, including C2-C8, C2-C7, C2-C6, and C2-C4 may be referred to as lower alkenyl. Alkenyl may be unsubstituted, or substituted as described for alkyl or as described in the various embodiments provided herein. Illustrative alkenyl groups include, but are not limited to, ethenyl. 1 -propenyl, 2-propenyl, 1-, 2-, or 3-butenyl, and the like.

[0037] As used herein, the term “alkynyl” includes a chain of carbon atoms, which is optionally branched, and contains from 2 to 20 carbon atoms, and also includes at least one carbon-carbon triple bond (i.e., C=C). It will be understood that in certain embodiments, alkynyl may each be advantageously of limited length, including C2-C12, C2-C9. C2-C8. C2-C7. C2-C6, and C2-C4. Illustratively, such particularly limited length alky nyl groups, including C2-C8, C2-C7, C2-C6, and C2-C4 may be referred to as lower alkynyl. Alkynyl may be unsubstituted, or substituted as described for alkyl or as described in the various embodiments provided herein. Illustrative alkynyl groups include, but are not limited to, ethynyl. 1-propynyl, 2-propynyl, 1-, 2-, or 3-butynyL and the like.

[0038] As used herein, the term “cycloalkyl” refers to a 3 to 15 member all-carbon monocyclic ring, including an all-carbon 5-member / 6-member or 6-member / 6-member fused bicyclic ring, or a multicyclic fused ring (a “fused’' ring system means that each ring in the system shares an adjacent pair of carbon atoms with each other ring in the system) group, or a carbocyclic ring that is fused to another group such as a heterocyclic, such as ring 5- or 6-membered cycloalkyl fused to a 5- to 7- membered heterocyclic ring, where one or more of the rings may contain one or more double bonds but the cycloalkyl does not contain a completely conjugated pi-electron system. It will be understood that in certain embodiments, cycloalkyl may be advantageously of limited size such as C3-C13, C3-C9, C3-C6 and C4-C6. Cycloalkyl may be unsubstituted, or substituted as described for alky l or as described in the various embodiments provided herein. Illustrative cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyd. cyclopenteny 1. cyclopentadienyl, cyclohexyl, cyclohexenyl, cycloheptyl, adamantyl, norbomyl. norbomenyl, and the like. Illustrative examples of cycloalkyl groups shown in graphical representations include the following entities, in the form of properly bonded moieties:

[0039] As used herein, the term “heterocycloalkyl” refers to a monocyclic or fused ring group having in the ring(s) from 3 to 12 ring atoms, in which at least one ring atom is a heteroatom, such as nitrogen, oxygen or sulfur, the remaining ring atoms being carbon atoms. Heterocycloalkyl may optionally contain 1, 2. 3 or 4 heteroatoms. A heterocycloalkyl group may be fused to another group such as another heterocycloalkyl, or a hetaryl group. Heterocycloalkyl may also have one of more double bonds, including double bonds to nitrogen (e.g., C=N or N=N) but does not contain a completely conjugated pi-electron system. It will be understood that in certain embodiments, heterocycloalkyd may be advantageously of limited size such as 3- to 7- membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl, 3-, 4-, 5- or 6-membered heterocycloalkyl, and the like. Heterocycloalkyl may be unsubstituted, or substituted as described for alkyd or as described in the various embodiments provided herein. Illustrative heterocycloalkyl groups include, but are not limited to, oxiranyl, thianaryl, azetidinyl, oxetanyl. tetrahydrofuranyl, pyrrolidinyl, tetrahydropyranyl, pipendinyl, dioxanyL morpholinyl. dithianyl. piperazinyl, oxepanyl, and the like. Illustrative examples of heterocycloalkyl groups shown in graphical representations include the following entities, in the form of properly bonded moieties:

[0040]

[0041] As used herein, the term "ary l" refers to an all-carbon monocyclic or fused-ring polycyclic groups of 6 to 12 carbon atoms having a completely conjugated pi-electron system. It will be understood that in certain embodiments, and may be advantageously of limited size such as Ce- Cio aryl. Illustrative aryl groups include, but are not limited to, phenyl, naphthylenyl and anthracenyl. The aryl group may be unsubstituted, or substituted as described for alky l or as described in the various embodiments provided herein.

[0042] As used herein, the term “hetaryl” refers to a monocyclic or fused ring group of 5 to 12 ring atoms containing one, two, three or four ring heteroatoms selected from nitrogen, oxygen and sulfur, the remaining ring atoms being carbon atoms, and also having a completely conjugated pi-electron system. It will be understood that in certain embodiments, hetaryl may be advantageously of limited size such as 3- to 7-membered hetaryl. 5- to 7-membered hetaryl. and the like. Hetaryl may be unsubstituted, or substituted as described for alkyl or as described in the various embodiments provided herein. Illustrative hetaryl groups include, but are not limited to, pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, quinolinyl. isoquinolinyl, and the like. Illustrative examples of hetaryl groups shown in graphical representations, include the following entities, in the form of properly bonded moieties:

[0043]

[0044] It will be understood that in certain embodiments, a hetaryl group may refer to a complexed salt thereof. For example, a pyridinyl group, represented as a pyridinium chloride salt, may be depicted by the structure: . it will be understood that in certain embodiments, a hetaryl group may include a quaternary or quatemized amine (nitrogen atom). For example, a hetaryl comprising a quaternary or quatemized amine (nitrogen atom) includes pyridine, where the nitrogen atom is substituted by X’, as depicted by the pyridinium structure: , wherein

[0045] X" represents oxide, carboxylate, alkyl-carboxylate, alkenyl-carboxylate, or alkynyl-carboxylate. Additional illustrative examples of hetaryl groups shown in graphical representations, include the following entities:

[0046] As used herein, “halo” or “halogen” refers to fluorine, chlorine, bromine, or iodine.

[0047] As used herein, “cyano” refers to a -CN group.

[0048] As used herein, “hydroxy” or “hydroxyl” refers to an -OH group.

[0049] As used herein, “oxide” refers to an oxygen atom attached to another atom, represented by the formula -O’. For example, an “N-oxide” refers to an oxygen atom attached to a nitrogen atom represented by the formulaN-0’. A representative example of an oxide, such as an N-oxide, can be pyridine-N-oxide as depicted by the structure: (X O .

[0050] As used herein, “carboxylate” refers to a salt or ester of a carboxylic acid represented by the formula -COO’.

[0051] The term “carboxy,” as used herein, refers to a group represented by the formula — CO2H. The term “acyl” is art-recognized and refers to a group represented by the general formula hydrocarbylC(O) — , preferably alkylC(O) — .

[0052] The term “acylamino” is art-recognized and refers to an amino group substituted with an acyl group and may be represented, for example, by the formula hydrocarbylC(O)NH — .

[0053] The terms “amide” and “amido,” as used herein, refers to a group wherein R9and R10each independently represent a hydrogen or hydrocarbyl group, or R9and R10taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure.

[0054] The terms “amine” and “amino” are art-recognized and refer to both unsubstituted and substituted amines and salts thereof, e.g., a moiety that can be represented by wherein R9and R10, each independently represent a hydrogen or a hydrocarbyl group, or R9and R10taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure. Amines include, but are not limited to, ammonia, methylamine, dimethyl amine, trimethylamine, ethylamine, diethylamine, triethylamine, pyrrolidine, pyrrole, imidazole, pyridine, pyrimidine, pyridazine, pyrazine, and the like. It will be understood that in certain embodiments, an amine may be quatemized (i.e., a quaternary amine). Representative illustrative examples of amines, include but are not limited to, the following structures: represents oxide, carboxylate, alkyl-carboxylate, alkenyl-carboxylate, or alkynyl-carboxylate.

[0055] The term “alkylamino” refers to an amino group substituted with at least one alk l group.

[0056] The term “ester,” as used herein, refers to a group -C(O)OR9wherein R9represents a hydrocarbyl group.

[0057] The term “hydrocarbyl,” as used herein, refers to a group that is bonded through a carbon atom that does not have a =0 or =S substituent, and typically has at least one carbon-hydrogen bond and a primarily carbon backbone, but may optionally include heteroatoms. Thus, groups like methyl, ethoxyethyl, 2-pyridyl. and even trifluoromethyl are considered to be hydrocarbyl for the purposes of this application, but substituents such as acetyl (which has a =0 substituent on the linking carbon) and ethoxy (which is linked through oxygen, not carbon) are not. Hydrocarbyl groups include, but are not limited to aryl, hetaryl, carbocycle. heterocycle, alkyl, alkenyl, alkynyl. and combinations thereof.

[0058] The term “alkoxy” refers to an alkyl group having an oxygen attached thereto. Representative alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy and the like.

[0059] The term “oxo” represents a carbonyl oxygen.

[0060] The term “carbonyl” is art-recognized and refers to a group -C(0)- where a double bond exists between the carbon and oxygen.

[0061] As used herein, “bond” refers to a covalent bond.

[0062] The term “sulfate” is art-recognized and refers to the group -OSO3H, or a pharmaceutically acceptable salt thereof. An example of a sulfate surfactant includes but is not limited to sodium alkyl sulfate (e.g., sodium dodecyl sulfate).

[0063] The term “sulfonamide” is art-recognized and refers to the group represented by the general formulae wherein R9and R10independently represents hydrogen or hydrocarbyl.

[0064] The term “sulfoxide” is art-recognized and refers to the group — S(0) — .

[0065] The term “sulfonate” is art-recognized and refers to the group SO3H, or a pharmaceutically acceptable salt thereof. An example of a sulfonate surfactant includes but is not limited to sodium alkyl benzyl sulfonate (e.g., sodium dodecyl benzyl sulfonate (SDBS)).

[0066] The term “sulfone” is art-recognized and refers to the group — S(0)2 — .

[0067] The term “sultaine” or “sulfobetaine” refers to a compound with a positively charged cationic functional group that bears no hydrogen atom, such as a quaternary nitrogen (e.g.. ammonium or pyridinium) or phosphonium cation, and with a negatively charged functional group, such as a sulfonate, that may not be directly adjacent to the cationic site. Illustrative examples of sultaines include, but are not limited to a sulfopropyl quaternary ammonium salt group represented by the general formula

[0068] , wherein R is optionally substituted alkyl (e.g., alkylamidopropyl), and R’ is hydrogen or hydroxyl group, , and An example of a sultaine surfactant includes but is not limited to cocamidopropyl hydroxysultaine (e.g., laurylamidopropyl hydroxysultaine).

[0069] The term "ester." as used herein, refers to a group — C(O)OR9wherein R9represents a hydrocarbyl group.

[0070] The term “ether,” as used herein, refers to a hydrocarbyl group linked through an oxygen to another hydrocarbyl group. Accordingly, an ether substituent of a hydrocarbyl group may be hydrocarbyl-0 — . Ethers may be either symmetrical or unsymmetrical. Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethers include “alkoxyalkyl” groups, which may be represented by the general formula alkyl-O-alkyl.

[0071] The term “Cx y” or “Cx-Cy,” when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups that contain from x to y carbons in the chain. Co alkyl indicates a hydrogen where the group is in a terminal position, a bond if internal. A Ci-6 alkyl group, for example, contains from one to six carbon atoms in the chain.

[0072] As used herein, the suffix “-yl” refers to substituent groups where a radical that is bonded to a radical of an atom on molecule to form a covalent bond. For example, -CEE represents a methyl radical that is bonded to a radical atom so that a covalent bond is formed to form a methyl group bonded to the remaining portion of the molecule.

[0073] As used herein, the suffix “-ylene” refers to a diradical group that is bonded to two substituents to form two covalent bonds. For example, -CH2- represents a methylene diradical that is bonded to a radical atom on each side of the carbon so that two covalent bonds are formed to the remaining portions of the molecule. It should be understood that functional groups and substituents described herein with the “-yl” suffix can be readily envisaged to the corresponding “-ylene” suffix to bond to two separate substituents, for example alkyd and alkenyl (forming one bond) would become alkylene and alkenylene, respectively, when forming two bonds.

[0074] The term “substituted” means that the specified group or moiety bears one or more substituents. The term “unsubstituted” means that the specified group bears no substituents. Where the term “substituted” is used to describe a structural system, the substitution is meant to occur at any valency-allowed position on the system. In some embodiments, “substituted” means that the specified group or moiety bears one, two, or three substituents. In other embodiments, “substituted” means that the specified group or moiety bears one or two substituents. In still other embodiments, “substituted” means the specified group or moiety bears one substituent. Substituents can include any substituents described herein, for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxyl, a phosphoryl, a phosphate, a phosphonate. a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyL an aralkyl, or an aromatic or hetaryl moiety. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate.

[0075] As used herein, “optional” or “optionally” means that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not. For example, “wherein each hydrogen atom in Ci-Ce alkyd, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, 3-to 7-membered heterocycloalkyl, Ce-Cio aryl, or mono- or bicyclic hetaryl is independently optionally substituted by Ci-Ce alkyl” means that an alkyl may be but need not be present on any of the Ci-Ce alkyl. C2- Ce alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, 3-to 7-membered heterocycloalkyl, Ce-Cio aryl, or mono- or bicyclic hetaryl by replacement of a hydrogen atom for each alkyl group, and the description includes situations where the Ci-Ce alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl. 3-to 7-membered heterocycloalkyl, C6-C10 aryl, or mono- or bicyclic hetaryl is substituted with an alkyl group and situations where the Ci-Ce alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, 3-to 7-membered heterocycloalkyl, Ce-Cio aryl, or mono- or bicyclic hetaryl is not substituted with the alky l group.

[0076] As used herein, “ion” refers to a charged atom or compound. As used herein, “cation” refers to a positively charged ion and “anion” refers to a negatively charged ion. Representative examples of anions include, but are not limited to, halide, acetate, mesylate, tosylate, triflate, and bisulfate.

[0077] As used herein, “quaternary” or “quatemized” refers to a nitrogen-containing compound having a positively charged central nitrogen atom having four (non N-H) covalent bonds. Representative examples of quaternary or quatemized compounds (e.g., quaternary amines) include, but are not limited to, ammonium, imidazolium, pyrrolium, pyridinium, pyrazolium, pyrimidinium, and pyrazinium. A representative example of a quaternary or quatemized nitrogen group, such as a quaternary amine, includes a pyridine where the nitrogen atom is substituted by X', as depicted by the pyridinium structure: . wherein X’ represents oxide. carboxylate, alkyl-carboxylate, alkenyl-carboxylate, or alkynyl-carboxylate.

[0078] As used herein, "quatemizing agent” refers to a compound or reagent used to provide a quaternary7or quatemized compound. A quatemizing agent may be an oxidizing agent, an alkylating agent, or an acylating agent. It will be understood that in certain embodiments, that an oxidizing agent (e.g., H2O2) may be used to provide a compound (e.g., quaternary amine) with an oxide substituent, such as O It will be understood that in certain embodiments, that an alkylating agent (e.g., an alkyl carboxylate, such as a haloalkyl carboxylate) may be used to provide a compound (e.g., quaternary amine) with an alkyl substituent, such as It will be understood that in certain embodiments, that an acylating agent may be used to provide a compound with an acyl substituent.

[0079] As used herein, “polymer” means a substance or material composed of many repeating subunits, or “monomers.” As used herein, “copolymer” means a polymer composed of more than one monomer. Representative examples of polymers include, but are not limited to. polyvinylacetate, polyacrylamine, polyethylene, polyvinyl alcohol, polyvinylamine, polyvinylpyrrolidone, polyvinylpyridine-N-oxide, polyvinylimidazole, polyvinyl caprolactam, and polyvinyl pyridine. Representative examples of copolymers include, but are not limited to, any combination of two or more polymers listed herein.

[0080] As used herein, the term “betaine” refers to a compound with a positively charged cationic functional group that bears no hydrogen atom, such as a quaternary nitrogen (e.g., ammonium or pyridinium) or phosphonium cation, and with a negatively charged functional group, such as a carboxylate, that may not be directly adjacent to the cationic site. Illustrative examples of betaines include, but are not limited to, . Examples of a betaine surfactant include but are not limited to cocamidopropyl betaine (CAPB) (e.g., lauramidopropyl betaine) or castor amidopropyl betaine.

[0081] As used herein, the term “glycoside” refers to compounds formed from a sugar and another molecule. As used herein, the term “glucoside” refers to a glycoside where the sugar part is glucose. Examples of glycosides include but are not limited to alkyl glycoside (e.g., capryl, capric or lauryl glycoside, including any polymer thereof). An example of a glycoside surfactant, also referred to as a “sugar-derived” surfactant, includes alkyl polyglucoside based on a natural Cs-Cio fatty alcohol (J215UP).

[0082] As used herein, the term “biodegradable” refers to compounds that break down under certain conditions after the intended purpose by a decomposition process. Biodegradable polymers are found both naturally and synthetically, and largely consist of ester, anhydride, amide, and ether functional groups (e.g., cleavable linkages). For example, a biodegradable polymer, such as polymer comprising a polymer backbone functionalized with aromatic groups (e.g., aryl or hetaryl) through cleavable linkages, may degrade, thereby resulting in the release of the aromatic groups and the unfunctionalized polymer backbone. An example of a biodegradable polymer includes a PVOH polymer backbone functionalized with hetaryl groups through cleavable linkages (e.g., esters).

[0083] As used herein and in connection with chemical structures depicting the various embodiments described herein, the polymer comprising one or more units of formula I, formula II, and / or formula III may be arranged in any linear or branched configuration. For example, the polymer comprising one or more units of formula I. formula II, and / or formula III may be arranged as a homopolymer, a block copolymer of two homopolymers linked to form a single polymer chain, a random copolymer of monomers randomly linked in a given polymer chain, or an alternate copolymer of different monomers linked together in an alternating fashion. In one embodiment, the polymers described herein may include repeating blocks, such as in a tri-block copolymer, of units selected from formula I, formula II, and formula III.

[0084] As used herein and in connection with chemical structures depicting the various embodiments described herein, “*”, “**” and “^vw ”, each represent a point of covalent attachment of the chemical group or chemical structure in which the identifier is shown to an adjacent chemical group or chemical structure. For example, in a hypothetical chemical structure A-B, where A and B are joined by a covalent bond, in some embodiments, the portion of A-B

[0085] H A _ *" H A _ defined by the group or chemical structure A can be represented by , , or

[0086] >■ . _ s_ " _

[0087] A’ , where each of and “ ” represents a bond to A and the point of covalent bond attachment to B. Alternatively, in some embodiments, the portion of A-B defined by the group or chemical structure B can be represented by , where each of represents a bond to B and the point of covalent bond attachment to A. As used herein, ‘‘independently” means that the subsequently described event or circumstance is to be read on its own relative to other similar events or circumstances. For example, in a circumstance where several equivalent hydrogen groups are optionally substituted by another group described in the circumstance, the use of “independently optionally” means that each instance of a hydrogen atom on the group may be substituted by another group, where the groups replacing each of the hydrogen atoms may be the same or different. Or for example, where multiple groups exist all of which can be selected from a set of possibilities, the use of “independently” means that each of the groups can be selected from the set of possibilities separate from any other group, and the groups selected in the circumstance may be the same or different.

[0088] As used herein, “weight average molecular weight (Mw)” refers to a measure of the average molecular weight of a polymer. The weight average molecular weight (Mw) accounts for the relative abundance of different molecular weight fractions. It is calculated by summing the products of the number of molecules in each molecular weight fraction and their respective molecular weights, divided by the total number of molecules in the sample. In one example, the molecular weight of polymers was determined by Size Exclusion Chromatography using a Malvern Panalytical Omnisec GPC / SEC System. The average molecular weight and molecular weight distribution was determined by comparing their elution volume to a calibration curve generated with known polymer standards.

[0089] As used herein, “Delta E (AE)” refers to a measurement that quantifies the difference between two colors. For example, Delta E may be used to quantify the difference in color between a control cloth before contacting or interacting with a dye, and the same cloth after contacting or interacting with a dye. Delta E can be measured using a colorimeter, and determined as the difference in colorimeter (L, a, and b) values of a control (i.e., virgin white) cloth before and after the washing with a donor (i.e.. dyed or colored) cloth or dye solution. It would be understood that the greater the Delta E value, the greater color change observed. For example, a greater Delta E may represent a greater transfer of dye from the donor cloth or dye solution to the control cloth. Delta E can be calculated using the following formula, where L. a, and b represent the lightness and color-opponent dimensions in the Lab color space:

[0090] DETAILED DESCRIPTION

[0091] Before the present disclosure is further described, it is to be understood that this disclosure is not limited to particular embodiments described, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims.

[0092] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents, applications, published applications and other publications referred to herein are incorporated by reference in their entireties. If a definition set forth in this section is contrary to or otherwise inconsistent with a definition set forth in a patent, application, or other publication that is herein incorporated by reference, the definition set forth in this section prevails over the definition incorporated herein by reference.

[0093] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” "only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation.

[0094] As used herein, the terms “including,” “containing,” and “comprising” are used in their open, non-limiting sense.

[0095] To provide a more concise description, some of the quantitative expressions given herein are not qualified with the term “about.” It is understood that, whether the term “about” is used explicitly or not, every quantity given herein is meant to refer to the actual given value, and it is also meant to refer to the approximation to such given value that would reasonably be inferred based on the ordinary skill in the art. including equivalents and approximations due to the experimental and / or measurement conditions for such given value. Whenever a yield is given as a percentage, such yield refers to a mass of the entity for which the yield is given with respect to the maximum amount of the same entity7that could be obtained under the particular stoichiometric conditions. Concentrations that are given as percentages refer to mass ratios, unless indicated differently.

[0096] In some embodiments, the disclosure provides a composition comprising a polymer of the present disclosure (e.g., a polymer comprising formula I, formula II, and formula III).

[0097] In some embodiments, the disclosure provides a polymer comprising formula I, formula II, and formula III: or salts thereof, wherein A, B, L1, L2, L3, R1, R2, R3m, n, and o are as described herein. In some embodiments, formula I is of formula la or a salt thereof, wherein A. L1, X', and m are as described herein.

[0098] In some embodiments, formula I is of formula la- 1 or a salt thereof, wherein L1. X", and m are as described herein.

[0099] In some embodiments, formula I is of formula la-2 or a salt thereof, wherein X". and m are as described herein. In some embodiments, formula I is of formula lb or a salt thereof, wherein A, L1, X", and m are as described herein.

[0100] In some embodiments, formula I is of formula Ib-1

[0101] or a salt thereof, wherein L1. X", and m are as described herein.

[0102] In some embodiments, formula I is of formula Ic or a salt thereof, wherein L1, X", and m are as described herein.

[0103] In some embodiments, formula II is of formula Ila (iia), or a salt thereof, wherein A, L2, and n are as described herein. In some embodiments, formula II is of formula IIa-1 or a salt thereof, wherein n is as described herein.

[0104] In some embodiments, formula II is of formula IIa-2 or a salt thereof, wherein n is as described herein.

[0105] In some embodiments, formula II is of formula IIa-3 or a salt thereof, wherein n is as described herein.

[0106] In some embodiments, formula III is of formula Illa or a salt thereof, wherein A. L3, and o are as described herein.

[0107] In some embodiments, formula III is of formula IIIa-1 or a salt thereof, wherein L3and o are as described herein.

[0108] In some embodiments, formula I is of formula IIIa-2 or a salt thereof, wherein o is as described herein. In some embodiments, formula III is of formula Illb or a salt thereof, wherein A, L3, and o are as described herein.

[0109] In some embodiments, formula III is of formula IIIb-1 or a salt thereof, wherein L3and o are as described herein.

[0110] In some embodiments, formula III is of formula IIIc or a salt thereof, wherein L3and o are as described herein.

[0111] In some embodiments, the polymer comprises formula la-2, and formula Illa-2 or salts thereof, wherein X' is oxide, carboxylate, alkylene-carbox late. alkenylene- carboxylate, or alkynylene-carboxylate.

[0112] In some embodiments, the polymer comprises formula la-2, formula IIa-2, and formula

[0113] IIIa-2

[0114] or salts thereof, wherein X' is oxide, carboxylate, alk lene-carboxy late, alkenylene- carboxylate, or alkynylene-carboxylate.

[0115] A representative example of the polymer described herein may be a homopolymer of units selected from wherein A, B. L1. L2, L3,

[0116] R1, R2, and R3are as described herein. Another representative example of the polymer described herein may include blocks or repeating units, such as in a tri-block copolymer or alternating copolymer, of units selected from wherein A. B, L1, L2, L3, R1, R2. and R3are as described herein. Another representative example of the polymer described herein may include blocks or repeating units, such as in a diblock copolymer or alternating copolymer, of units selected from: ; wherein

[0117] A, B, L1, L2, L3, R1, R2, and R3are as described herein.

[0118] Another representative example of the polymer described herein may include a random configuration of units selected from: , wherein A,

[0119] B, L1, L2, L3, R1, R2, and R3are as described herein. Another representative example of the polymer described herein may include a random configuration of units selected from: ; wherein A, B, L1, L2, L3,

[0120] R1, R2, and R3are as described herein.

[0121] In some embodiments. A is O, NH, or alkylene (e.g., Ci-Ce alkylene, such as methylene or ethylene). In some embodiments. A is O. NH, or Ci-Ce alkylene. In some embodiments, A is O, NH, methylene, or ethylene. In some embodiments, A is O or Ci-Ce alkylene. In some embodiments, A is O, methylene, or ethylene.

[0122] In some embodiments, A is O, NH, or alkylene (e.g., Ci-Ce alkylene), provided that if B is N, then A is alkylene (e.g., Ci-Ce alkylene). In some embodiments, A is Ci-Cs alkylene (e.g.. methylene or ethylene), and B is N.

[0123] In some embodiments, B is alkylene (e.g., Ci-Ce alkylene such as methylene or ethylene) or N. In some embodiments, B is Ci-Ce alkylene or N. In some embodiments, B is methylene, ethylene, or N.

[0124] In some embodiments, B is alkylene or N, provided that if A is O or NH, then B is alkylene. In some embodiments, B is Ci-Ce alkylene (e.g., methylene or ethylene), and A is O or NH.

[0125] In some embodiments, each A and B is independently alky lene (e.g., Ci-Ce alky lene such as methylene or ethylene). In some embodiments, each A and B is methylene. In some embodiments, A is O and B is alkylene (e.g., Ci-Ce alkylene such as methylene or ethylene). In some embodiments, A is O and B is ethylene. In some embodiments, B is N and A is alky lene (e.g., Ci-Ce alkylene such as methylene or ethylene). In some embodiments, B is N and A is ethylene.

[0126] In some embodiments, each of L1, L2, and L3is independently a bond, alkylene, amino, amido, ester, carbonyl, alkylene-ester, alkylene-amido, or alkylamino. In some embodiments, each of L1and L3is independently alkylene, amino, amido, ester, carbonyl, alkylene-ester, alkylene-amido, or alkylamino. In some embodiments, each of L1and L3is independently alkylene, carbonyl, alkylene-ester. or alkylene-amido. In some embodiments, each of L1. L2. and L3is independently a bond, alkylene, amido, ester, carbonyl, alkylene-ester, or alkylene-amido. In some embodiments, each of L1and L3is independently alkylene, amino, alkylene-ester, alkylene-amido, or alkylamino. In some embodiments, each of L1and L3is independently alkylene, carbonyl, alkylene-ester, or alkylene-amido. In some embodiments, L1and L3are the same. In some embodiments, each of L1and L3are independently not a bond. In some embodiments, L1is a bond, alkylene, amino, amido, ester, carbonyl, alkyleneester, alkylene-amido, or alkylamino. In some embodiments, L1is alkylene, amino, amido, ester, carbonyl, alkylene-ester, alkylene-amido, or alkylamino. In some embodiments, L1is alkylene, carbonyl, alkylene-ester. or alkylene-amido. In some embodiments. L1is a bond, alkylene, amido, ester, carbonyl, alkylene-ester, or alkylene-amido. In some embodiments, L1is alkylene, amino, alkylene-ester, alkylene-amido, or alkylamino. In some embodiments, L1is alkydene, carbonyl, alkylene-ester, or alkylene-amido. In certain preferred embodiments, L1is ester or amido. In some embodiments, L1is not a bond.

[0127] In some embodiments, L2is a bond, ester, carbonyl, amido, alkylamino, or amino. In some embodiments, L2is a bond or ester. In certain preferred embodiments, L2is a bond or amino.

[0128] In some embodiments, L3is a bond, alkylene, amino, amido, ester, carbonyl, alkylene- ester, alkylene-amido, or alkylamino. In some embodiments, L3is alkylene, amino, amido, ester, carbonyl, alkylene-ester, alkylene-amido, or alkylamino. In some embodiments, L3is alkylene, amido, ester, carbonyl, alkylene-ester, or alkylene-amido. In some embodiments, L3is an alkylene, amido, ester, alkylene-ester, or alky lene-amido. In some embodiments, L3is alkylene, amino, alkylene-ester, alkylene-amido, or alkylamino. In certain preferred embodiments, L3is ester or amido. In some embodiments, L3is not a bond.

[0129] In some embodiments, each L1and L3is an ester and L2is a bond. In some embodiments, each L1and L3is amido and L2is amino.

[0130] In certain preferred embodiments. L1is ester or amido, wherein “ * ” represents a point of attachment to L1.

[0131] In certain preferred embodiments, L2is a bond or amino, and R2is H or OH.

[0132] In certain preferred embodiments, L3is ester or amido, wherein “ * represents a point of attachment to L3.

[0133] In some embodiments, X’ is oxide, carboxylate, alkylene-carboxylate, alkenylene- carboxylate, or alkynylene-carboxylate. In some preferred embodiments, X’ is oxide or alkylenecarboxylate. In some preferred embodiments, X" is oxide. In some preferred embodiments, X" is alkylene-carboxylate (e.g., Ci-Ce alkylene-carboxylate such as methylene-carboxylate). In some embodiments, R1is hetaryl (e.g., a six-membered hetaryl such as pyridyl) and comprises a quaternary' amine. In some embodiments, R1is pyridinium substituted with X".

[0134] In some embodiments, , wherein ” represents a point of attachment to L1. In certain preferred embodiments, , wherein “ * ” represents a point of attachment to L1. In some embodiments, R1is selected from the group consisting of attachment to L1. In some embodiments, R2is H, OH, or alkyl (e.g., methyl). In certain preferred embodiments, R2is H or OH. In some embodiments, when L2is a bond, then R2is OH (e.g., L2- R2is -OH). In some embodiments, when L2is amino, then R2is H (e g., L2-R2is -NH3). In some embodiments, when L2is ester, then R2is alkyl (e.g., L2-R2is -OC(O)CH3).

[0135] In some embodiments, R3is hetaryl (e.g., a six-membered hetaryl such as pyridyl). For example, R3can wherein “ * ” represents a point of attachment to L3. In certain preferred embodiments, wherein “ * ” represents a point of attachment to L3.

[0136] In some embodiments, m is an integer greater than 0. In some embodiments, m is an integer between 1 and 500. In some embodiments, m is an integer between 1 and 400. In some embodiments, m is an integer between 1 and 300. In some embodiments, m is an integer between 10 and 500. In some embodiments, m is an integer between 10 and 400. In some embodiments, m is an integer between 10 and 300.

[0137] In some embodiments, n is zero or an integer greater than 0. In some embodiments, n is zero or an integer between 1 and 500. In some embodiments, n is zero or an integer between 1 and 400. In some embodiments, n is zero or an integer between 1 and 300. In some embodiments, n is an integer between 10 and 500. In some embodiments, n is an integer between 10 and 400. In some embodiments, n is an integer between 10 and 300.

[0138] In some embodiments, o is zero or an integer greater than 0. In some embodiments, o is zero or an integer between 1 and 500. In some embodiments, o is zero or an integer between 1 and 400. In some embodiments, o is zero or an integer between 1 and 300. In some embodiments, o is an integer between 10 and 500. In some embodiments, o is an integer between 10 and 400. In some embodiments, o is an integer between 10 and 300.

[0139] In some embodiments, the sum of n, m, and o is an integer between 1 and 500. In some embodiments, the sum of n, m, and o is an integer between 1 and 400. In some embodiments, the sum of n, m, and o is an integer between 10 and 500. In some embodiments, the sum of n, m, and o is an integer between 10 and 400. In some embodiments, the sum of n, m. and o is an integer between 20 and 500. In some embodiments, the sum of n, m, and o is an integer between 20 and 400.

[0140] In some embodiments, the ratio of n to o is from about 1 : 1 to about 20: 1. In some embodiments, the ratio of n to o is from about 1: 1 to about 15: 1. In some embodiments, the ratio of n to o is from about 1: 1 to about 10: 1. In some embodiments, the ratio of n to o is from about 2: 1 to about 20: 1. In some embodiments, the ratio of n to o is from about 2: 1 to about 15: 1. In some embodiments, the ratio of n to o is from about 2: 1 to about 10: 1. In some embodiments, the ratio of n to o is from about 3: 1 to about 20: 1. In some embodiments, the ratio of n to o is from about 3 : 1 to about 15 : 1. In some embodiments, the ratio of n to o is from about 3 : 1 to about 10 : 1.

[0141] In some embodiments, the polymer has a weight average molecular weight (Mw) of greater than about 500 Da. In some embodiments, the polymer has a weight average molecular weight of greater than about 1 ,000 Da. In some embodiments, the polymer has a weight average molecular weight of from about 2,000 Da to about 50,000 Da. In some embodiments, the polymer has a weight average molecular weight of from about 8,000 Da to about 10,000 Da. In some embodiments, the polymer has a weight average molecular weight of from about 10.000 Da to about 35,000 Da. In some embodiments, the polymer has a weight average molecular weight of from about 10,000 Da to about 25,000 Da, about 15,000 Da to about 25,000 Da, or about 10,000 Da to about 20,000 Da. Molecular weight can be determined from the degree of modification (e.g.. acylation or alkylation) of the base polymer with a known molecular weight, and as further described herein.

[0142] In some embodiments, the polymer comprises at least about 30 mol% of formula I. In some embodiments, the polymer comprises at least about 50 mol% of formula I. In some embodiments, the polymer comprises about 30 mol% to about 90 mol% of formula I. In some embodiments, the polymer comprises about 30 mol% to about 85 mol% of formula I. In some embodiments, the polymer comprises about 30 mol% to about 80 mol% of formula I. In some embodiments, the polymer comprises about 30 mol% to about 75 mol% of formula I. In some embodiments, the polymer comprises about 50 mol% to about 90 mol% of formula I. In some embodiments, the polymer comprises about 50 mol% to about 85 mol% of formula I. In some embodiments, the polymer comprises about 50 mol% to about 80 mol% of formula I.

[0143] In some embodiments, the polymer comprises less than about 50 mol% of formula II. In some embodiments, the polymer comprises less than about 40 mol% of formula II. For example, the polymer may comprise 0 mol% to about 50 mol%, 0 mol% to about 45 mol%. 0 mol% to about 40 mol%, 0 mol% to about 35 mol%, 0 mol% to about 30 mol%, 0 mol% to about 25 mol%, 0 mol% to about 20 mol%, 0 mol% to about 15 mol%, 0 mol% to about 10 mol%, or 0 mol% to about 5 mol% of formula II.

[0144] In some embodiments, the polymer comprises less than about 50 mol% of formula III. In some embodiments, the polymer comprises less than about 40 mol% of formula III. For example, the polymer may comprise 0 mol% to about 50 mol%, 0 mol% to about 45 mol%, 0 mol% to about 40 mol%, 0 mol% to about 35 mol%, 0 mol% to about 30 mol%, 0 mol% to about 25 mol%, 0 mol% to about 20 mol%, 0 mol% to about 15 mol%, 0 mol% to about 10 mol%, or 0 mol% to about 5 mol% of formula III.

[0145] In some embodiments, the polymer is biodegradable. In some embodiments, the polymer is water soluble. The advantage of a biodegradable dye transfer inhibitor is to minimize the introduction of microplastics into the environment. With polymers of the present disclosure, a composition that yields similar performance to comparative dye transfer inhibitors and functions well with other biodegradable components like the alkyl glucoside surfactants would be advantageous.

[0146] In some embodiments, the composition comprises a first polymer and a second polymer, each independently comprising formula 1. formula II. and formula III, wherein the first polymer is present at a first range of molecular weights (e.g., about 2,000 to about 10,000) and the second polymer is present a second range of molecular weights (e.g., about 20,000 to about 30,000) that is different from the first range.

[0147] In some embodiments, the composition according to the present disclosure is a laundry product, such as a laundry detergent. In some embodiments, the composition according to the present disclosure is an additive that may be added to a laundry product, such as a laundry detergent.

[0148] In some embodiments, the composition comprises an aqueous solvent (e.g., water). In some embodiments, the composition comprises an additive selected from the group consisting of enzymes, neutralizers, brighteners, builders, chelants, scavengers, perfumes, and any combination thereof.

[0149] In some embodiments, the polymer is present at a concentration of about 1 ppm to about 10.000 ppm in the composition, for example, at a concentration of about 1 ppm to about 1000 ppm, about 1 ppm to about 500 ppm, or about 20 ppm to about 200 ppm in the composition. In some embodiments, the polymer is present at a concentration of about 0.001 wt% to about 10 wt% in the composition, for example, at a concentration of about 0.01 wt% to about 3 wt% in the composition, about 0.1 wt% to about 3 wt%. about 0.5 wt% to about 3%, or about 0.5 wt% to about 2.5 wt%.

[0150] In some embodiments, the composition comprises a surfactant, for example a surfactant that is present in a detergent such as a laundry' detergent. The surfactant may be a sulfate surfactant, a sulfonate surfactant, a sultaine surfactant, a betaine surfactant, a sugar-derived surfactant, or any combination thereof. In some embodiments, the surfactant is a not a sulfonate. In some embodiments, the surfactant is selected from the group consisting of, sodium alkyd sulfate (e.g., sodium dodecyl sulfate), sodium alkyd benzyl sulfonate (e.g., sodium dodecyl benzyl sulfonate), cocamidopropyl hydroxysultaine (e.g., laurylamidopropyl hydroxysultaine). cocamidopropyl betaine (e.g., laurylamidopropyl betaine), castor amidopropyl betaine, and alkyl glycoside (e.g., capryl, capric or laury l glycoside, including any polymer thereof). In some embodiments, the surfactant comprises an alkyl group (e.g., Ce-Ci8 alkyl).

[0151] In some embodiments, the surfactant is present at a concentration of about 1% to about 50% in the composition, for example, at a concentration of about 10% to about 50% in the composition. In some embodiments, a process for preparing a polymer of the present disclosure comprises the steps of i. contacting a polymer backbone with a hetaryl under conditions suitable to provide a functionalized polymer; and ii. contacting the functionalized polymer with a quatemizing agent under conditions suitable to provide the polymer.

[0152] In some embodiments, the polymer backbone is polyvinyl alcohol (PVOH) or polyvinyl amine (PVAm). In certain preferred embodiments, the polymer backbone is polyvinyl alcohol (PVOH). In some embodiments, the polyvinyl alcohol (PVOH) is about 60% to about 100% hydrolyzed, or about 70% to about 90% hydrolyzed (e.g., about 80% hydrolyzed).

[0153] In some embodiments, the polymer backbone is a polymer comprising formula II.

[0154] In some embodiments, the hetaryl is a pyridine carbonyl chloride, such as picolinoyl chloride, nicotinoyl chloride, or isonicotinoyl chloride. In some embodiments, the hetaryl is of

[0155] ° -CI the formula 0N

[0156] In some embodiments, the functionalized polymer is a polymer comprising formula III. In some embodiments, the functionalized polymer is a polymer comprising formula II and formula III.

[0157] In some embodiments, step i comprises contacting the polymer backbone with a hetaryl in a solvent, such as pyridine. In some embodiments, step i comprises contacting the polymer backbone with a hetaryl at a temperature of about 30 °C to about 100 °C (e.g., about 40 °C to about 50 °C). In some embodiments, step i comprises contacting the polymer backbone with a hetaryl for about 2 hours to about 24 hours (e.g., about 8 hours to about 20 hours).

[0158] In some embodiments, step i comprises contacting the polymer backbone with a hetaryl to provide an ester or an amide. In some embodiments, step i comprises esterification of the polymer backbone with a hetaryl.

[0159] In some embodiments, the quatemizing agent is an oxidizing agent, an alkylating agent, or an acylating agent, and is preferably an oxidizing agent, for example H2O2. In some embodiments, the oxidizing agent is used in the presence of a catalyst, for example, Na2WO4. In some embodiments, the quatemizing agent is an alkylating agent. In some embodiments, the quatemizing agent is an alkyl carboxylate (e.g., a haloalkyl carboxylate), such sodium 2- chloroacetate. In some embodiments, step ii comprises contacting the functionalized polymer with a quatemizing agent in the presence of a salt, such as sodium iodide, or potassium iodide. In some embodiments, step ii comprises contacting the functionalized polymer with a quatemizing agent in a solvent, such as water, methanol, ethanol, or a combination thereof. In some embodiments, step ii comprises contacting the functionalized polymer with a quatemizing agent at a temperature of about 30 °C to about 100 °C (e.g., about 40 °C to about 50 °C). In some embodiments, step ii comprises contacting the functionalized polymer with a quatemizing agent for about 2 hours to about 24 hours (e.g.. about 4 hours to about 16 hours).

[0160] In some embodiments, the disclosure relates to an article of the composition according to the present disclosure conjugated to a solid support.

[0161] In some embodiments, the polymer described herein is used in a method of inhibiting a transfer of a dye in an aqueous solution. For example, the polymer can be used in a method that comprises the polymer contacting the dye in an aqueous solution, which may cause the polymer to bind (complex) the dye. In some embodiments, the binding (complexing) of the dye prevents the redeposit of the dye. In some embodiments, the method comprises the polymer contacting the dye in an aqueous solution, thereby binding the dye, and inhibiting a redeposit of a dye.

[0162] In some embodiments, the polymer is present at a concentration of about 1 ppm to about 500 ppm in the aqueous solution, for example, at a preferably concentration of about 20 ppm to about 200 ppm, or about 50 ppm to about 150 ppm in the aqueous solution. In some embodiments, the polymer is present at a concentration of about 25 ppm, about 50 ppm, about 60 ppm, about 70 ppm, about 75 ppm, about 80 ppm. about 90 ppm, about 100 ppm, about 110 ppm, about 120 ppm, about 125 ppm, about 130 ppm, about 140 ppm, about 150 ppm, about 200 ppm, about 250 ppm, about 300 ppm, about 400 ppm, or about 500 ppm in the aqueous solution.

[0163] In some embodiments, the surfactant is present at a concentration of about 0.001 wt% to about 10 wt% in the aqueous solution, for example, at a concentration of about 0.01 wt% to about 5 wt%, or preferably at a concentration of about 0.01 wt% to about 1 wt% in the aqueous solution. In some embodiments, the surfactant is present at a concentration of about 0.01 wt%, about 0.05 wt%, about 0. 1 wt%, about 0. 15 wt%, about 0.2 wt%, about 0.25 v %, about 0.3 v %, about 0.35 wt%, about 0.4 wt%, about 0.45 wt%, or about 0.5 wt% in the aqueous solution.

[0164] In some embodiments, the polymer binds to a dye, for example a dye used to dye fabric. The dye may be a red dye, an orange dye, a yellow dye, a green dye, a blue dye, a purple dye, a brown dye, a gray dye, a black dye, or any combination thereof. In some embodiments, the dye is a red dye, a blue dye, or combination thereof.

[0165] In some embodiments, the method provides a AE (i.e., a measurement of dye transfer) of less than about 40, wherein AE is determined according to the method of ASTM D5548 (e.g.. ASTM D5548-95 or ASTM D5548-13). In some embodiments, the AE is less than about 20. In some embodiments, the AE is less than about 30. In some embodiments, the AE is less than about 15. In some embodiments, the AE is less than about 10. In some embodiments, the AE is less than about 10. In some embodiments, the AE is less than about 5. In some embodiments, the AE is less than about 2. In some embodiments, the AE is between zero and about 1, about 1.2, about

[0166] 1.4, about 1.6, about 1.8, about 2.0, about 2.2, about 2.4, about 2.6, about 2.8, and about 3.0. For example, the AE may be between 0 and about 1.0, 0 and about 1.5, 0 and about 2.0, 0 and about

[0167] 2.5, or 0 and about 3.0.

[0168] In some embodiments, the disclosure relates to a polymer having a backbone, the polymer comprising: a first monomer comprising a hetaryl group comprising a quaternary amine, wherein the hetaryl group is conjugated to the backbone through alkylene, ester, carbonyl, amino, amido, alkylene-ester, alkylene-amido, or alkylamino; a second monomer comprising a hetaryl group, wherein the hetaryl group is conjugated to the backbone through alkylene, ester, carbonyl, amino, amido, alkylene-ester, alkyleneamido, or alkylamino; and a third monomer comprising H, OH, ester, carbony l, amino, or amido conjugated to the backbone.

[0169] In some embodiments, the first monomer is of formula I according to the present disclosure. In some embodiments, the third monomer is of formula II according to the present disclosure. In some embodiments, the second monomer is of formula III according to the present disclosure.

[0170] In some embodiments, the backbone is a polyvinyl polymer.

[0171] EXAMPLES

[0172] The examples and preparations provided below further illustrate and exemplify particular aspects of embodiments of the disclosure. It is to be understood that the scope of the present disclosure is not limited in any way by the scope of the following examples. Example 1:

[0173] X" = oxide or -CH2CO2

[0174] 13.1 g (200 mmol func. eqv.) poly(vinyl alcohol), having a molecular weight average of A / w= 2,000 to 20,000 g / mol, and a degree of hydrolysis of 60 to 100%, is dissolved in 300 mL pyridine at reflux and subsequently cooled down to room temperature.

[0175] To this solution, 35.8 g (200 mmol) of a pyridine carbonyl chloride HC1 salt, selected from the group of picolinoyl chloride hydrochloride, nicotinoyl chloride hydrochloride, and isonicotinoyl chloride hydrochloride, is added in portions maintaining a temperature below 30 °C. After full addition, the mixture is stirred at 50 °C for 8 hours yielding a tan slurry.

[0176] The mixture is cooled dow n to room temperature and the suspended solids are filtered off, after which the solvent is removed by distillation. The concentrated product is redissolved in dimethylsulfoxide and purified by precipitation in water. The light yellow, highly viscous precipitate is then dried to an amber glass at 50 °C under vacuum, yielding poly(vinyl pyridinate hydrochloride).

[0177] In one embodiment, 0.066 g (0.2 mmol) sodium tungstate dihydrate is dissolved in 500 mL water and the mixture is heated to a temperature of about 50 °C to about 80 °C. Then, 20.8 g (100 mmol func. eqv.) poly(vinyl pyridinate hydrochloride) is powdenzed and is added in portions under strong agitation to form a suspension. Then, 13.0 g 30% hydrogen peroxide (115 mmol) is subsequently added and the mixture is stirred for 8 hours until homogenous. The mixture is then heated to 80 °C for another 2 hours, yielding a pale yellow aqueous solution of poly(vinyl pyridinate A-o.xide).

[0178] In another embodiment, 20.8 g (100 mmol func. eqv.) poly(vinyl pyridinate hydrochloride) and 0.9 g sodium iodide (6 mmol) is dissolved in a mixture of 450 mL methanol and 100 mL water.

[0179] A solution of 16.4 g sodium 2-chloroacetate (140 mmol) in 50 mL water is added dropwise over a period of 1 hour. After full addition, the mixture is stirred at 50 °C for 6 hours. The methanol is subsequently removed by fractional distillation, yielding a pale yellow aqueous solution of poly(vinyl pyridinate A-methylenecarboxylate).

[0180] Example 2:

[0181] Step 1: Preparation of polyvinyl (9-10K) nicotinate

[0182] To a 500mL 4N flask pyridine (280 g, 285 mL, 15.0 eq., 3.54 mol), and Poly(vinyl alcohol). 9- 10k, 80% hydrolyzed (13.0 g, 1 eq., 236 mmol) were charged. The mixture was stirred and brought to reflux until fully dissolved. Heating was discontinued and the solution was cooled to 20 °C. To this solution, nicotinoyl chloride hydrochloride (45.6 g, 95% Wt, 1.03 Eq, 243 mmol) was added portion wise over 30 minutes (5-10 g portions), maintaining temperatures between 20- 30 °C. Reaction mixture was then warmed to 40 °C for 18 hours until conversion to ester product had ceased. The product slurry mixture was filtered through a pad of Celite to remove the pyridine hydrochloride. The resultant solution was concentrated to dryness to afford an orange, gummy material. To this, DMSO (75 g) was added to RBF and rotated on a rotary' evaporator at 50 °C until fully dissolved. A dark amber viscous solution resulted. This solution was added to 750 mL H2O in a 2L 4N-RBF over 2 hours. The tacky were filtered away from the supernatant and dried under at 50 °C affording poly(vinyl nicotinate) as an amber glass (16.4 g, 47% yield).

[0183] Step 2: Preparation of polyvinyl nicotinoyl betaine

[0184] In a 1000 mL 4 N RBF fit was charged poly(vinyl nicotinate) (32.3 g, 1 eq., 217 mmol), methanol (180 g), water (20 g) and sodium iodide (6.5 g, 43 mmol) was stirred at 60 °C. To this, a solution of sodium 2-chloroacetate (35.3 g, 98% Wt, 1.4 Eq, 303 mmol) in water (78 g) was added via a syringe pump over 60 minutes. The resulting reaction solution was stirred at 60 °C for 12 hours. Methanol was removed to yield polyvinyl nicotinoyl betaine as a clear reaction pale yellow solution (212 g).

[0185] Example 3:

[0186] The effectiveness of the polymers of the invention as a dye transfer inhibition additive in a laundry detergent composition was evaluated using ASTM D5548-95 or ASTM D5548-13 to measure tested samples against control in a test simulating actual laundry washing conditions.

[0187] Testing parameters used in Examples 4 and 5 are shown in Table 1.

[0188] Table 1. Parameters of the ASTM testing methods.

[0189] Example 4:

[0190] The effectiveness of the polymers of the invention as a dye transfer inhibition additive in a laundry detergent composition was evaluated using ASTM D5548-95 to measure tested samples against control in a test simulating actual laundry washing conditions. Delta E (AE) was measured as the difference in colorimeter values (Z, a, and b) of a virgin white cloth before and after the washing with a donor cloth with the dye color as indicated in Tables 2-4. A Delta E value was categorized, and Delta E values of 0-2.00 were indicated as “A,” 2.01-5.00 were indicated as “B,” 5.01-10.00 were indicated as “C,” 10.01-20.00 were indicated as “D,” and greater than 20.00 were indicated as “E.’" Delta E was calculated using the following formula, where L. a, and b represent the lightness and color-opponent dimensions in the Lab color space:

[0191] The exemplary DTI was polyvinyl ni cotinoyl betaine (DTI-1 and DTI-2). Comparison was made against poly(4-vinylpyridine A-oxide) (PVNO), poly(4-vinylpyndine betaine) (CHROMABOND™ S-100, available from Aurorium), poly(vinylpyrrolidone) (PVP, K-30 available from NKY Pharma), and copolymer of N-vinylpyrrolidone and N-vinylimidazole (NOKESHO® 55, available from NKY Pharma). The surfactant, such as sodium dodecyl benzenesulfonate (SDBS). alkyl polyglucoside based on a natural Cs-Cio fatty alcohol (J215UP). or cocamidopropyl betaine (CABP), was present as 0.2 wt%. The DTI was present at 100 ppm. Table 2. Results of ASTM D5548-95 testing with Blue 71 dye cloth.

[0192] Table 3. Results of ASTM D5548-95 testing with Blue 90 dye cloth.

[0193]

[0194] Table 4. Results of ASTM D5548-95 testing with Red 151 dye cloth. Example 5:

[0195] The effectiveness of the polymers of the invention as a dye transfer inhibition additive in alaundry detergent composition was evaluated using ASTM D5548-13 to measure tested samples against control in a test simulating actual laundry washing conditions. Delta E (AE) was measured as the difference in colorimeter (L. a, and b) values of a virgin white cloth before and after the washing with a donor cloth with the dye color as indicated in Tables 5-7. A Delta E value was categorized, and Delta E values of 0-2.00 were indicated as “A,” 2.01-5.00 were indicated as “B,” 5.01-10.00 were indicated as “C,’?10.01-20.00 were indicated as “D,” and greater than 20.00 were indicated asC'E.” Delta E was calculated using the following formula, where L, a, and b represent the lightness and color-opponent dimensions in the Lab color space:

[0196] The exemplary DTI was polyvinyl ni cotinoyl betaine (DTI-1 and DTI-2). Comparison was made against poly(4-vinylpyridine A-oxide) (PVNO), poly(4-vinylpyridine betaine) (CHROMABOND™ S-100, available from Aurorium), poly(vinylpyrrolidone) (PVP, K-30 available from NKY Pharma), and copolymer of N-vinylpyrrolidone and N-vinylimidazole (NOKESHO® 55, available from NKY Pharma). The surfactant, such as sodium dodecyl benzenesulfonate (SDBS), alkyl poly glucoside based on a natural C8 - CIO fatty alcohol (J215UP), or cocamidopropyl betaine (CABP), was present as 0.2 wt%. The DTI was present at 100 ppm.

[0197] Table 5. Results of ASTM D5548-13 testing with Blue 71 dye cloth.

[0198] Table 6. Results of ASTM D5548-13 testing with Blue 90 dye cloth.

[0199] Table 7. Results of ASTM D5548-13 testing with Red 151 dye cloth.

Claims

WHAT IS CLAIMED IS:I . A composition comprising a polymer, wherein the polymer comprises formula I, formulaII, and formula III:III. or salts thereof, whereinA is O, NH, or alkylene; provided that if B is N, then A is alkylene;B is alkylene or N, provided that if A is O or NH, then B is alkylene; each of L1, L2, and L3is independently a bond, alkylene, amino, amido, ester, carbonyl, alkylene-ester. alkylene-amido, or alkylamino;R1is hetaryl, and comprises a quaternary amine;R2is H, OH, or alkyl;R3is hetary l, and does not include a quaternary amine; m is an integer greater than 0; n is 0 or an integer greater than 0; and o is 0 or an integer greater than 0; wherein “” denote points of attachment of each formula, when present, to the rest of the polymer; and wherein the polymer has a weight average molecular weight of greater than about 500 Da.

2. The composition of claim 1, wherein R1is a six -membered hetaryl and comprises a quaternary7amine.

3. The composition of any one of the preceding claims, wherein R1is pyridyl and comprises a quaternary' amine.

4. The composition of any one of the preceding claims, wherein R3is a six-membered hetaryl and does not include a quaternary amine.

5. The composition of any one of the preceding claims, wherein R3is pyridyl and does not include a quaternary amine.

6. The composition of any one of the preceding claims, wherein formula I is of formula la and formula III is of formula IllaIlla or salts thereof, wherein X‘ is oxide, carboxylate, alkylene-carboxylate. alkenylene- carboxylate, or alkynylene-carboxylate.

7. The composition of any one of the preceding claims, wherein formula I is of formula la-1 and formula III is of formula Illa- 1or salts thereof, wherein X‘ is oxide, carboxylate, alkylene-carboxylate, alkenylene- carboxylate, or alkynylene-carboxylate.

8. The composition of claim 7, wherein each of L1and L3is independently alkydene, amino, amido, ester, carbonyl, alkyl ene-ester, alkylene-amido, or alkylamino.

9. The composition of any one of claims 1-5, wherein formula I is of formula lb and formula III is of formula IllbIllb or salts thereof, wherein X‘ is oxide, carboxylate, alky lene-carboxylate, alkenylene- carboxylate, or alkynylene-carboxylate.

10. The composition of claim 9, wherein each of L1and L3is independently alkydene, carbonyl, alkylene-ester, or alky lene-amido.

11. The composition of any one of claims 1-5 and 9, wherein formula I is of formula Ib-1 and formula III is of formula IIIb-1IIIb-1 or salts thereof, wherein X' is oxide, carboxylate, alkylene-carboxylate. alkenylene- carboxylate, or alkynylene-carboxylate.

12. The composition of claim 11, wherein each of L1and L3is independently alkylene, amino, alkylene-ester, alkylene-amido, or alkylamino.

13. The composition of any one of claims 1-6, wherein formula I is of formula Ic and formula III is of formula IIIcIIIcor salts thereof, wherein X‘ is oxide, carboxylate, alkylene-carboxylate. alkenylene- carboxylate, or alkynylene-carboxylate.

14. The composition of claim 13, wherein each of L1and L3is independently alkylene, carbonyl, alkylene-ester, or alkylene-amido.

15. The composition of any one of claims 1-8, wherein each of L1and L3is an ester.

16. The composition of any one of claims 1-8 and 15, wherein formula I is of formula la-2 and formula III is of formula IIIa-2IIIa-2 or salts thereof, wherein X‘ is oxide, carboxylate, alkylene-carboxylate. alkenylene- carboxylate, or alkynylene-carboxylate.

17. The composition of any one of the preceding claims, wherein R1iswherein:“ * ” represents a point of attachment to L1; andX" is oxide, carboxylate, alkylene-carboxylate, alkenylene-carboxylate, or alkynylene- carboxylate.

18. The composition of any one of the preceding claims, wherein R1iswherein:“ * ” represents a point of attachment to L1: andX" is oxide, carboxylate, alkylene-carboxylate, alkenylene-carboxylate, or alkynylene- carboxylate.

19. The composition of any one of claims 6 to 18, wherein X" is oxide or alkylenecarboxylate.

20. The composition of any one of claims 6 to 18, wherein X" is oxide.

21. The composition of any one of claims 6 to 18, wherein X" is alkylene-carboxylate.

22. The composition of any one of claims 6 to 18 and 21, wherein X" is Ci-Cs alkylenecarboxylate.

23. The composition of any one of claims 6 to 18, 21 and 22, wherein X" is methylenecarboxylate.

24. The composition of claim 1, wherein R1is selected from the group consisting ofwherein “ * ” represents a point of attachment to L1.

25. The composition of any one of the preceding claims, wherein R3iswherein ” represents a point of attachment to L3.

26. The composition of any one of the preceding claims, wherein L2is a bond, ester, carbonyl, amido, alkylamino, or amino.

27. The composition of any one of the preceding claims, wherein L2is a bond, ester, or amino.

28. The composition of any one of the preceding claims, wherein R2is H, OH, or Ci-Ce alkyl.

29. The composition of any one of the preceding claims, wherein R2is H, OH, or methyl.

30. The composition of any one of the preceding claims, wherein R2is H or OH.31 . The composition of any one of the preceding claims, wherein the polymer comprises at least about 30 mol% of formula I.

32. The composition of any one of the preceding claims, wherein the polymer comprises at least about 50 mol% of formula I.

33. The composition of any one of the preceding claims, wherein the polymer comprises about 50 mol% to about 75 mol% of formula I.

34. The composition of any one of the preceding claims, wherein the polymer has a weight average molecular weight of from about 2,000 Da to about 50,000 Da.

35. The composition of claim 34, wherein the polymer has a weight average molecular weight of from about 8,000 Da to about 10,000 Da.

36. The composition of claim 34, wherein the polymer has a weight average molecular weight of from about 10,000 Da to about 35,000 Da.

37. The composition of any one of the preceding claims, wherein the polymer is water soluble.

38. The composition of any one of the preceding claims, wherein the polymer is biodegradable.

39. The composition of anyone of the preceding claims, wherein the composition comprises a first and a second polymer, each independently comprising formula I, formula II, and formula III, wherein the first polymer is present at a first range of molecular weights (e.g., about 2,000 to about 10,000) and the second polymer is present a second range of molecular weights (e.g., about 20,000 to about 30,000) that is different from the first range.

40. The composition of any one of the preceding claims, wherein the composition comprises a surfactant.

41. The composition of claim 40, wherein the surfactant is a sulfate surfactant, a sulfonate surfactant, a sultaine surfactant, a betaine surfactant, a sugar-derived surfactant, or any combination thereof.

42. The composition of claim 40, wherein the surfactant is a not a sulfonate.

43. The composition of any one of claims 40 to 42, wherein the surfactant is present at a concentration of from about 0.001% to about 10%.

44. The composition of claim 43, wherein the surfactant is present at a concentration of from about 0.01% to about 5%.

45. The composition of claim 43, wherein the surfactant is present at a concentration of from about 0.01% to about 1%.

46. An article comprising the polymer of any one of the preceding claims conjugated to a solid support.

47. A polymer having a backbone, the polymer comprising: a first monomer comprising a hetaryl group comprising a quaternary amine, wherein the hetaryl group is conjugated to the backbone through alkylene, ester, carbonyl, amino, amido, alkylene-ester, alkylene-amido, or alkylamino; a second monomer comprising a hetaryl group, wherein the hetaryl group is conjugated to the backbone through alky lene, ester, carbonyl, amino, amido, alkylene-ester, alkyleneamido. or alkylamino; and a third monomer comprising H, OH, ester, carbonyl, amino, or amido conjugated to the backbone; wherein the polymer has a weight average molecular weight of greater than about 500 Da.

48. The polymer of claim 47, wherein the first monomer is of formula II or a salt thereof, whereinA is O, NH, or alkylene;B is alkylene or N. provided that if A is O or NH. then B is alkylene;L1is alkylene, ester, carbonyl, alkylene-ester, alkylene-amido, alkylamino, amino, or amido;R1is hetar l. and comprises a quaternary amine; and wherein ”” denote points of attachment of the first monomer to the rest of the polymer.

49. The polymer of claim 47 or 48, wherein the third monomer is of formula IIor a salt thereof, wherein:A is O, NH, or alkylene;B is alkylene or N, provided that if A is O or NH, then B is alkylene;L2is a bond, ester, carbonyl, amido, alkylamino, or amino;R2is H, OH. or alkyl; and wherein the “ ” denote points of attachment of the third monomer to the rest of the polymer.

50. The polymer of any one of claims 47 to 49, wherein the second monomer is of formula IIIIII or a salt thereof, wherein:A is O, NH, or alkylene;B is alkylene or N, provided that if A is O or NH, then B is alkylene;L3is alkylene, ester, carbonyl, alkylene-ester, alkylene-amido. alkylamino, amino, or amido;R3is or hetaryl, and does not include a quaternary amine; and wherein the “” denote points of attachment of the second monomer to the rest of the polymer.

51. A process for preparing the polymer of any one of claims 1 to 45 comprising i. contacting a polymer backbone with a hetaryl under conditions suitable to provide a functionalized polymer; andii. contacting the functionalized polymer with a quatemizing agent under conditions suitable to provide the polymer.

52. The process of claim 51 , wherein the quatemizing agent is an oxidizing agent, an alkylating agent, or an acylating agent.

53. The process of claim 51 or 52. wherein the quatemizing agent is an oxidizing agent.

54. The process of claim 53, wherein the oxidizing agent is H2O2.

55. The process of claim 51 or 52, wherein the quatemizing agent is an alkylating agent.

56. A method for inhibiting a transfer of a dye in an aqueous solution, the method comprising: contacting the dye in an aqueous solution with the composition of any one of claims 1 to45.

57. The method of claim 56, wherein the method comprises the polymer binding to the dye.

58. The method of claim 56 or 57, wherein the transfer of a dye comprises the redeposit of the dye.

59. The method of any one of claims 56 to 58, wherein the polymer is present at a concentration of from about 1 ppm to about 500 ppm in the aqueous solution.

60. The method of any one of claims 56 to 59, wherein the polymer is present at a concentration of from about 20 ppm to about 200 ppm in the aqueous solution.

61. The method of any one of claims 56 to 60, wherein the dye is a red dye, an orange dye, a yellow dye, a green dye, a blue dye, a purple dye, a brown dye, a gray dye, a black dye, or any combination thereof.

62. The method of any one of claims 56 to 61 , wherein the dye is a red dye, a blue dye, or combination thereof.

63. The method of any one of claims 56 to 62, wherein the method provides a AE of less than about 40, wherein AE is determined according to the method of ASTM D5548.

64. The method of any one of claims 56 to 63, wherein the AE is of less than about 20.

65. The method of any one of claims 56 to 64, wherein the AE is of less than about 15.

66. The method of any one of claims 56 to 65, wherein the AE is of less than about 10.

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