Biodegradable and emulsifiable ionizable polyesters

Abstract

The disclosure relates to ionizable polyesters containing repeat units having polymeric or oligomeric polyester segments or residues and linkers between the polyester segments having ionizable groups such as carboxylic acid groups and their related salts, for example ammonium salts. The ionizable polyesters can further include repeat units with functional groups other than polyesters to impart additional barrier properties, pH-responsive properties, and / or reactive properties. The ionizable polyesters can be used as water- and oil-resistant barrier coatings on cellulosic substrates such as paper, providing good barrier properties while also providing coatings and coated articles that are biodegradable, compostable, recyclable, and / or repulpable. The ionizable polyesters can be provided in an aqueous emulsion containing a salt form of the ionizable polyesters, which is a particularly suitable form for applying a coating of the ionizable polyesters onto a substrate such as paper.

Description

BIODEGRADABLE AND EMULSIFIABLE IONIZABLE POLYESTERSCROSS REFERENCE TO RELATED APPLICATION

[0001] Priority is claimed to U.S. Provisional Application No. 63 / 638,534 (filed April 25, 2024), U.S. Provisional Application No. 63 / 650,066 (filed May 21 , 2024), and U.S.Provisional Application No. 63 / 665,034 (filed June 27, 2024), each of which is incorporated herein by reference in its entirety.STATEMENT OF GOVERNMENT INTEREST

[0002] This invention was made with government support under NSF-2208697 awarded by the National Science Foundation and DE-EE0009947 awarded by Department of Energy. The government has certain rights in the invention.BACKGROUND OF THE DISCLOSUREField of the Disclosure

[0003] The disclosure relates to ionizable polyesters containing repeat units having polymeric or oligmeric polyester segments or residues and linkers between the polyester segments having ionizable groups such as carboxylic acid groups and their related salts. The ionizable polyesters can be used as water- and oil-resistant barrier coatings on cellulosic substrates such as paper, providing good barrier properties while also providing coatings and coated articles that are biodegradable, compostable, recyclable, and / or repulpable.Background

[0004] Plastics, particularly laminated materials and per- and polyfluoroalkyl substances (PFAS) used in packaging, have imposed a significant burden on the environment. In response, some single-use plastic items have been banned. However, this ban has limited effectiveness as there is no reasonable alternative available to manufacturers. Moreover, according to the U.S. Centers for Disease Control and Prevention (CDC), over 95% of the U.S. population has harmful fluorochemicals (PFAS) in their bodies.

[0005] Paper products fulfill indispensable roles in everyday lives because of their affordability, biodegradability, and renewability. However, paper is porous and polar in nature, and thus it has poor water and grease resistance. The water resistance of paper is measured as the Cobb60 value, representing the amount of grams of water per square meter that a paper absorbs in 60 seconds when it is brought into contact with water. Meanwhile, grease resistance is represented by a kit rating value, where a value of 12 / 12denotes the maximum grease resistance, and 0 / 12 corresponds to no grease resistance. Several approaches are employed to improve water resistance, such as the use of sizing agents, chemical modification, physicochemical modification, and layer-by-layer assembly.

[0006] The lamination and coating of paper substrates is a popular strategy to fabricate water- and grease-resistant paper. For example, low-density polyethylene (LDPE) is the most common plastic used as a liner for paper substrates to enhance their liquid repellency. Waxed paper is also used for low temperature packaging applications. However, the separation of coatings and laminates from paper fibers or pulp during the repulping process presents a significant challenge and these materials are not biodegradable. Biobased polymers such as polylactic acid (PLA) have also been used to laminate paper. However, PLA does not fully biodegrade under ambient conditions under home compost conditions in a reasonable amount of time, thus requiring an industrial composting environment, while the separation of PLA from pulp is a challenging task. Wax coatings are sometimes combined with biodegradable coatings to coat paper, but the coated substrates are adequate for low- temperature applications only. Parchment paper is also water- and oil-proof (for a short period of time). However, parchment paper is not suitable due to the extensive use of chemicals (e.g., ZnCI2, sulfuric acid) and energy during its production and due to its poor recyclability. PFAS are also used to fabricate water- and grease-resistant paper. However, there have been calls for alternatives to these materials due to environmental concerns.

[0007] U.S. Publication No. 2021 / 0253901 is directed to biodegradable omniphobic coatings. The omniphobic coating includes a reaction product between an amino-functional polymer and an amino-reactive functionalized omniphobic polymer having a glass transition temperature (Tg) of 60° C. or less. A corresponding omniphobic coated article can include the omniphobic coating on a porous substrate such as a cellulosic or paper substrate, for example to provide a water- and oil / fat / grease-resistant coating for a paper-based product.

[0008] U.S. Publication No. 2021 / 0246333 is directed to biodegradable omniphobic and high-barrier coatings. The omniphobic coating includes an oleophobic and hydrophilic first layer, and a hydrophobic and optionally oleophilic second layer adjacent to the first layer. A corresponding omniphobic coated article can include the omniphobic coating on a substrate such as a porous cellulosic or paper substrate, for example to provide a water- and oil / fat / grease-resistant coating for a paper-based product.

[0009] International Publication No. WO 2024 / 215970 is directed to synthetic wax compositions including at least one long-chain hydrocarbon residue having 12 to 40 carbon atoms, and at least one oligomeric residue containing 4 to 20 or 4 to 50 glycolic acid unitsand / or lactic acid units. The synthetic wax can be used as a coating on substrates such as paper substrates, to impart water and / or oil resistance to the substrate.SUMMARY

[0010] In an aspect, the disclosure relates to an ionizable polyester comprising: first (e.g., polymeric) repeat units according to Formula (1 ): -[-A-L1-]- (1 ); optionally, second (e.g., polymeric or monomeric) repeat units according to Formula (2): -[-B-L2-]- (2); and optionally, third (e.g., polymeric) repeat units according to Formula (3): -[-C-L3-]- (3). In Formula (1 ), A comprises one or more polyesters (or polyester residues) selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations (e.g., copolymers) thereof. In Formula (2), B is different from A, and comprises one or more functional groups selected from the group consisting of ethylenically unsaturated groups (e.g., C=C ), acetal (or ketal) groups (e.g., O C(R1 R2) O ), ketone (or carbonyl) groups (e.g., C(=O) ), dicarbonyl groups (e.g., C(=O) C(=O) , or with intervening carbon atom(s) between carbonyl groups), cyano groups (e.g., - CN), halogen groups (e.g., Cl), and combinations (e.g., oligomers or co-oligomers) thereof. In Formula (3), C is different from A and B, and comprises one or more polyesters (or polyester residues) selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations (e.g., copolymers) thereof. In each of the formulas, L1, L2, and L3are the same or different ringopening esterification reaction products of a polyanhydride (e.g., dianhydride) and contain at least two (pendant) carboxylic groups (e.g., -C(=O)OH), salts thereof (e.g., -C(=O)OM, where M is an ammonium salt, (monovalent) metal, etc.), and combinations thereof (e.g., distribution of groups between acid and one or more salt forms). In various embodiments described below, the ionizable polyester can include the main polyester / dianhydride -[-A-L1-]- units, with or without functional polyester -[-B-L2-]- units, and with or without copolyester -[-C-L3-]- units.

[0011] In an aspect, the disclosure relates to an ionizable polyester comprising: first repeat units according to Formula (1 ): -[-A-L1-]-(1 ); wherein: A comprises one or more aromatic, semi-aromatic, or aliphatic polyesters or copolyesters (or (co)polyester residues); and L1is an aromatic, aliphatic, semi-aromatic, cyclic, linear, branched, or acyclic hydrocarbon group containing 1 to 50 carbon atoms and comprising one or more polar functional groups. The ionizable polyester can further include repeat units according toFormulas (1) and (2) as described above, for example C similarly can comprise one or more aromatic, semi-aromatic, or aliphatic polyesters or copolyesters (or (co)polyester residues). The non-ionic polar groups in the synthesized polymer could be converted to ionic groups when emulsified, for example via salt formation from carboxylic groups, ammonium salt formation from amino groups, reaction of hydroxyl groups with (for example) a monoanhydride to form an ester and pendant carboxylic group (e.g., which can be converted to / from salt form). In a refinement, A has a molecular weight in a range of 500 g / mol to 20,000 g / mol; and the polar functional group is selected from group consisting of carboxylic groups, salts thereof, hydroxyl groups, amino groups, ammonium salts thereof, phosphate groups, and combinations thereof.

[0012] In an aspect, the disclosure relates to an ionizable polyester comprising: first repeat units according to Formula (1): -[-A-L1-]- (1); optionally, second repeat units according to Formula (2): -[-B-L2-]- (2); optionally, third repeat units according to Formula (3): -[-C-L3-]- (3); wherein: A comprises one or more polyesters selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations thereof; B is different from A, and comprises one or more functional groups selected from the group consisting of ethylenically unsaturated groups, acetal groups, ketone groups, dicarbonyl groups, cyano groups, halogen groups, and combinations thereof; C is different from A and B, and comprises one or more polyesters selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations thereof; and L1, L2, and L3are the same or different esterification reaction products of a polycarboxylic acid (e.g., triacid such as citric acid, alone or in combination with one or more diacids such as adipic acid and / or monoacids such as stearic acid) and contain at least one more (pendant) carboxylic groups (e.g., -C(=O)OH), salts thereof (e.g., -C(=O)OM, where M is an ammonium salt, (monovalent) metal, etc.), and combinations thereof (e.g., distribution of groups between acid and one or more salt forms).

[0013] Various refinements of the ionizable polyesters and ionizable polysiloxanes are possible.

[0014] In a refinement, A is selected from the group consisting of polybutylene adipate terephthalate and polylactic acid; L1is a ring-opening esterification reaction product of a dianhydride; the second repeat units are not present; and the third repeat units are notpresent. This can represent a base embodiment in which just the main polyester -[-A-L1-]- units, for example as illustrated by the CPBAT and CPLA ionizable polyesters in the examples below.

[0015] In a refinement, L1is a ring-opening esterification reaction product of meso-butane- 1 ,2,3,4-tetracarboxylic dianhydride and has the following structure:

[0016] In a refinement, L1is present in the first repeat unit in a range of 0.1 wt.% to 25 wt.% (e.g., 2-15 wt.% or 5-10 wt.%).

[0017] In a refinement, the second repeat units are present; B contains 1 to 20 repeat units, each repeat unit containing 4 to 20 carbon atoms and comprising the one or more functional groups; and the third repeat units are not present. This can represent a functional polyester embodiment in which the functional -[-B-L2-]- units are also present with the main polyester -[-A-L1-]- units. In alternative embodiments, the ionizable polyester can include the third repeat units in a block or random copolymer structure. In a further refinement, the first repeat units are present in the ionizable polyester in a range of 30 wt.% to 99 wt.%; the second repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; and a weight ratio of first repeat units : second repeat units is in a range of 1 :3 to 100:1 .

[0018] In a refinement, the second repeat units are not present; the third repeat units are present; and the ionizable polyester is in the form of a block copolymer between the first repeat units and the third repeat units. This can represent a block copolyester embodiment in which the additional polyester -[-C-L3-]- units are also present with the main polyester -[-A-L1-]- units. In other embodiments, the first and third repeat units can have a random copolymer relationship between each other. In alternative embodiments, the ionizable polyester can include the second repeat units. In a further refinement, the first repeat units are present in the ionizable polyester in a range of 30 wt.% to 99 wt.%; the third repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; and a weight ratio of first repeat units : third repeat units is in a range of 1 :3 to 100:1 .

[0019] In a refinement, the second repeat units are present; and the third repeat units are present. In a further refinement, the first repeat units are present in the ionizable polyester in a range of 30 wt.% to 99 wt.%; the second repeat units are present in the ionizable polyesterin a range of 1 wt.% to 70 wt.%; the third repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; a weight ratio of first repeat units : second repeat units is in a range of 1 :3 to 100:1 ; a weight ratio of first repeat units : third repeat units is in a range of 1 :3 to 100:1 ; and a weight ratio of second repeat units : third repeat units is in a range of 1 :100 to 100:1.

[0020] In a refinement, L1, L2, and L3are the same or different ring-opening esterification reaction products of a dianhydride selected from the group consisting of butane-1 ,2,3,4- tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

[0021] In a refinement, the ionizable polyester comprises ring-opening esterification reaction products of a polyanhydride and a monoanhydride. The ring-opening esterification reaction product of the monoanhydride contains one (pendant) carboxylic group (e.g., -C(=O)OH) or a salt thereof (e.g., -C(=O)OM, where M is an ammonium salt, (monovalent) metal, etc.).

[0022] In a refinement, A has a molecular weight in a range of 200 g / mol to100,000 g / mol; the ionizable polyester has a molecular weight in a range of 200 g / mol to 100,000 g / mol; and a ratio between the molecular weight of the ionizable polyester to the molecular weight of A is in a range of 1 .02 to 10.

[0023] In a refinement, A has a molecular weight in a range of 1 ,000 g / mol to 10,000 g / mol; the ionizable polyester has a molecular weight in a range of 1 ,000 g / mol to 50,000 g / mol; and a ratio between the molecular weight of the ionizable polyester to the molecular weight of A is in a range of 1 .1 to 3.

[0024] In a refinement, the ionizable polyester has a melting temperature in the range of 80-400‘C (e.g., 100-300‘C, or 120-200‘C).

[0025] In a refinement, L1, L2, and L3comprise ammonium salts of the ring-opening esterification reaction products.

[0026] In a refinement, L1, L2, and L3comprise carboxylic groups in acid form of the ringopening esterification reaction products.

[0027] In a refinement, the ionizable polyester is unbranched and / or not crosslinked.

[0028] In a refinement, each L1, L2, and / or L3contains two carboxylic groups or salts thereof.

[0029] In a refinement, the polyesters A are selected from the group consisting of polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), polybutylene adipate succinate (PBAS), poly(lactic acid-co- glycolic acid), polyhydroxyalkanoates, poly(1 ,4-cyclohexanedimethylene succinate) (PCHS), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyethylene succinate) (PES), polybutylene naphthalate (PBN), polybutylene succinate (PBS), polybutylene terephthalate (PBT), polycaprolactone (PCL), polycyclohexylenedimethylene terephthalate (PCT), polyethylene adipate (PEA), polyethylene furanoate (PEF), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyhydroxyalkanoates (PHA), polylactic acid (PLA), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), poly(trimethylene carbonate) (PTMC), poly(glycolide-co-lactide) (PGLA), unsaturated polyesters, alkyd resins; PETG (polyethylene terephthalate glycol-modified), and combinations (e.g., copolymers) thereof.

[0030] In an aspect, the disclosure relates to a method for forming an ionizable polyester according to any of the variously disclosed embodiments, the method comprising: reacting a polyanhydride with a first polyester diol according to Formula (1 A) and, optionally, one or both of a second functional diol according to Formula (2B) and a third polyester diol according to Formula (3A) to form an ionizable polyester product: HO-[-A-]-OH (1 A), HO-[-B-]-OH (2A), and HO-[-C-]-OH (3A). The groups A, B, and C in Formulas (1 A)-(1 C), respectively, can generally be selected from the same options as described herein for the first, second, and third repeat units of Formulas (1 )-(3), respectively. In a refinement, A comprises one or more polyesters (or polyester residues) selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations thereof. In a refinement, B is different from A, and comprises one or more functional groups selected from the group consisting of ethylenically unsaturated groups, acetal (or ketal) groups, ketone (or carbonyl) groups, dicarbonyl groups, and combinations thereof. In a refinement, C is different from A and B, and comprises one or more polyesters (or polyester residues) selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations (e.g., copolymers) thereof.

[0031] In a refinement, the method can comprise: reacting at a temperature of up to 200 °C or 240 °C; reacting in the presence of 0.01 to 0.1 wt.% catalyst relative to totalreactants; and / or adding a catalytic deactivator in an amount of 0.01 to 0.05 wt.% with respect to solid polymer.

[0032] In a refinement, the first polyester diol (or second functional diol or third polyester diol) has a molecular weight in a range of 200 g / mol to 100,000 g / mol; the ionizable polyester has a molecular weight in a range of 200 g / mol to 100,000 g / mol; and a ratio between the molecular weight of the ionizable polyester to the molecular weight of the first polyester diol (or second functional diol or third polyester diol) is in a range of 1 .02 to 10.

[0033] In a refinement, the ionizable polyester resulting from the method comprises: first repeat units according to Formula (1): -[-A-L-]- (1); optionally, second repeat units according to Formula (2): -[-B-L-]- (2); and optionally, third repeat units according to Formula (3): -[-C-L-]- (3); wherein: L is a ring-opening esterification reaction product of the polyanhydride and contains at least two (pendant) carboxylic groups, salts thereof, and combinations thereof.

[0034] In an aspect, the disclosure relates to an ionizable polyester dispersion comprising: an aqueous medium; and an ionizable polyester according to any of the disclosed embodiments dispersed (or emulsified) in the aqueous medium. In a refinement, water is present in the aqueous medium in an amount of 50 wt.% to 99 wt.% relative to the dispersion; and the ionizable polyester is present in the aqueous medium in an amount of 1 wt.% to 50 wt.% relative to the dispersion, n a refinement, the ionizable polyester is in an ammonium salt form (e.g., containing some or all pendant -C(=O)OM groups in the L units).

[0035] In an aspect, the disclosure relates to coated article comprising: a substrate; and a coating on the substrate, the coating comprising an ionizable polyester according to any of the disclosed embodiments.

[0036] In a refinement, the substrate is a cellulosic substrate. In a further refinement, the cellulosic substrate further comprises at least one of a cationic starch and polyethylene imine (PEI) present in one or both of (i) a blend with the ionizable polyester in the coating and (ii) a separate layer between the cellulosic substrate and the coating.

[0037] In a refinement, the coated article has a kit rating in a range of 4 to 12; the coated article has a cobb rating of 20 g / m2or less; the coated article has an OTR value between 0.0001 -20 cc*mm / m2*24h at 23°C and 50% RH (e.g., 0.1 -5 cc*mm / m2*24h); and / or the coated article has a WVTR value between 0.0001 -40 g»mm / m2»24h at 37 °C and 90% RH (e.g., 0.01-5 g*mm / m2*24h).

[0038] In a refinement, the coated article further comprises at least one of a gas barrier layer such as PVOH, EVOH, G-POLYMER (a vinyl alcohol polymer), etc. (e.g., adhered to the substrate on a side / face opposing that on which the ionizable polyester is coated) and an oil-resistant layer (e.g., interposed between the substrate and the ionizable polyester).

[0039] In a refinement, the coated article further comprises one or more additives (e.g., fillers or additives in the ionizable polyester and / or in an additional coating layer such as the gas barrier layer or oil-resistant layer). The additives can be present in an amount of 1 wt.% to 50 wt.% or 5 wt.% to 20 wt.% relative to the ionizable polyester composition. More generally, the additives can be present in an amount of at least 0.1 , 1 , 2, 3, 5, 7, 10, 12, 15, or 20 wt.% and / or up to 1 , 2, 4, 6, 8, 10, 12, 16, 20, 25, 30, 40, or 50 wt.%, where the foregoing amounts can apply independently to individual additives and / or all additive combined. The additives are not particularly limited and can include fibers, particles, etc. For example, the additives can be selected from the group consisting of inorganic fillers (e.g., silica, calcium carbonate, calcium chloride, titanium dioxide), polymeric fillers (e.g., polyvinyl acetate, polymerized waxes, biodegradable polymers, such as biodegradable polymers including carboxylic and / or hydroxyl functional groups), nanoparticles (e.g., cellulose nanocrystals / cellulose nanofibrils (functionalized and non-functionalized), carbon nanotubes, graphene oxides (functionalized and non-functionalized), clays or nanoclays (functionalized and non-functionalized)), natural waxes (e.g., carnauba), plasticizers (e.g., hydrophobic or hydrophilic), and combinations thereof.

[0040] In a refinement, the ionizable polyester in the coating is in an acid form. For example. For example, the ionizable polyester can contain some or all -COOH groups, for example as a result of drying an as-applied ammonium salt form of the ionizable polyester, which removes ammonia and converts the ionizable polyester back to acid form. In embodiments, at least 90% of carboxylic groups are in acid form.

[0041] In a refinement, the coating further comprises a wax blended with the ionizable polyester. For example, the coating can contain 10-99 wt.% ionizable polyester, such as at least and / or up to 10, 25, 40, 65, 90, 95, or 99 wt.% and ranges therebetween. Similarly, the coating can contain 1 -90 wt.% wax, such as at least and / or up to 1 , 5, 10, 15, 20, 30, 50, 70, or 90 wt.% and ranges therebetween. The wax can be a synthetic wax or a biodegradable synthetic wax, for example as disclosed in International Publication No. WO 2024 / 215970, incorporated herein by reference in its entirety.

[0042] In a further refinement, the wax comprises a synthetic wax according to Formula I: A-a-B-b-C (I). In Formula I, A is a hydrocarbon ester group having 12 to 40 carbon atoms; Bis an oligomeric residue of (i) n glycolic acid units, (ii) n lactic acid units, or (iii) n glycolic acid units and lactic acid units in total, where n is 4 to 20 (or 4 to 50, or 6 to 14); C is either OH or a hydrocarbon ester group having 2 to 40 carbon atoms, with the proviso that when C is OH, then A contains at least one of a carboxylic group and an unsaturated carbon-carbon double bond; a is either absent, or present as a linking group between A and B; and b is either absent, or present as a linking group between B and C.

[0043] In Formula I of the synthetic wax, A can include linear, branched, or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon groups having at least one ester functional group. For example, A can include linear, branched, or cyclic, substituted or unsubstituted alkyl or alkenyl (e.g., having one or more C=C unsaturated bonds) groups with a terminal ester functional group at the point of bonding to a or B. The A group can be substituted with or otherwise include a carboxylic group (e.g., in acid or salt form) or an unsaturated (polymerizable) C=C unsaturated bond. The relatively long hydrocarbon character of A imparts at least some of the waxy character to the synthetic wax. The A group can include at least 8, 12, 14, 16, 18, 20, or 24 and / or up to 16, 20, 24, 28, 32, 36, or 40 carbon atoms (e.g., where at least one of which is a carbonyl carbon C(=O) in the ester group C(=O)O).

[0044] In Formula I of the synthetic wax, B can include one or both of glycolic and lactic units. When B contains both glycolic and lactic units, the units in the oligomeric residue can have a block or random arrangement. The total number n of glycolic / lactic units in B can be at least 4, 5, 6, 7, 8, 9, 10, 12, or 14 and / or up to 5, 6, 8, 10, 12, 14, 16, 18, 20, 30, 40, or 50.

[0045] In Formula I of the synthetic wax, when C is not an OH group, C can generally include the same options as A, but it can include comparatively shorter hydrocarbon segments as compared to A (e.g., when A is long enough to substantially provide the desired waxy character). In addition to the carboxylic and unsaturated functional groups that are possible for A, C can also include an additional oligomeric residue of glycolic / lactic units along its length (i.e., analogous to and in addition to B). For example, the C group can include at least 2, 3, 4, 6, 8, 10, 12, 14, 16, 18, 20, or 24 and / or up to 4, 6, 8, 12, 16, 20, 24, 28, 32, 36, or 40 carbon atoms (e.g., where at least one of which is a carbonyl carbon C(=O) in the ester group C(=O)O).

[0046] In Formula I of the synthetic wax, the linking groups a and b, when present, can include residues of diols or polyols, for example condensation reaction products linking carboxylic functional groups in A, B, and / or C via resulting ester linkages (e.g., via resulting alkylene groups). Both linking groups need not be present, since a terminal hydroxyfunctional group the oligomeric B group can react directly with a terminal carboxylic group in precursor reactants forming the A and / or C groups.

[0047] In various refinements of Formula I of the synthetic wax, either or both of linkers a and b can be present or absent (e.g., only a present, only b present, both a and b present). For example, linker a can be present when a diol linker is used to react with carboxylic terminal groups in A and B. Similarly, linker b can be present when a diol linker is used to react with carboxylic terminal groups in B and C.

[0048] In a further refinement, the wax comprises a synthetic wax according to the following Formula IA and / or IB (e.g., alone or in admixture): R1C(=O)O-R2-[-OC(=O)-CHR3- ]n-O-R4(IA); and / or R1C(=O)O-[-CHR3-OC(=O)-]n-R2-O-R4(IB). In Formulas IA and IB, R1is a hydrocarbon group having 11 to 39 carbon atoms; R2is a hydrocarbon linking group having 2 to 18 carbon atoms; n is 4 to 20 (or 4 to 50, or 6 to 14); R3is independently H (i.e., glycolic acid residue) or CH3(i.e., lactic acid residue) for each of the n repeat units (i.e., where one or both of glycolic acid and lactic acid units can be included in the n repeat units); and R4is H or hydrocarbon group having 2 to 40 carbon atoms, with the proviso that when R4is H, then R1contains at least one of a carboxylic group and an unsaturated carboncarbon double bond.

[0049] In an aspect, the disclosure relates to a method for forming a coated article, the method comprising: applying an aqueous ionizable polyester dispersion to a surface of a substrate (e.g., as a layer or coating thereon), wherein the ionizable polyester dispersion comprises: an aqueous medium; and an ionizable polyester in ammonium salt form (e.g., NR1R2R3H+); dispersed (or emulsified) in the aqueous medium; removing the aqueous medium from the surface of the substrate (e.g., via applied heat or other drying step), thereby removing an amine from the ionizable polyester (NR1R2R3) and converting the ionizable polyester to an acid form. The solvent removal step for drying the coating can be performed at any suitable temperature and pressure sufficient to remove the amine (e.g., such that the vapor pressure of ammonia or other amine NR1R2R3is sufficiently high to remove the amine).

[0050] In an aspect, the disclosure relates to an ionic polysiloxane comprising: first repeat units according to Formula (1 ): -[-A-L1-]- (1 ); optionally, second repeat units according to Formula (2): -[-B-L2-]- (2); optionally, third repeat units according to Formula(3): -[-C-L3-]- (3); wherein: A comprises one or more polysiloxanes (e.g., polydialkylsiloxanes such as PDMS); B is different from A, and comprises one or more functional groups (e.g., diester or polyester residues containing one or more functional groups other than esters;functional groups on the non-siloxane part can be backbone or pendant groups) selected from the group consisting of ethylenically unsaturated groups (e.g., -C=C-), acetal (or ketal) groups (e.g., -O-C(R1R2)-O-), ketone (or carbonyl) groups (e.g., -C(=O)-), dicarbonyl groups (e.g., -C(=O)-C(=O)-, or with intervening carbon atom(s) between carbonyl groups), cyano groups (e.g., -CN), halogen groups (e.g., Cl), and combinations (e.g., oligomers or cooligomers) thereof; C is different from A and B, and comprises one or more polysiloxanes; and L1, L2, and L3are the same or different ring-opening esterification reaction products of a polyanhydride (e.g., dianhydride) and contain at least two (pendant) carboxylic groups (e.g., -C(=O)OH), salts thereof (e.g., -C(=O)OM, where M is an ammonium salt, (monovalent) metal, etc.), and combinations thereof (e.g., distribution of groups between acid and one or more salt forms).

[0051] While the disclosed articles, apparatus, methods, and compositions are susceptible of embodiments in various forms, specific embodiments of the disclosure are illustrated (and will hereafter be described) with the understanding that the disclosure is intended to be illustrative, and is not intended to limit the claims to the specific embodiments described and illustrated herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0052] For a more complete understanding of the disclosure, reference should be made to the following detailed description and accompanying drawings wherein:

[0053] Figure 1 is a schematic of a coated article including an ionizable polyester coating according to an embodiment of the disclosure.

[0054] Figure 2 is a schematic of a coated article including an ionizable polyester coating according to another embodiment of the disclosure.

[0055] Figure 3 is a schematic of a coated article including an ionizable polyester coating according to another embodiment of the disclosure.

[0056] Figure 4 is a schematic of a coated article including an ionizable polyester coating according to another embodiment of the disclosure.

[0057] Figure 5 is a scheme illustrating steps for forming an ionizable polyester incorporating polylactide (PLA) segments according to an embodiment of the disclosure.

[0058] Figure 6 is a scheme illustrating neutralization and emulsification of the ionizable polyester from Figure 5.

[0059] Figure 7 is a scheme illustrating steps for forming an ionizable polyester incorporating polybutylene adipate terephthalate (PBAT) segments according to an embodiment of the disclosure.

[0060] Figure 8 is a scheme illustrating neutralization and emulsification of the ionizable polyester from Figure 7.

[0061] Figure 9 is a scheme illustrating steps for forming an ionizable polysiloxane incorporating polydimethylsiloxane (PDMS) segments according to an embodiment of the disclosure.

[0062] Figure 10 is a scheme illustrating neutralization and emulsification of the ionizable polysiloxane from Figure 9.

[0063] Figure 11 is a scheme illustrating steps for forming an ionizable polyester incorporating polylactide (PLA) segments according to an embodiment of the disclosure.

[0064] Figure 12 is a scheme illustrating steps for forming a synthetic wax for blending with an ionizable polyester according to an embodiment of the disclosure.

[0065] Figure 13 is a scheme illustrating steps for forming a polyfunctional limonene anhydride according to an embodiment of the disclosure.

[0066] Figure 14 is a schematic illustrating the structure and components of an ionizable polyester according to the disclosure.

[0067] Figure 15 illustrates representative chemical structures for functional repeat units of an ionizable polyester according to the disclosure.

[0068] Figure 16 illustrates synthetic routes for forming a functionalized ionizable polyester according to the disclosure.

[0069] Figure 17 is a scheme illustrating steps for forming an ionizable polyester incorporating polybutylene adipate terephthalate (PBAT) segments and citric acid linkers according to an embodiment of the disclosure.DETAILED DESCRIPTION

[0070] Approximately 40% of all plastics produced today are used in the packaging sector. The most significant sustainable packaging hurdle is access to new materials that are universally compostable, are repulpable and / or recyclable, are available at commodity prices, and have performance matching or exceeding those of the existing polymers. The disclosure generally relates to biodegradable and emulsifiable ionic or ionizable polyesterswith the ability to form waterborne coatings. A paper coated with a water-borne emulsion of the disclosed ionizable polyesters has water and oil resistance matching that of conventional plastic-coated paper. The materials developed by this approach are biodegradable (e.g., biodegrade in the ocean, soil, and industrial compost environment), as well as on-demand degradable during repulping (washing off from paper etc.). The biodegradability aspect mitigates microplastics that are currently building up in the ocean and soil, while repulping provides a closed-loop recycling process for paper coated with the disclosed polyesters.

[0071] The disclosure relates to ionizable polyesters containing repeat units having polymeric or oligmeric polyester segments or residues and linkers between the polyester segments having ionizable groups such as carboxylic acid groups (e.g., -C(=O)OH) and / or their related salts (e.g., -C(=O)OM, where M is an ammonium salt, (monovalent) metal, etc.). As used herein, an ionizable polyester or ionizable group can represent a (polar) group capable of being converted to an ionic form (e.g., acid form of a carboxylic group) or a corresponding group that is in ionic form (e.g., carboxylate salt form of a carboxylic group). The ionizable polyesters can further include repeat units with functional groups other than / in addition to polyesters, for example to impart additional barrier properties, pH-responsive properties, reactive properties, etc. The ionizable polyesters can further include different polyester repeat units to provide a block or random copolymer structure between different types of polyester segments. In some aspects, the disclosure also relates to ionizable polysiloxanes analogous to the ionizable polyesters, but with polymeric or oligmeric polysiloxane segments or residues and linkers between the polysiloxane segments having ionizable groups.

[0072] The ionizable polyesters are particularly suitable for use as water- and oil-resistant barrier coatings on cellulosic substrates such as paper, providing good barrier properties while also providing coatings and coated articles that are biodegradable, compostable, recyclable, and / or repulpable. The coated articles can be used as packaging containers (cups, plates, boxes, etc.), lids, thermoforms, pouches, and / or rigid bottles. The coated articles can have OTR values between 0.0001 -20 cc*mm / m2*24h at 23qC and 50% RH, preferably between 0.01-0.5 cc*mm / m2*24h. The coated articles can have WVTR values between 0.0001 -40 g*mm / m2*24h at 37°C and 90% RH, preferably between 0.01-5 g»mm / m2»24h. The coated articles can have a Cobbl 800 value of 20 g / m2or less, and a kit rating of at least 9. The coated articles can be recyclable where paper is pulped (e.g., when the article substrate includes paper), and the recovered paper fiber can be used for making new paper without any significant stickies formation. The ionizable polyesters can be provided in the form of an aqueous emulsion of the ionizable polyesters in salt form (e.g., theionizable groups of the polyester are in salt form), which is a particularly suitable form for applying a coating of the ionizable polyesters onto a substrate.Ionizable Polyester

[0073] With reference to Fig. 14, an ionizable polyester 20 according to the disclosure can include first repeat units 20A (e.g., polymeric repeat units) according to Formula (1), optionally second repeat units 20B (e.g., polymeric or monomeric repeat units) according to Formula (2), and optionally third repeat units 20C (e.g., polymeric repeat units) according to Formula (3):-[-A-L1-]- (1 );-[-B-L2-]- (2);-[-C-L3-]- (3).As illustrated in Fig. 14, segment A 22 in the Formula (1) repeat unit can be or otherwise include one or more aromatic, semi-aromatic, or aliphatic polyesters or copolyesters or (co)polyester residues. Linker L128i is linked via ester bonds to segment A in its repeat unit and segment A, B, or C in a neighboring repeat unit (or a terminal group). Segment B 24 in the Formula (2) repeat unit can include one or more functional groups other than or in addition to ester groups, which can provide improved barrier or other properties to the ionizable polyester 20. Linker L2282 is linked via ester bonds to segment B in its repeat unit and segment A, B, or C in a neighboring repeat unit (or a terminal group). Segment C 26 in the Formula (3) repeat unit can be or otherwise include one or more aromatic, semiaromatic, or aliphatic polyesters or copolyesters or (co)polyester residues. Segment C is selected to be a different polyester group relative to segment A (e.g., having different molecular weights and / or different chemical structures), and it can form a random or block copolyester with the segment A polyesters. Linker L3283 is linked via ester bonds to segment C in its repeat unit and segment A, B, or C in a neighboring repeat unit (or a terminal group). The linkers L1, L2, and L3can be the same or different aromatic, aliphatic, semi-aromatic, cyclic, linear, branched, or acyclic hydrocarbon groups containing 1 to 50 carbon atoms which include one, two, three, four, or more (pendant) polar functional groups such as carboxylic groups. In various embodiments, the ionizable polyester 20 can include (i) only first repeat units 20A, (ii) only first and second repeat units 20A, 20B, (iii) only first and third repeat units 20A, 20C, or (iv) first, second, and third repeat units 20A, 20B, 20C.

[0074] The polyester segments or residues A in the first repeat units 20A are not particularly limited and can include any aromatic, semi-aromatic, or aliphatic polyesters or copolyesters. The polyester segments A can have a molecular weight in a range of 200-100,000 g / mol, or 500-20000 g / mol, or 1000-10,000 g / mol, for example representing a weight-average molecular weight (Mw) or a number-average molecular weight (Mn). For example, the molecular weight can be at least and / or up to 200, 500, 800, 1000, 2000, 3000, 5000, 7000, 10000, 15000, 20000, 25000, 30000, 40000, 50000, 60000, 80000, or 100000 g / mol. The foregoing weights can represent the molecular weights of specific polyester residue or an average (e.g., number- or weight-average) molecular weight for polyester containing a distribution of different sizes / molecular weights. The weights and weight ranges can similarly apply to polyester diol precursors used to form the corresponding ionizable polyester.

[0075] Examples of specific polyesters suitable for the polyester segments A include consisting of polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), polybutylene adipate succinate (PBAS), poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, poly(1 ,4-cyclohexanedimethylene succinate) (PCHS), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyethylene succinate) (PES), polybutylene naphthalate (PBN), polybutylene succinate (PBS), polybutylene terephthalate (PBT), polycaprolactone (PCL), polycyclohexylenedimethylene terephthalate (PCT), polyethylene adipate (PEA), polyethylene furanoate (PEF), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyhydroxyalkanoates (PHA), polylactic acid (PLA), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), poly(trimethylene carbonate) (PTMC), poly(glycolide-co-lactide) (PGLA), unsaturated polyesters, alkyd resins; PETG (polyethylene terephthalate glycol- modified), and combinations (e.g., copolymers) thereof. Particularly suitable polyesters include those that are biodegradable and / or compostable, for example one or more of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and copolymers thereof. Fig. 14 illustrates representative structures for polyester segment A 22 and segment C 26, including a PLA polyester segment (second row) and a PBAT polyester segment (third row).

[0076] The segments or residues B in the second repeat units 20B generally include functional groups other than ester groups, although they typically include two terminal ester groups linking to adjacent linking groups L2(within the same repeat unit) and L1, L2, or L3(in the adjacent repeat unit). When present, the functional groups can impart additional barrier properties, pH-responsive properties, reactive properties, etc. to the ionizable polyester 20. The functional groups can be backbone or pendant groups, and they can include one or more of ethylenically unsaturated groups (e.g., internal -C=C- or pendant vinyl -C=CH2),acetal (or ketal) groups (e.g., -O-C(R1R2)-O-, where R1and R2independently can be H or an alkyl group such as with 1 , 2, 3, or 4 carbon atoms), ketone (or carbonyl) groups (e.g., -C(=O)-), dicarbonyl groups (e.g., -C(=O)-C(=O)-, or with intervening carbon atom(s) between carbonyl groups), cyano groups (e.g., -CN), halogen groups (e.g., Cl), and combinations (e.g., oligomers or co-oligomers) thereof. In embodiments, the segments B can be monomeric or oligomeric, for example containing 1 to 20 repeat units (e.g., at least and / or up to 1 , 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or 20 repeat units and ranges therebetween). Each repeat unit in segment B can contain 4 to 20 carbon atoms (e.g., at least and / or up to 4, 6, 8, 10, 12, 14, 16, 18, or 20 carbon atoms and ranges therebetween) and includes one, two, three, four, or more the functional groups. Alternatively or additionally, the segments B can be as having a molecular weight within the ranges and subranges defined above for the segments A. Fig. 15 illustrates some representative chemical structures for functional second repeat units 24 of an ionizable polyester 20 according to the disclosure.

[0077] Fig. 16 illustrates synthetic routes for forming an ionizable polyester 20 including the functional segments B. The various initial step on the left side of the figure lead to the formation of a polyester diol that is precursor to the ionizable polyester. Route I on the left works for cyclic monomers such as lactide, glycolide, or their derivatives or their blends. Here, stoichiometric control of diol initiator to that of cyclic monomer can be used to control the chain length of polyester diol which will be coupled with a functional diol via dianhydride. Route II on the left provides a pathway to make functional polyesters starting from monomeric diols and monomeric diacid / diesters, the molecular weight of which can be controlled via the starting stoichiometric imbalance using equations proposed by Carothers and Flory. Once the desired polyester diol is prepared it can react with the functional diol monomer and dianhydride coupling agent. Routes III and IV on the left operate on the same principles, where virgin polyesters (Route III) or post-consumer polyester (Route IV) can be subjected to glycolysis in such a way to provide a desired molecular weight for the polyester diol. Then these diols will be coupled with functional diol via dianhydride. In subsequent functionalization step on the right side of the figure, functional biopolyesters can be made by reacting a polyester diol with e (a dianhydride) and f (a functional diol). Alternatively, a functional blocky biopolyester can be made by reacting polyester diol with e (dianhydride), f (functional diol), and g (a second polyester diol).

[0078] The polyester segments or residues C in the third repeat units 20C are not particularly limited and can include any aromatic, semi-aromatic, or aliphatic polyesters or copolyesters. The polyester segments C are different from the polyester segments A,although the polyester segments C can be selected from the same polyester types, molecular weight ranges, etc. as above for the polyester segments A. When the third repeat units 20C are present in the ionizable polymer 20, the first and third repeat units 20A, 20C can have a random or block copolymer relationship between each other.

[0079] In some embodiments, the ionizable polyester 20 includes only first repeat units 20A. In other embodiments, the ionizable polyester 20 includes the first repeat units 20A along with one or both of the second and third repeat units 20B and 20C. In embodiments including multiple types of repeat units, individual repeat units can be included in any suitable proportions relative to the ionizable polyester as a whole. For example, the first repeat units 20A can be present in the ionizable polyester 20 in a range of 30 wt.% to 99 wt.%, such as at least and / or up to 30, 40, 50, 60, 70, 80, 90, 95, 98, or 99 wt.% and ranges therebetween. Alternatively or additionally, the second repeat units 20B can be present in the ionizable polyester 20 in a range of 1 wt.% to 70 wt.%, such as at least and / or up to 1 , 2, 5, 10, 20, 30, 40, 50, 60, or 70 wt.% and ranges therebetween. Alternatively or additionally, the third repeat units 20C can be present in the ionizable polyester 20 in a range of 1 wt.% to 70 wt.%, such as at least and / or up to 1 , 2, 5, 10, 20, 30, 40, 50, 60, or 70 wt.% and ranges therebetween. Alternatively or additionally, a weight ratio of first repeat units : second repeat units can be in a range of 1 :3 to 100:1 , such as at least and / or up to 1 :3, 1 :2, 1 :1 , 2:1 , 3:1 , 5:1 , 7:1 , 10:1 , 20:1 , 40:1 , 60:1 , 80:1 , or 100:1 and ranges therebetween. Alternatively or additionally, a weight ratio of first repeat units : third repeat units can be in a range of 1 :3 to 100:1 , such as at least and / or up to 1 :3, 1 :2, 1 :1 , 2:1 , 3:1 , 5:1 , 7:1 , 10:1 , 20:1 , 40:1 , 60:1 , 80:1 , or 100:1 and ranges therebetween. Alternatively or additionally, a weight ratio of second repeat units : third repeat units can be in a range of 1 :100 to 100:1 , such as at least and / or up to 1 :100, 1 :80, 1 :60, 1 :40, 1 :20, 1 :10, 1 :5, 1 :3, 1 :2, 1 :1 , 2:1 , 3:1 , 5:1 , 7:1 , 10:1 , 20:1 , 40:1 , 60:1 , 80:1 , or 100:1 and ranges therebetween.

[0080] The linkers L1, L2, and L3can be the same or different aromatic, aliphatic, semiaromatic, cyclic, linear, branched, or acyclic hydrocarbon groups containing 1 to 50 carbon atoms (e.g., at least and / or up to 1 , 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 30, 40, or 50 carbon atoms and ranges therebetween) which included one, two, three, four, or more (pendant) polar functional groups such as carboxylic groups. More generally, the carboxylic groups, salts thereof, hydroxyl groups, amino groups, ammonium salts thereof, phosphate groups, and combinations thereof. The carboxylic group can be represented by -C(=O)OH, and the corresponding carboxylic salt can be represented by -C(=O)OM, where M is an ammonium salt, metal ion (e.g., monovalent metal ion such as Na, K, etc.), etc. The acid form of the carboxylic group can be converted to a corresponding salt form by neutralization with a basesuch as sodium bicarbonate, sodium carbonate, sodium hydroxide, ammonium bicarbonate, ammonium hydroxide, triethyl amine, etc., for example in an aqueous medium forming an emulsified ionizable polyester. In some embodiments, M can be NH4+, which in turn can liberate ammonia (NH3) upon drying and conversion of the carboxylic salt form of the ionizable polyester back to a carboxylic acid form (described in more detail below). More generally, M can be an (alkyl)ammonium group NR1R2R3H+, where R1, R2, and R3independently can be H or an alkyl group, such as with 1 , 2, 3, or 4 carbon atoms. In such cases, the corresponding alkylamine (e.g., volatile alkylamine such as trimethylamine, triethylamine, etc.) can be liberated upon conversion of the carboxylic salt form of the ionizable polyester back to a carboxylic acid form.

[0081] In embodiments, the linkers L1, L2, and / or L3can include ammonium salts of the corresponding carboxylic group. The ammonium salt form is particularly suitable for forming a waterborne emulsion of the ionizable polyester, which facilitates its application as a coating on a substrate such as paper. In embodiments, substantially all of the carboxylic groups in the ionizable polyester are in an ammonium salt or other ionic form, for example at least and / or up to 90, 95, 98, 99, or 100% and ranges therebetween of the carboxylic groups are in ionic form.

[0082] In embodiments, the linkers L1, L2, and / or L3can include the acid form of the corresponding carboxylic group. The acid form is particularly suitable for a coating after application on a substrate such as paper, because the acid form can provide improved barrier and resistance properties relative to the salt forms. In embodiments, substantially all of the carboxylic groups in the ionizable polyester are in acid form, for example at least and / or up to 90, 95, 98, 99, or 100% and ranges therebetween of the carboxylic groups are in acid form.

[0083] In embodiments, the linkers L1, L2, and / or L3can be the same or different ringopening esterification reaction products of a polyanhydride (e.g., dianhydride) with a (polyester) diol precursor to segment A, B, or C, respectively, the result of which is a linking group including at least two (pendant) carboxylic groups, which can be in acid form as originally formed, or in salt form after neutralization (e.g., treatment with ammonium bicarbonate or otherwise). Depending on the degree of neutralization, there can be a distribution of groups between acid and one or more salt forms (e.g., at least and / or up to 10, 25, 50, 75, or 90% independently for acid and salt forms). Examples of suitable dianhydrides (e.g., having two cyclic anhydride groups) include butane-1 ,2,3,4- tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylicdianhydride, and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Figs. 7 and 1 1 illustrate the structure of meso-butane-1 ,2,3,4-tetracarboxylic dianhydride (MBTCA) used in several examples, and Fig. 14 illustrates the corresponding linking group L1, L2, and / or L328 resulting from the ring-opening esterification reaction with MBTCA. More generally, the linking group L1, L2, and / or L3structure resulting from a dianhydride can include the structure L': -O(C=O)CH(»)CH2(C=O)OH (acid form), where represents the link to an adjacent (polyester) segment A, B, or C, and represents a direct or indirect link to a complementary L' group that is linked to the other adjacent (polyester) segment A, B, or C (e.g., directly bonded at thelocations, or indirectly bonded via a linking group between the locations). In the case of MBTCA, the two complementary L' groups forming the overall linking group L1, L2, and / or L3structure are joined directly to each other at the location.

[0084] In embodiments, the linkers L1, L2, and / or L3can be ring-opening esterification reaction products of a multianhydride (or polyanhydride with three, four, or more (cyclic) anhydride groups) such as polymer grafted with maleic anhydride. Polymers on which maleic anhydride include carbon-carbon back bone polymer such as polyethylene-g-maleic anhydride, polypropylene-g-maleic anhydride, or polyesters grafted maleic anhydride PBAT- g-maleic anhydride, PBS-g-maleic anhydride, etc. When using a multi-anhydride, coupling with polyesters yields graft copolymers.

[0085] In embodiments, the linkers L1, L2, and / or L3can be the same or different (condensation) esterification reaction products of a esterification reaction products of a polycarboxylic acid or ester thereof (e.g., triacid or triester thereof) with a (polyester) diol precursor to segment A, B, or C, respectively, the result of which is a linking group including at least one, two, or more (pendant) carboxylic groups, which can be in acid form as originally formed, or in salt form after neutralization (e.g., treatment with ammonium bicarbonate or otherwise). Depending on the degree of neutralization, there can be a distribution of groups between acid and one or more salt forms (e.g., at least and / or up to 10, 25, 50, 75, or 90% independently for acid and salt forms). Example of suitable polycarboxylic acids includes citric acid, aconitic acid, isocitric acid, trimesic acid, and hemimellitic acid; tetracarboxylic acids such as pyromellitic acid, prehnitic acid, mellitic acid, and 1 ,2,4,5-benzenetetracarboxylic acid, and esters thereof (e.g., methyl, ethyl, or other alkyl esters) The polyacids can be used alone or in combination with one or more diacids such as adipic acid and / or monoacids such as stearic acid.

[0086] To avoid crosslinking when using a polycarboxylic acid as a reagent, two strategies can be used. First, the reactions can be run to a lower degree of conversion to avoid gelpoint, but this often is not completely sufficient. Second, the Carother and Flory gel theories can be used to calculate and adjust the gel point by adding monofunctional acids / ester (e.g., stearic acid / ester) along with a trifunctional acid or ester (e.g., such as citric acid / ester), where monofunctional acids / ester helps to reduce / minimize / eliminate crosslinking. Preferentially, using more COOH groups than OH is preferred, which can be used for emulsification. The ratio of OH and COOH is set such that overall, the system has one ionizable COOH functional group (e.g., COOH, amine, etc.) per 200-3000 g / mol of the polyester. In the case of other ionizable functional groups, the OH and COOH ratios are nearly the same. At the same time, per 200-3000 g / mol, there is one ionizable amine, sulfonic acid, phonic acid, phenoxy group, or their combination. Optionally, a diacid / diester also can be added to the monoacid and polyacid reagents to adjust the molecular weights of the polymer. In embodiments, the ionizable polyester can be formed in a phased approach where an oligomeric or polymeric polyester diol is formed (e.g., from polyester by controlled depolymerization or from feedstock monomers by controlled polymerization), and then the polycarboxylic acid / ester, monofunctional acid / ester, and optionally difunctional acid / ester are added. To increase the thermal and hydrolytically stability of the carboxyl functionalized polyesters and their salts, suitably a low amount of catalyst (e.g., 0.01 -0.1 wt% of feedstock monomers / precursors) is used and optionally catalytic deactivators such as phosphoric acid acid are added (e.g., 0.01-0.05 wt% with respect to solid polymer).

[0087] In embodiments, the linker L1can be present in the first repeat unit in a range of 0.1 wt.% to 25 wt.%, 2-15 wt.%, 5-10 wt.% (e.g., relative to combined weight of A and L1in the first repeat unit), for example at least and / or up to 0.1 , 0.2, 0.5, 1 , 2, 3, 5, 7, 10, 12, 15, 20, or 25 wt.% and ranges therebetween. Similarly, segment A can be present in the first repeat unit in a range of 75 wt.% to 99.9 wt.%, such as at least and / or up to 75, 80, 85, 90, 95, 98, 99, or 99.9 wt.% and ranges therebetween. Analogous ranges can apply for segment B, segment C, linker L2, and linker L3relative to their respective repeat units when they are present. Alternatively or additionally, the ranges for the linkers L1, L2, and L3can apply relative to the ionizable polyester as a whole as well.

[0088] In embodiments, the ionizable polyester can further include ring-opening esterification reaction products of a monoanhydride containing one (pendant) carboxylic group (e.g., -C(=O)OH) or a salt thereof (e.g., -C(=O)OM, where M is an ammonium salt, (monovalent) metal, etc.). Monoanhydrides such as octadecenylsuccinic anhydride (ODSA) or otherwise can be included along with the dianhydride during synthesis. Monoanhydrides undergo ring opening and can react with a single hydroxyl group, terminating the ionizable polyester chain and adding a further terminal carboxylic group in addition to the interiorcarboxylic groups along the length of the ionizable polyester chain. Monoanhydrides can be incorporated in a selected amount relative to the dianhydrides to control the degree of molecular weight increase via dianhydride chain extension as well as to limit / prevent crosslinking.

[0089] In embodiments, the ionizable polyester can be substantially unbranched and / or not crosslinked. The rapid / low-temperature ring-opening chain extension reaction using the dianhydride does not generally result in condensation reactions with the ring-opened carboxylic groups, thus limiting or preventing undesirable crosslinking, although some minimal amount branching may occur in some cases.

[0090] In embodiments, the ionizable polyester can have a melting temperature in the range of 80-400 °C, 100-300 °C, or 120-200 °C. In embodiments, the ionizable polyester can have a melting temperature of at least 110 °C or 115°C. For example, the melting temperature can be at least and / or up to 80, 90, 100, 110, 115, 120, 130, 140, 150, 200, 250, 300, 350, or 400 °C and ranges therebetween.

[0091] In embodiments, the ionizable polyester can have a molecular weight in a range of 200-100,000 g / mol, or 500-20000 g / mol, or 1000-10,000 g / mol, for example representing a weight-average molecular weight (Mw) or a number-average molecular weight (Mn). For example, the molecular weight can be at least and / or up to 200, 500, 800, 1000, 2000, 3000, 5000, 7000, 10000, 15000, 20000, 25000, 30000, 40000, 50000, 60000, 80000, or 100000 g / mol. Alternatively or additionally, a ratio between the molecular weight of the ionizable polyester to the molecular weight of segment A is in a range of 1 .02 to 10 or 1 .1 to 3, for example at least and / or up to 1 .02, 1 .05, 1.1 , 1.2, 1 .3, 1 .4, 1 .5, 1 .7, 2, 2.5, 3, 4, 5, 6, 7, 8, 9, or 10 and ranges therebetween. This ratio reflects that the resulting ionizable polyester generally has a larger molecular weight relative to the initial polyester diols that are chain- extended via the dianhydrides or other linkers. The molecular weight ratios independently can be based on Mn or Mw ratios. Similar molecular weight ratios and ranges can apply for ratios between the ionizable polyester and segment B and / or between the ionizable polyester and segment C.

[0092] The ionizable polyesters according to the disclosure can be formed by reacting a polyanhydride (e.g., dianhydride) or a polyacid (e.g., triacid) with one or more diol precursors to the various repeat unit structures, for example a polyester diol for the first and third repeat units and a functional diol for the second repeat unit. In embodiments, ionizable polyesters can be formed by reacting a polyanhydride with a first polyester diol according to Formula (1 A) and, optionally, one or both of a second functional diol according to Formula (2B) and athird polyester diol according to Formula (3A) to form an ionizable polyester product:HO-[-A-]-OH (1A),HO-[-B-]-OH (2A),HO-[-C-]-OH (3A).The groups or segments A, B, and C in Formulas (1 A)-(1 C) are the same as those described above for Formulas (1)-(3). The reaction is suitably performed at a temperature of up to 200 °C or 240 °C, for example at about 150 °C to 200 °C or 240 °C for about 2 minutes to 240 minutes, or more generally for a time and at a temperature sufficient to promote dianhydride ring-opening and chain polyester diol chain extension, but without substantial crosslinking or degradation of the polyester portion of the polyester diol reactants. The reaction can be performed in the presence of 0.01 to 0.1 wt.% catalyst relative to total reactants (e.g., all diols and anhydrides combined). The method can include adding a catalytic deactivator (e.g., phosphoric acid) in an amount of 0.01 to 0.05 wt.% with respect to solid polymer (e.g., where catalyst and / or deactivator can be used to increase the thermal and hydrolytically stability of the carboxyl functionalized polyesters and their salts).

[0093] The ionizable polyesters according to the disclosure can be provided in the form of an ionizable polyester dispersion. The dispersion includes an aqueous medium, in which water can be present in an amount of about 50 wt.% to 99 wt.% relative to the dispersion, for example at least and / or up to 50, 60, 70, 80, 90, 95, 98, or 99 wt.% and ranges therebetween. The dispersion also includes the ionizable polyester dispersed or emulsified in the aqueous medium, for example being present in an amount of 1 wt.% to 50 wt.% relative to the dispersion, such as at least and / or up to 1 , 2, 5, 15, 25, 35, 45, or 50 wt.% and ranges therebetween. Suitably, the ionizable polyester is in an ammonium salt form, for example containing some or all pendant -C(=O)OM groups in which M can be NH4+or NR1R2R3H+as described above, for example where at least and / or up to 90, 95, 98, 99, or 100% and ranges therebetween of the carboxylic groups are in ammonium salt form.Coated Article

[0094] As illustrated in Figs. 1 -4, the disclosure provides a coated article 10 including a substrate 100, a coating or layer 200 on or adjacent to the substrate 100, optionally an additional coating or layer 300 on or adjacent to the substrate 100 or coating 200 . The coating 200 can include the ionizable polyester according to any of the variously disclosed embodiments. The coating can be applied by any suitable method, for example from a solvent solution or an aqueous dispersion or emulsion of the ionizable polyester (e.g., solvent casting). In other embodiments, the coating can be applied in the form of a meltcoating of the ionizable polyester (e.g., extrusion and non-extrusion melt-coating). The substrate 100 is suitably a cellulosic substrate such as a paper substrate. These ionizable polyester can be used as a coating directly on a cellulosic substrate, or as a top layer on an already-coated cellulosic substrate (e.g., with a first coating on the substrate such as a polymer like starch, and then a top or second coating of the ionizable polyester). The ionizable polyester can also be applied as a coating on other materials such as plastic films / bottles; water repellent fabrics; automotive polishes, as mold release agents in mold making, and other non-packaging applications. Typical coating 200 thicknesses can be 1 pm to 1000 pm or 20 pm to 50 pm. For example, the coating 320 can have thickness of at least 1 , 2, 5, 10, 20, 30, 50, 100, 200, or 300 pm and / or up to 30, 50, 70, 100, 200, 500, 700, or 1000 pm. Typical cast coatings can have thicknesses of 10 pm to 100 pm. As described herein, multiple coating layers can be applied to substrate 100 to form even thicker layers of the coating 320 (e.g., above 1000 pm, 2000 pm, or otherwise) if desired.

[0095] The coated article 10 of the disclosure includes a substrate 100. Examples of suitable substrates include, but are not limited to, porous substrates and other substrates. In the case of a coating on paper or other porous substrate, a layer or layers including polyethylene imine (PEI), polyacrylic acid (PAA), PEI-PAA, chitosan, starch, polyvinyl alcohol (PVOH), and / or blends thereof can be applied on the substrate as a first layer and then coated with the ionizable polyester as a second layer (e.g., with the first layer positioned between and / or adhered to the substrate and the second layer). When the substrate 100 is a porous substrate, the coating 200 and / or the first layer thereof, as described herein, can at least partially fill the pores of the substrate. The coated articles generally can use any porous substrate, cellulosic or non-cellulosic, for example porous metal substrates, porous plastic (e.g., polymeric foam) substrates, and porous cellulosic substrates. A cellulosic substrate generally includes at least one of cellulose and hemicellulose, and it can further include lignin (e.g., as a lignocellulosic substrate).

[0096] In general, when the substrate is a cellulosic substrate, the cellulosic substrate is not particularly limited, and can be formed from any cellulosic material desired for protection with an ionizable polyester coating. For example, the substrate can be a molded fiber containers, paper, paperboard, wood, or fabric (or textile). Examples of paper substrates can include, but are not limited to, generally thinner, flexible papers, for example useful as wrapping materials, as well as generally thicker, rigid papers or cardboard (e.g., corrugated paper cardboard, paperboards), for example useful as box, container, plate, cup, or other storage or food-service items. Suitable wood materials can be any type of wood commonly used in home, office, and outdoor settings. Suitable fabric or textile materials can includeany cellulosic materials commonly used in garments or otherwise, such as cotton, jute, flax, hemp, etc. In some embodiments, cationic starches, PEI, and other polymeric or inorganic basic ingredients can be used either as a blend with ionizable polyesters or as a separate base layer in paper coatings. These components help to complex with the carboxylic acid (COOH) groups of the ionizable polyesters, facilitating their solubilization and thus enabling the recycling of coated paper. In some embodiments, the cationic starches, PEI, and other polymeric or inorganic basic ingredients can be added during recycling (e.g., in an amount of about 0.1-5 wt.% relative to coated paper being recycled), which will facilitate repulping, recycling, and contamination removal during recycling.

[0097] In embodiments, the porous substrate includes a porous cellulosic substrate. In embodiments, the cellulosic substrate includes paper, corrugated board, cardboard, wood, fabric, and any combination thereof. The cellulosic substrate can be selected from the group of paper (bleached, unbleached, coated (pores still remain) and uncoated, supercallendered), corrugated board, cardboard, wood, and fabric (or textile). In some embodiments, the cellulosic substrate is in the form of a packaging box (e.g., corrugated boxes, cardboard boxes, cartons).

[0098] In embodiments, the substrate 100 has opposing first and second surfaces, and both surfaces of the substrate 100 are coated with an ionizable polyester coating 200 as described herein (Fig. 4). The coatings 200 on opposing surfaces can be the same as or different from each other. In embodiments, the article 10 can include the additional layer 300 in between the substrate 100 and the coating 200 (Fig. 2), or the article 10 can include the additional layer 300 on an opposing surface of the substrate 100 relative to the coating 200 (Fig. 3). The additional layer 300 can be a gas barrier layer or an oil-resistant layer. For example, the additional layer 300 can be chosen from a vinyl alcohol-bearing polymer such as PVOH or EVOH, or oil-resistant hydrophilic polymers such as starch, chitosan, etc. Layer 300 can have fillers such as graphene oxide, nano clay, and / or cellulose nanocrystals and inorganic fillers such as CaCO3 and NaCO3 in the range of 0.1-20wt%. Optionally, layer 300 also can have polyethylene imine or sodium bicarbonate in amount 0.1-20wt%.

[0099] The coating 200 and / or additional layer 300 can further include an additive (e.g., a filler). Examples of suitable additives include, but are not limited to, nanoclays, graphene oxide, graphene, silicon dioxide (silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes, titanium dioxide (titania), diatomaceous earth, biocides, pigments, dyes, and thermoplastics. The additives can be included in any one layer or all layers of the ionizable polyester coating as applied to the (porous and / or cellulosic) substrate. For example, theadditives can be included in a solution or mixture containing the ionizable polyester before it is applied to the substrate. Advantageously, the additives (e.g., fillers) can aid in sealing the substrate pores. Also, fillers can bring color to the substrate (e.g., paper), for example using titanium dioxide filler particles as a whitening agent. Biocidal properties can also be incorporated via nanofiber fillers. Other functions of the fillers (such as antioxidants, vitamin E, anti-fungals) include increasing the shelf-life and nutritional value of the product inside the coated paper. In addition, the first and / or second layers can be loaded with active components that kill certain microorganisms (e.g., bacteria, fungi or other microorganism) such as cimmaldehyde, carvacrol, sorbic acid, and nisin. Furthermore, cellulose nanocrystals, graphene, nanoclay, etc. as fillers can increase the gas and water vapor barrier properties. In embodiments, the coating includes one or more additives selected from the group consisting of nanoclay, graphene oxide, graphene, silicon dioxide (silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes, titanium dioxide (titania), diatomaceous earth, biocides, pigments, dyes, thermoplastics, and combinations thereof. The various fillers and additives can be present in any suitable amount, for example at least 0.001 , 0.01 , 0.1 , 0.2, 0.3, 0.5, 1 , 2, 3, or 5 wt.% and / or up to 0.1 , 0.2, 0.3, 0.5, 1 , 2, 3, 5, 10, 15, or 20 wt.% relative to the coating. The foregoing amounts and ranges can independently apply to all fillers and additives collectively or to individual fillers or additives.

[0100] In embodiments, the coated article 10 can have a kit rating in a range of 4 to 12; and / or the coated article has a. For example, the kit rating can be at least 4, 5, 6, 7, 8, 9, 10, or 11 and / or up to 8, 9, 10, 1 1 , or 12. Suitable methods for determining the kit rating include TAPPI methods T599 pm-96 and UM 557.

[0101] In embodiments, the coated article 10 can have a cobb (or cobbl 800) rating of 20 g / m2or less. For example, the cobb rating (or cobb1800 rating) can be at least 0.1 , 0.2, 0.5, 1 , 2, 3, 6, 8, 10, 12, or 15 g / m2and / or up to 3, 5, 7, 10, 15, or 20 g / m2. In other embodiments, the coated article 10 can have a cobb600 rating that is at least 0.1 , 0.2, 0.5, 1 , 2, 3, 6, 8, 10, 12, or 15 g / m2and / or up to 3, 5, 7, 10, 15, or 20 g / m2. A suitable methods for determining the cobb rating includes TAPPI method T441 om-09.

[0102] In embodiments, the coated article 10 can have a water vapor transmission rate (WVTR) between 0.0001 -40 g»mm / m2»24h at 37 °C and 90% RH, for example at least and / or up to 0.0001 , 0.001 , 0.01 , 0.1 , 0.2, 0.5, 1 , 2, 5, 10, 20, 30, or 40 g*mm / m2*24h at 37T3 and 90% RH. In embodiments, the coated article 10 can have an oxygen transmission rate (OTR) between 0.0001 -20 cc*mm / m2»24h at 23 °C and 50% RH, for example at least and / or up to 0.0001 , 0.001 , 0.01 , 0.1 , 0.2, 0.5, 1 , 2, 5, 10, or 20 cc*mm / m2*24h).

[0103] In embodiments, the coated article 10 can have a relative permeability for water vapor of 0.5 or less, relative to a corresponding (porous) substrate without the coating thereon. For example, the coated article can have a relative permeability for water vapor of at least 0.00001 , 0.0001 , 0.001 , 0.01 , 0.1 , 0.2, or 0.3 and / or up to 0.3, 0.4, or 0.5, such as 0.00001 , 0.00005, 0.0001 , 0.0005, 0.001 , 0.005, 0.01 , 0.05, 0.1 , 0.2, 0.3, 0.4, or 0.5, relative to a corresponding (porous) substrate without the coating thereon (e.g., determined as a ratio of two water vapor transmission rate (WVTR) values). That is, the coated article can have a relative permeability for water vapor of 0.5 or less based on absolute water vapor transmission rates for the coated article and uncoated (porous) substrate. Alternatively or additionally, the coated article can have a relative permeability for non-water gas of at least 0.00001 , 0.0001 , 0.001 , 0.01 , 0.1 , 0.2, or 0.3 and / or up to 0.3, 0.4, or 0.5, such as 0.00001 , 0.00005, 0.0001 , 0.0005, 0.001 , 0.005, 0.01 , 0.05, 0.1 , 0.2, 0.3, 0.4, or 0.5, relative to a corresponding (porous) substrate without the coating thereon. This relative permeability for non-water gas can be applicable for one or more gases such as oxygen, nitrogen, carbon dioxide, and other common components of air. Alternatively or additionally, the coated article 10 can have an absolute permeability for water vapor of up to 100 g / m2 / day, for example at least 0.1 , 1 , 2, 5, 7, 10, or 15 g / m2 / day and / or up to 10, 15, 20, 25, 30, 40, 50, 60, 80, or 100 g / m2 / day.

[0104] The water- and oil-resistance properties of the coated article 10 or corresponding coating 200 can be characterized in terms of one or more contact angles for water and / or oil droplets (e.g., vegetable oil such as castor oil) on the coating 200.

[0105] In embodiments, the article or coating has a water contact angle in a range from 80° or 90° to 120°, for example at least 80°, 85°, 90°, 95°, 100°, or 105° and / or up to 110°, 115°, or 120°, such as 90°, 95°, 100°, 105°, 110°, 115°, or 120°. The water contact angle can apply, for example, to a measurement after an interval of 30 sec or 5 min after application of a test droplet on the coating surface. In some cases, the water contact angle can be up to about 125° for non-smooth or rough surfaces.

[0106] In embodiments, the article or coating is resistant to the spreading of oil on its surface. In embodiments, the article or coating has an oil contact angle in a range from 1 °to 65° or 10° to 75°, for example at least 1 °, 10°, 20°, 30°, 40°, or 50° and / or up to 40°, 50°, 60°, 65°, 70°, or 75°. The oil contact angle can apply, for example, to a measurement after an interval of 30 sec or 5 min after application of a test droplet on the coating surface.

[0107] The contact angles for the article or coating can be higher when additives or nanofillers (e.g., clay, silica, etc.) are included in the composition as compared to acorresponding composition without any nanofillers. For example, in the case of articles or coatings further including one or more additives nanofillers (e.g., nanoclay, graphene oxide, graphene, silicon dioxide (silica), aluminum oxide, cellulose nanocrystals, carbon nanotubes, titanium dioxide), the contact angles suitably can range from 100°to 150°for water (e.g., at least 100°, 110°, 120°, 130° or 140° and / or up to 150°, 140°, 130°, 120°, or 110°), and from 20° to 120° for oil (e.g., at least 20°, 30°, 40°, 50°, 60°, 70°, and / or up to 80°, 90°, 100°, 110°, or 120°).Test Methods

[0108] Water Resistance: The water resistance of a coating can be measured as a Cobb1800 value that represents grams of water per square meter that a coating or coated article absorbs in 1800 seconds when brought in contact with water. Cobb 1800 values were determined via a TAPPI standard T441 om-09 protocol, where a Cobb sizing tester (Buchel BV Inc. Utrecht, Netherlands) was used to allow DI water (100 mL) to come into contact with a 100-cm2or 133-cm2specimen for 1800 seconds (30 minutes). The paper samples were submerged in 100 mL of deionized water (DI) for 1800 seconds and then water was quickly discharged from each sample, with paper towel being used to absorb excess water. The weight of the water absorbed by the wax was calculated by the difference in the weight of each specimen before and after the test. Cobb 600 and Cobb 60 values can be analogously determined using 600- and 60-second water contact times, respectively. Cobb values are expressed herein in grams per square meter (g / m2) unless otherwise indicated.

[0109] Droplet behavior test: The droplet behavior test was used to assess the water resistance of coated papers to liquid water by applying a water droplet with a volume of 0.1 mL onto paper samples and observing the water absorption. To evaluate how deeply the droplet penetrated the coated paper, photographs were taken before the droplet was applied, five minutes after it was applied, and after it was removed. The presence of any stains indicated that the sample had poor water resistance. A castor oil droplet test was also measured using castor oil as a liquid instead of deionized water via the same procedure that was used for the water droplet test to visualize oil resistance.

[0110] Oil / Grease Resistance (Kit Rating): Oil / grease resistance tests were performed in accordance with the T 559 pm-96 standard method or the TAPPI UM 557 standard method. Oil / grease resistance is represented by a kit rating value, where 12 / 12 denotes the maximum grease resistance, and 0 / 12 corresponds to no grease resistance. According to the methods, a series of numbered solutions (1-12) with various surface tensions andviscosities (aggressiveness) were prepared by mixing specific proportions of castor oil, n- heptane, and toluene. Higher numbered solutions are more aggressive with lower surface energies (i.e., solution #1 is the least aggressive oil while #12 is the most aggressive oil). A test specimen was placed on a black bench, and various test solutions were gently allowed to drop onto the surface of the specimen from a height of 1 .27 cm and quickly removed with a clean tissue after 15 s. The tested area was examined immediately and a specimen with darkened spots was considered to have failed the test. The tested surface was viewed, and if any dark spots emerged after the test had been performed using the liquid with a certain kit number, it was considered to have failed that particular test. The number of the most aggressive solution that remained on the surface of a specimen without causing any failure was reported as the “kit rating.” A higher kit rating indicates stronger grease resistance.

[0111] Nuclear Magnetic Resonance (NMR) Analysis:1H-NMR spectra for all samples were recorded using 500 MHz NMR spectrometer (Varian 7600-AS, USA). Samples were prepared by dissolving 5 mg of the corresponding polymer in 0.7 mL of deuterated chloroform (CDC ). Chemical shift values for all the spectrums were recorded in ppm.

[0112] Fourier-transform Infrared (FTIR) analysis: Attenuated total reflectance-Fourier- transform infrared (ATR-FTIR) spectra of the paper samples and polymers used as a coating material were recorded with a Jasco FTIR-6600 spectrometer (Easton, Maryland, USA). The spectra were acquired spanning the wavelength range of 4000-500 cm'1with a total of 16 scans, and with 16 background scans having been recorded prior to insertion of the sample.

[0113] Differential scanning calorimetry analysis (DSC): Differential scanning calorimetry analysis was carried out to find the melting temperatures (Tm) of synthesized samples using a TA Instruments DSC-Q100 system. The analysis was performed at a heating rate of 10 °C / min and the heating range was between 0 °C and 250 °C.

[0114] Thermogravimetric analysis (TGA): Thermogravimetric analysis of all the samples were recorded using thermogravimetric analyzer (Q 50). Samples (8 mg) were heated at a ramping rate of 10 °C per minute in a standard pan, spanning a temperature range of 10°C to 600 °C. The test was performed at a flow rate of 40 mL / min in a nitrogen environment.

[0115] Water vapor transmission rates analysis (WVTR): A PERMATRAN-W system (Model 3 / 34, Mocon Inc., MN, USA) was used to determine water vapor transmission rates (WVTR) at 23 °C and at 50% RH or at 90% RH and 38 °C. Paper samples with dimensions of 2.5 x 2.5 cm2were fixed in an aluminum mask sheet, and a 0.5 cm2open hole was left in the sample to expose it to water vapor. Water vapor permeation was calculated by multiplying thickness of paper samples with water vapor transmission values.

[0116] Contact angle measurements: An approximately 10 pL droplet of deionized water or castor oil was introduced on the tested paper samples. A 590-U1 AST VCA 2500XE Video Contact Surface Inspection Goniometer Fuji 611847(AST Products, Inc. MA, USA) instrument was used for contact angle analysis. The images were recorded after placing the droplet and at different time intervals i.e., 30 sec and 5 min, generally at about room temperature (e.g., 20-30°C or about 25 °C). The tested surface was also examined to trace the appearance of any dark stains once the test was completed. The contact angles were taken in triplicates and results were reported as mean of left and right angles.

[0117] Scanning electron microscopy (SEM): The SEM analysis was performed using JEOL SEM System (6610), to explore the surface morphology of paper samples. Prior to SEM analysis, each sample was loaded with a thin layer of gold (15 nm) using sputtering technique.

[0118] Gel permeation chromatography (GPC) analysis and molecular weight determination: The molecular weights were determined using a size exclusion chromatography (SEC) system (Waters 717 plus Autosampler, Massachusetts, USA). The SEC system was attached to a refractive index detector (Waters 2414), an isocratic pump (Waters 1515), an autosampler (Waters 717), and a series of HR STYRAGEL HR4, HR3, and HR2 (300 mm x 7.8 mm I.D.) columns with a controlled temperature of 35 °C and tetrahydrofuran (THF) was employed as an eluent at a flow rate of 1 mL / min. Approximately 2 mg of the copolymer was dissolved in 20 mL of THF and kept overnight before being filtered using a PTFE-GF (polytetrafluoroethylene-glass fiber) syringe filter (pore size = 0.45 pm and diameter = 13 mm). The polystyrene standard-SHODEX SM-105 supplied by Waters was used for the calibration (which was performed via three replications).

[0119] Basis weight and thickness: The thickness of the paper samples was measured using a digital micrometer (Testing Machine Inc., New Castle, DE, USA). Ten random locations on the paper samples were used to measure the thickness of each sample, which was then reported as an average value in pm. Using a sample with dimensions of 10 x 5 cm2, the basis weight was determined using the mass per square meter method as per the standard ASTM D646 technique. Each paper sample was weighed prior to coating, and then after the coating had been applied the paper sample was weighed again. This weighing measurement was repeated after the coating procedure had been performed until the sample was completely dry (and a constant weight was reached) to find the basis weight (g paper sample per m2paper sample). The coating load of each paper sample was determined based on the difference between the basis weight before and after coating.

[0120] Mechanical properties: A 5565 Universal Instron Testing Machine (Instron, MA, USA) was used to investigate the coated paper sample's tensile properties in accordance with the TAPPI standard T494 protocol. Using a JDC precision sampler cutter, paper samples with dimensions of 2.54 cm x 10.16 cm were created. Each sample was examined while being stretched at a steady rate of 10 mm / min and with a grip separation of 25 mm. The BLUEHILL Universal software program (Instron, MA, USA) was utilized to record the tensile properties. A TMI crush tester was used to measure the ring crush resistance. Emerson's Model 1210 Crush Tester (MA, USA) was used to analyze the RCT value in both the machine direction (MD) and the cross direction (CD) using the TAPPI T882 standard methodology. Three measurements were recorded for each sample, and an average value was obtained. Measurements from the Ring Crush Test (RCT) were obtained to provide insight into the resistance of a paper ring of a given length and width.

[0121] Thermal sealing properties: A bar sealer (SENCORP, MA, USA) was used to evaluated the thermal sealing capabilities of a sample via the ASTM F88 / F88M-21 methodology. Both the maximum and average seal strengths were noted. The prepared sealed specimens measured one inch in width and four inches in length. At 400 °F (204 °C), samples were sealed with a bar sealer for a duration of 5 seconds. For every sample set, five duplicates were employed, and the seal width was maintained at 1 .0 cm. Prior to the seal strength testing, the produced sealed samples were kept for 24 h at 25 °C and 50% RH. The seal strength was measured using a 5565 Universal Instron Testing Machine (Instron, MA, USA) at a grip separation of 2.54 cm and steady rate of 30.5 cm per minute.

[0122] Repulpability: The standard test entitled “BA voluntary standard for repulping and recycling corrugated fiberboard treated to improve its performance in the Presence of water and water vapor-part I repulpability” was used for this analysis. Coated paper (25g) was cut into strips of 3.2 cm x 10.2 cm strips, then soaked in warm water 1500 mL for 4 h. The temperature was maintained at 52°C (+ / -6qC). After soaking the paper was repulped using a pre heated Modified Waring Blender maintaining a speed of 15000 rpm for four minutes, it was subsequently washed with 500 mL of water. After washing the fibers were deflaked in a British Disintegrator for five minutes (2000 mL, total volume) at 3000 rpm, maintaining the pH of 7 + / - 0.5 at 52 °C (+ / -6°C). The pulped material was separated in a flat screen with 0.010-inch slots, to determine the fiber recovery as a percentage of the amount of fiber charged. Net accepts and net rejects were stored in aluminum weighing pans and subsequently dried in a laboratory oven at 105 °C for 12 h. The dried net rejects and net accepts were weighed to calculate the yield of repulping. An 85% repulping yield is required to pass this test.

[0123] Recyclability: A lab-scale recyclability test was carried out using the modified “FBA voluntary standard for repulping and recycling corrugated fiberboard treated to improve its performance in the presence of water and water vapor- part ii recyclability” test procedure. During the process, 20% coated paper sample (CPBAT-A-S or CPBAT-B-S, each used separately) and 80% uncoated base paper (Uncoated kraft paper, KP) were mixed and repulped in a lab-scale pulper at pH of 7 + / - 0.5 at 52 °C (+ / -6°C) for 15 minutes. The pulped suspension was passed through a vibration flat screen with 0.0254 cm slots. Handsheets were subsequently made from screen accepts. These handsheets were tested for various properties following TAPPI standards, including coefficient of friction (slide angle) by the TAPPI T815 protocol, short span compression strength (STFI) by the TAPPI T831 protocol, the water drop penetration test, burst strength (TAPPI T403), water-drop penetration (TAPPI T831), and stickies count tests (TAPPI T277). The results were compared to those obtained with a control sample, which was a 100% base paper (uncoated kraft paper) that had been pulped and screened using identical conditions.Examples

[0124] The following examples illustrate the disclosed ionizable polyesters and methods for synthesizing same, but are not intended to limit the scope of any claims thereto. Equivalents (eq.) are listed as molar equivalents unless indicated otherwise.Example 1 : PLA-Based Ionizable Polyesters

[0125] This example illustrates the synthesis and emulsification of ionizable polyesters according to the disclosure including (i) polyester repeat units having polylactide (PLA) segments with pendant hydrophobic groups and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. The ionizable polyesters were coated on paper substrates and tested for various properties.

[0126] Synthesis of ionizable polyesters: A mixture of stearic acid (“ST”) (1 mol equiv.), 1 ,4-butanediol diglycidyl ether (“BDGE”) and tin(ll)-2-ethylhexanoate (0.5 wt.%) was heated at 170 °C for 6 h to form a corresponding diol (“HO-ST-BDGE-ST-OH”) (Fig. 5 (step 1)). Different molar equivalent of L-lactide (15, 20, 30 mol equiv.), HO-ST-BDGE-ST-OH (1 mol equiv.) and tin(ll)-2-ethylhexanoate (0.5 wt.%) were combined and heated at 170 °C for 3 h to form polylactide (PLA)-based polyester diols A, B, and C (“HO-PLA-ST-BDGE-ST-PLA-OH”) (Fig. 5 (step 2)). The polyester diols of step 2 (1 mole equiv.), meso-butane-1 ,2,3,4- tetracarboxylic dianhydride (MBTCA) (1 mole equiv.) and tin-2-ethylhexanoate (0.5 wt.%) were combined and heated at 170 °C for 1 h to form ionizable polyesters CPE A, B, and C having repeat units with polylactide-based polyester residues (A) and dicarboxylic linkinggroups (L1) (Fig. 5 (step 3)). The polyester diols and the corresponding ionizable polyesters formed after reaction with MBTCA were tested via GPC to evaluate their molecular weight distributions, and the results are shown in Table 1 .Table 1. Molecular weight of polyester diols and CPE ionizable polyesters

[0127] lonization / neutralization and emulsification: Each carboxylic functionalized polyester (1.1 g) was added to a solution of ammonium bicarbonate (equivalent to the weight of MBTCA) dissolved in water (4.5 mL). The solutions were stirred under heating for 1 min at 120 °C (oil bath) and stirred for 15 min at room temperature (about 20-25 °C) until 100 % ionization / emulsification. The acid forms of the ionizable polyesters CPE A, B, and C were converted to corresponding ammonium salt forms (Fig. 6).

[0128] Paper coating: The 100 % ionization / emulsification solutions were coated over an unbleached kraft paper by using a silicone spatula. The coated papers were dried in oven at 95°C for 2 h and then the temperature was increased to ^O-MOC for 10-15 min to give the homogeneous coated papers. The coated papers were tested for their Cobb600 and kit ratings, and the results are shown in Table 2.Table 2. Cobb and Kit values of coated papers with CPE ionizable polyesters

[0129] Repulping test: The coated paper was cut into small pieces and dipped into water (3 mL). The solution was heated at 70 °C for 10 min, then sodium bicarbonate (15 mg) was added, and then the mixture was stirred for 5-10 min. An emulsified solution was formed, demonstrating the ability to remove the ionic polyester coating from the paper substrate in a recycling or repulping process.Example 2: PBAT-Based Ionizable Polyesters

[0130] This example illustrates the synthesis and emulsification of ionizable polyesters according to the disclosure including (i) polyester repeat units having polybutylene adipate terephthalate (PBAT) segments and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. The ionizable polyesters were coated on paper substrates and tested for various properties.

[0131] Synthesis of ionizable polyesters: Commercial PBAT (20 g), 1 ,4-butanediol (0.491 g or 0.88 g) and zinc acetate (1wt%) were heated in a closed, high pressure vessel at 180-210qC for 6 hours to yield PBAT-diol A (0.491 g 1 ,4-butanediol) or PBAT-diol B (0.88 g 1 ,4-butanediol) (Fig. 7 (step 1)). PBAT-diol A (8 g), MBTCA (0.646 g) and tin-2- ethylhexanoate (0.5 wt.%) were heated at 170 °C for 1 h to yield CPBAT A, while PBAT-diol B (8 g), MBTCA (0.323 g) and tin-2-ethylhexanoate (0.5 wt.%) were heated at 170°C for 1 h to yield CPBAT B (Fig. 7 (step 2)). The polyester diols and the corresponding ionizable polyesters formed after reaction with MBTCA were tested via GPC to evaluate their molecular weight distributions, and the results are shown in Table 3.Table 3. Molecular weight of polyester diols and CPBAT ionizable polyesters

[0132] lonization / neutralization and emulsification: Each carboxylic functionalized polyester (1 .2 g) was added to a solution of ammonium bicarbonate (equivalent to the weight of MBTCA) dissolved in water (5 mL). The solutions were stirred under heating for 1-10 min at 120 °C (oil bath) and stirred for 15 min at room temperature (about 20-25 °C) until 100 % ionization / emulsification. The acid forms of the ionizable polyesters CPBAT A, B, and C were converted to corresponding ammonium salt forms (Fig. 8).

[0133] Paper coating: The 100 % ionization / emulsification solutions were coated over an unbleached kraft paper by using a silicone spatula. The coated papers were dried in oven at 95 °C for 1 h and then the temperature was increased to ^O-MOC for 20-30 min to give the homogeneous coated papers. The ionizable polyesters (1.1 g) also were dissolved in chloroform (2.5 mL) and coated over an unbleached kraft paper by using silicone spatula,followed by drying in oven at 70 °C for 1 h. A mixture of the ionizable polyesters (1 .0 g) and carnauba wax (0.1 g) also were dissolved in chloroform (2.5 mL) and coated over an unbleached kraft paper by using silicone spatula, followed by drying in oven at 70 °C for 1 h. The coated papers were tested for their Cobb600, Cobb1800, and / or kit ratings, and the results are shown in Table 4.Table 4. Cobb and Kit values of coated papers with CPBAT ionizable polyesters

[0134] Repulping test: The coated paper was cut into small pieces and dipped into water (3 mL). The solution was heated at 70 °C for 10 min, then sodium bicarbonate (15 mg) was added, and then the mixture was stirred for 5-10 min. An emulsified solution was formed, demonstrating the ability to remove the ionic polyester coating from the paper substrate in a recycling or repulping process.Example 3: PDMS-Based Ionizable Polysiloxanes

[0135] This example illustrates the synthesis and emulsification of ionic polysiloxanes according to the disclosure including (i) polysiloxane repeat units having polydimethylsiloxane (PDMS) segments and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. The ionizable polysiloxanes were coated on paper substrates and tested for various properties.

[0136] Synthesis of ionic polysiloxane: A commercial hydroxyl-terminated PDMS (or PDMS diol) (1 mol. eq.) was reacted with MBTCA (1 mol. eq.) and tin-2-ethylhexanoate at 170 °C for 1 h to yield a corresponding ionic polysiloxane CPDMS (Fig. 9). The carboxylic functionalized polysiloxane was added to a solution of ammonium bicarbonate dissolved in water to ionize and emulsify the polymer, converting the acid forms of the ionic polysiloxane CPDMS to corresponding ammonium salt forms (Fig. 10). A 5% starch-coated paper was formed using the ionic polysiloxane as generally described above for coatings with the ionizable polyesters, and the coated papers had Cobb60, Cobb600, Cobb1800, and kit ratings of 1.8, 3.5, 14.4, and 12, respectively.Example 4: PBAT-Based Ionizable Polyesters

[0137] This example illustrates the synthesis and emulsification of ionizable polyesters according to the disclosure including (i) polyester repeat units having polybutylene adipate terephthalate (PBAT) segments and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. The ionizable carboxylic acid- functionalized poly(butylene adipate-co-terephthalate) (CPBAT) polyesters were coated on paper substrates and tested for various properties. Paper coated with waterborne CPBAT exhibited excellent water, oil, moisture, and gas barrier properties suitable for packaging applications. The recyclability and repulpability of the CPBAT -coated paper were successfully validated via certified TAPPI methods. The example demonstrates coated paper with favorable barrier properties that is per- and polyfluoroalkyl substance (PFAS)- free, recyclable, and biodegradable, with significant benefits for the environment and human health.

[0138] Materials: Poly(butylene adipate-co-terephthalate) (PBAT) was obtained from Amcor Global. Meso-butane-1 ,2,3,4-tetracarboxylic dianhydride (MBTCA) was obtained from Fischer Scientific. 1 ,4-Butanediol and zinc acetate were obtained from Sigma-Aldrich. Unbleached kraft paper substrates were obtained from Uline (Wl, USA) with a basis weight of 137.0 ± 0.5 g / m2. Corn starch was obtained from Aldrich (USA). All chemicals / materials were used as received without further purification.

[0139] Synthesis of low molecular weight PBAT -diol A: A 250 mL one-neck round-bottom flask was charged with commercial PBAT (200 g), 1 ,4-butanediol (4.91 g), and zinc acetate (1 wt%). The mixture was heated at 200 °C under mechanical stirring for 6 h to yield PBAT- diol A.

[0140] Synthesis of low molecular weight PBAT-diol B: A 250 mL one-neck round-bottom flask was charged with commercial PBAT (200 g), 1 ,4-butanediol (8.80 g), and zinc acetate (1 wt%). The mixture was heated at 200 °C under mechanical stirring for 6 h to afford PBAT- diol B.

[0141] Synthesis of carboxylic PBAT A (CPBAT A): A 250 mL one-neck round-bottom flask was charged with PBAT-diol A (150 g) and MBTCA (8.43 g). The mixture was heated at 170 °C under mechanical stirring for 30 min to yield CPBAT-A. No further purification was performed.

[0142] Synthesis of carboxylic PBAT B (CPBAT B): A 250 mL one-neck round-bottom flask was charged with PBAT-diol B (150 g) and MBTCA (16.50 g). The mixture was heated at 170 °C under mechanical stirring for 30 min to form CPBAT-B.

[0143] Emulsification of CPBAT-A and CPBAT-B: A solution of aqueous ammonium hydroxide (10 mL, using 15 mL of deionized water) was used to emulsify weighed quantities of CPBAT-A in a 100 mL beaker, which was properly covered with aluminum foil. After 45 min of constant stirring at 77 °C, the final mixture exhibited a homogeneous milky color, indicating that it had underwent complete ionization and emulsification. The final emulsion had a pH of 7-8. A similar approach was used to make an emulsion from CPBAT-B.

[0144] Paper coating procedure: Starch-coated kraft paper samples were prepared by applying a 5 wt.% starch / 95 wt.% water aqueous solution onto uncoated kraft paper using a multicoated machine (K303 Multi Coater), and this coating process was followed by air drying for 24 h. Prior to the application of the designed coating solution, 5 wt% starch-coated kraft paper was trimmed into 20 x 15 cm2sections and fixed to aluminum plates with tape. The coating material was then applied using a silicon spatula. The resultant coated paper samples were dried in a preheated oven at 130 °C for 30-40 min. This coating procedure was performed in batches to ensure the application of the coating in a smooth and uniform manner. After they had been dried in an oven, all the samples were air dried for 24 h prior to testing and further analysis. For paper samples further including a CPBAT coating (e.g., with or without an underlying starch coating), the paper samples were coated with waterborne emulsions of the CPBAT polymers using the same multicoating machine. The resultant coated paper samples were dried for 10 min at 160 °C in a preheated oven until a shiny coated surface appeared. Prior to testing and additional examination, all the samples were allowed to air dry for a full day before they were subsequently dried in an oven for 10 min at 160 °C.

[0145] Results: The purpose of carboxylic (COOH) groups in CPBAT was to provide a waterborne emulsion via COOH neutralization. However, incorporating COOH into polyesters is not an easy task because COOH degrades polyesters under high temperature and prolonged duration. Essentially, there is no way one can make COOH-bearing polyester by routine polycondensation that requires longer hours (8-24 hrs) and high temperature (200-230 °C). To address this issue, the disclosure employs a strategy as generally shown in Fig. 7 to synthesize carboxylic acid-functionalized PBAT (CPBAT). Firstly, high molecular weight commercial PBAT was treated with 1 ,4-butanediol to provide low molecular weight PBAT -diols. Subsequently, the obtained low molecular weight PBAT -diols were reacted withMBTCA via ring-opening addition reactions to afford CPBAT polymers. The advantage for this method was that the ring opening occurs in minutes and at milder temperatures (about 170 °C) to avoid / minimize degradation.1H-NMR analysis (not shown) confirmed the structure of the CPBAT product.

[0146] Size exclusion chromatography (SEC) was used to determine the average molecular weights of neat PBAT, PBAT-diols, and CPBAT polymers. Neat PBAT has a Mn and Mw of 31 .23 and 59.08 kDa, respectively. The reaction of neat PBAT with 1 ,4-butanediol resulted in the degradation of the polymer chains to afford PBAT-diols with lower molecular weights. PBAT-diol A exhibited a Mn and Mw of 6.94 and 8.61 kDa, respectively. Similarly, the Mn and Mw of PBAT-diol B are 6.12 and 7.25 kDa, respectively. PBAT-diol B showed smaller Mn and Mw values than those of PBAT-diol A because a larger amount of 1 ,4- butanediol that was employed for the reaction with neat PBAT, which led to a higher degree of degradation and consequently yielded lower molecular weights. Moreover, CPBAT-A exhibited a Mn and Mw of 9.15 and 15.60 kDa, respectively, which corresponded to a reasonable increase as compared to that of PBAT-diol A. Furthermore, CPBAT-B exhibited a Mn and Mw of 8.48 and 13.90 kDa, respectively, which were significantly higher than the corresponding values for PBAT-diol B. The increase in the average molecular wights is due to the chain extension of PBAT-diol end-capped hydroxyl groups with the dianhydride rings of MBTCA.

[0147] The 100% waterborne ionic emulsions of CPBAT-A and CPBAT-B were used to coat paper substrates. Ammonium hydroxide was used to ionize the synthetic polymers CPBAT-A and CPBAT-B to create an emulsion under stirring at 80 °C. Ammonium hydroxide was used because ammonia evaporates during the paper drying process, leaving behind a water-resistant coating. In contrast, if this neutralization was performed with inorganic bases such as NaOH, it would leave sodium salt, which absorbs water. Thus, ammonia is suitable for creating CPBAT-A and CPBAT-B emulsion for paper coating. The CPBAT emulsion once coated onto the starch-coated paper were dried in an oven at 160 °C for 10 min to let ammonia evaporate leaving free carboxylic acid groups in CPBAT. Removing the ammonia from CPBAT helped to convert salt form to COOH form, that resulted in better water and oil resistance.

[0148] The properties of the coated paper samples are shown in Table 5 including the thickness, basis weight, and coating load that describes the total content incorporated onto the paper during the coating process. The original kraft paper (KP) used had a thickness of 181 .7 ± 3.4 pm and a basis weight of 129.20 ± 1 .04 g / m2. The incorporation of a starch layerhad slightly augmented the thickness of the paper up to 201 .0 ± 5.6 pm. The application of polymer emulsions resulted in further increases in the thickness, which reached 243.9 ± 9.9 pm for the CPBAT-A-S-coated paper sample (coated with starch and then CPBAT-A) and 255.8 ± 17.7 pm for the CPBAT-B-S-coated paper sample (coated with starch and then CPBAT-B). Correspondingly, there was a synchronized rise in the basis weight ranging from 145.92 ± 2.04 (for starch-coated paper, SKP) to 209.64 ± 2.36 g / m2(for CPBAT-B-S). The coating load exhibited a similar trend, with values ranging from 42.26 ± 1 .3 to 80.44 ± 2.36 g / m2. It was found that the coated paper samples that were exclusively coated with polymer materials exhibited smaller basis weights and coating loads compared to the samples that were coated with a starch layer prior to the application of the polymer layer. This difference is attributable to the increased coating content that was encountered in the latter case due to the presence of a starch base layer in addition to the polymer-based layer.Table 5. Paper properties and coatings using CPBAT ionizable polyesters

[0149] FTIR analysis (not shown) confirmed the structure of the formed CPBAT polymers and their successful lamination onto kraft paper.

[0150] The low water and oil resistance is an intrinsic property of uncoated paper due to the presence of numerous pores and voids on its surface. This porous nature of paper allows liquids (such as water and oil) to permeate through its surface. The application of the ionic polyester coating according to the disclosure caused all the pores present on paper’s surface to become covered, leading to a significant enhancement of the paper’s barrier properties.

[0151] The inherent porous nature of paper substrates also makes them susceptible to water absorption during environmental exposure in situations such as storage, transportation etc. These drawbacks severely limit their suitability for packaging applications. To address these shortcomings of paper substrates, a water-resistant coating material is used as a paper coating which modifies the surface porosity and increases water resistance of potential coated paper-based packaging material. This hydrophobic coating material helps withstand the challenges posed by environmental factors such as humidity.

[0152] Water resistance: The paper samples were tested for their water resistance by measuring their Cobbl 800 values (g / m2). Sample KP absorbs a lot of water due to its porous structure, with a relatively high Cobb1800 value of 81.68 ± 0.03 g / m2. The introduction of a starch prior layer has reduced the Cobb1800 value to 63.08 ± 3.82 g / m2, indicating that the pores on the paper’s surface have been effectively masked. However, it is important to note that despite a thorough coverage of all pores, the starch material is hydrophilic, and thus it provides only a modest 22% reduction in the Cobb1800 value. In contrast, the application of the ionic polyester coating remarkably reduced the Cobb1800 values to 4.33 ± 0.77 g / m2for the paper sample CPBAT-A-S and 5.15 ± 0.62 g / m2for sample CPBAT-B-S. These Cobb values are truly remarkable suitable for holding water long time without any leakage. Nevertheless, when KP was coated with CPBAT without the application of starch as a base layer as was the case with CPBAT-A-K and CPBAT-B-K, the Cobbl 800 values were still very good, but relatively weaker relative those of the CPBAT-A-S and CPBAT-B-S counterparts. An overall reduction in Cobb1800 value has been consistently observed for all coated paper samples, with the best performing sample (CPBAT-A-S) achieving a reduction of up to 95%.

[0153] To assess the effect of liquid water on the surface of coated paper samples, a droplet test was also conducted by placing a water droplet on the surface of the best performing sample (CPBAT-A-S) in contrast to KP. A 0.05 mL deionized water droplet was placed on the surface of paper and images were captured before placing the droplet, 5 minutes after the droplet had been placed on the sample, and then after removal of the droplet to investigate the trace of any residual. The results revealed that a dark spot became visible soon after the droplet had been placed on the KP sample surface, indicating a significant amount of water has been absorbed by KP. In contrast, the sample CPBAT-A-S exhibited no stains on placing of water. These results indicate that the coated paper enhanced water resistance, as was evident from the absence of any traces or stains after removal of the droplets.

[0154] Water vapor barrier properties: The water barrier properties of coated paper samples were evaluated by assessing their water vapor transmission rate (WVTR) values. All the samples were tested, and measurements were conducted at 50% RH and 23 °C. The WVTR values of all the samples were in line with the Cobbl 800 data. The KP showed the highest WVTR value of 772.34 ± 5.37 g / (m2-day), due to its inherently porous nature. The lamination of paper with starch led to a significant reduction in the WVTR value to 372.59 ± 4.71 g / (m2-day), due to the starch’s exceptional film-forming capabilities. However, this reduction was somewhat modest due to the hydrophilicity of starch. Meanwhile, the application of polymer coatings led to dramatic decreases in the WVTR value, to 36.37 ± 1 .25 and 48.67 ± 1.15 g / (m2-day) for the CPBAT-A-S and CPBAT-B-S samples, respectively. Overall, there was an exceptional decrease in the WVTR value by up to 95% in contrast to that observed with KP, which clearly indicates that the synthesized polymers have excellent water barrier properties.

[0155] Oil resistance: The oil resistances of KP and the resultant coated paper samples were evaluated via the kit rating test. The increase in the kit ratings shows that the coated paper exhibited a notable improvement in oil resistance in contrast to that of KP, which had a kit rating of 0. A higher kit rating corresponds to stronger oil resistance and vice versa. Among the samples, KP exhibits the weakest oil resistance as demonstrated by its kit rating of 0, which indicates that this sample failed the kit rating test which was performed with the test liquid which had the lowest kit number of 1 . Application of starch enhanced the oil resistance and the resultant SKP sample thus exhibited a kit rating of 8 due to its oil repellent nature. The application of a polymer (CPBAT-A or CPBAT-B) layer further enhanced the oil resistance yielded the highest possible the kit rating of 12 for the resultant samples CPBAT-A-S and CPBAT-B-S, which also each were initially coated by starch as a base layer. It is important to note that the polymer-coated samples CPBAT-A-K and CPBAT- B-K which lacked a starch base layer exhibited a somewhat more modest kit rating of 10. This slightly lower kit rating suggests that the lack of a starch base layer weakened the oil resistance to some extent.

[0156] Like the water droplet test, the effect of castor oil droplets placed on the surfaces of coated paper samples was explored to further support the kit rating tests. KP quickly absorbed all the oil and a stain was left behind, indicating that KP exhibited poor oil resistance as oil readily entered the pores of the paper. On the other hand, the coated paper sample (CPBAT-A-S) showed no stains, even after 5 min had elapsed. The effect was even more apparent after the oil droplet had been wiped away, as there was no sign of any oil absorption, signifying the high oil resistance of the coated paper sample. In general, the oilresistance of the coated paper has been remarkably improved in contrast to that of the uncoated paper samples.

[0157] Table 6 below summarizes the results for the Cobbl 800 values, WVTR values, and kit ratings.Table 6. Paper resistance and barrier properties using CPBAT ionizable polyesters

[0158] TGA analysis: In paper packaging, the thermal stability of a coating material and the resultant packaging is an important parameter that determines the suitability of a paper product in high-temperature applications. Therefore, TGA characterization was employed to investigate the thermal behavior of the coated paper samples, the associated coating materials, and uncoated kraft paper (KP) as a control. The control, KP, underwent complete decomposition at approximately 383 °C. The solid starch material exhibited two close decomposition points during its thermal degradation, which are observed at -310 and -360 °C. The introduction of starch as a base layer enhanced the thermal stability of KP, which was demonstrated by the thermal decomposition of SKP at around 405 °C, which was higher than the degradation temperatures of KP and solid starch. Similarly, the solid polymers CPBAT-A and CPBAT-B each exhibited two degradation points around -350 °C and -420 °C, indicating their high thermal stability. The coated paper products (CPBAT-A-S and CPBAT-B-S) also displayed a very high thermal stability and underwent complete degradation at around 400-410 °C.

[0159] DSC analysis: DSC analysis was performed to determine the melting temperatures (Tm) of synthesized CPBAT samples. The melting temperature of both samples was found in the range of 105-120 °C, approaching that of commercial PBAT (Tm=120°C).

[0160] Thermal sealing properties: Coated paper samples were thermally sealed, and their seal strength was investigated by recording the force to break the seal and tensile strength at maximum load and break points. Results revealed that paper samples coatedwith the polymer CPBAT-B showed higher seal strengths compared to paper samples coated with CPBAT-A. For example, the coated paper sample CPBAT-B-K exhibited a higher seal strength value of 9.09 ± 0.96 N at maximum load and 1.15 ± 0.05 N at break point, while sample CPBAT-A-K exhibited the strength of 7.26 ± 0.20 N at maximum load and 1 .49 ± 0.20 N at break. It was observed that samples which had starch as a base layer exhibited slightly lower seal strength values compared to their counterparts which lacked a starch layer. For example, sample CPBAT-B-S showed a seal strength of 7.51 ± 0.36 N at maximum load which is 17% lower than the corresponding paper sample CPBAT-B-K (9.09 ± 0.96 N) at maximum load. The results were compared to a commercial control (ECO SHIELD) paper which possess a seal strength of 10.19 ± 0.66 N at maximum load which reduced to 0.40 ± 0.07 at break point, which is comparable to our best performing sample CPBAT-B-K. The maximum tensile strength was shown by the sealed sample CPBAT-B-K (coated without starch) with the value of 1 .57 ± 0.15 MPa at maximum load and 0.25 ± 0.02 MPa at break. These results indicated that coated paper can be used in the packaging industry for making paper bags without incorporating any non-biodegradable adhesives.

[0161] Repulpability and Recyablity: With the growing demands for circular economy, coating paper recycling is pivotal to the new paper packaging designs. To validate that the CPBAT coated papers are recyclable, CPBAT-A-S and CPBAT-B-S were tested for their repulpability and recyclability. The minimum requirement to pass the repulpability test is to have a 85% fiber recovery. The CPBAT-A-S sample exhibited a higher repulpability 93.57% than its CPBAT-B-S counterpart (86.46%). Overall, both papers passed the certified repulpability test as the yields were all above the 85% threshold.

[0162] The samples CPBAT-A-S and CPBAT-B-S were also analyzed for their recyclability. The recycled paper was converted into sheets and tested for various properties, with the results shown in Table 7. The results indicated that the coated paper is recyclable. All samples met the requirements for burst strength, slide angle, and water penetration. No decrease in burst strength and STFI strength was observed for any of the samples. No significant increase in water penetration was observed for any of the samples. A decrease in the coefficient of friction was observed for the CPBAT-B-S sample, but this decrease was less than 15%. Both the tested samples CPBAT-A-S and CPBAT-B-S presented good appearance as there was no significant increase in the number of stickies was found.Table 7. Recyclability of coated papers using CPBAT ionizable polyestersExample 5: PBAT / P LA- Based Ionizable Polyesters

[0163] This example illustrates the synthesis and emulsification of ionizable polyesters according to the disclosure including (i) polyester repeat units having either polybutylene adipate terephthalate (PBAT) segments or polylactide (PLA) segments and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. Blends of the ionizable carboxylic acid-functionalized poly(butylene adipate-co-terephthalate) (CPBAT) and ionic carboxylic acid-functionalized polylactide (CPLA) polyesters were coated on paper substrates and tested for various properties. The resultant coated papers showed a significant decrease in Cobb600 values along with a boost in kit rating, which showed that papers coated with the emulsion of blend not only possess a very high-water resistance as well as high oil resistance, suggesting their application in food packaging. The coated papers were tested for repulping and recycling, and they showed that both CPLA-coated papers are repulpable and recyclable. CPBAT -coated paper is recyclable and repulpable, as demonstrated in Example 4.

[0164] Materials: Poly(butylene adipate-co-terephthalate) (PBAT) was obtained from Amcor Global. Meso-butane-1 ,2,3,4-tetracarboxylic dianhydride (MBTCA) was obtained from Fischer Scientific. 1 ,4-Butanediol, zinc acetate, 1 ,10-decanediol, and tin( 11)-2- ethylhexanoate were obtained from Sigma-Aldrich. Unbleached kraft paper substrates were obtained from Uline (Wl, USA) with a basis weight of 137.0 ± 0.5 g / m2. L-lactide wasobtained from ASW MEDchem, USA. Corn starch was obtained from Aldrich (USA). All chemicals / materials were used as received without further purification.

[0165] Synthesis of carboxylic acid-functionalized poly(butylene adipate-co- terephthalate) (CPBAT): CPBAT-A and CPBAT-B, along with their intermediate PBAT-diols A and B, respectively, were synthesized as described in Example 4.

[0166] Synthesis of carboxylic acid-functionalized polylactide (CPLA): The synthesis of CPLA was also carried out in two steps, and the overall conversion is shown in Fig. 11. To synthesize a PLA diol, a mixture of L-lactide (300 g, 20 mol equiv), 1 ,10-decanediol (18.14 g, 1 mol equiv.) and tin(ll)-2-ethylhexanoate (0.5 wt.%) was heated at 170 °C for 3 h in a round bottom flask while stirring (Fig. 11 (step 1)). To synthesize a carboxylic PLA (CPLA), the product of step 1 (1 mole equiv.) and meso-butane-1 ,2,3,4-tetracarboxylic dianhydride (MBTCA) (20.60 g, 1 mole equiv.) were heated at 170 °C for 30 min in around bottom flask on stirring (Fig. 11 (step 2)). The final CPLA was ionized using ammonium bicarbonate to generate ammonium CPLA (Fig. 11 (step 3)).

[0167] Emulsification of CPLA and CPBAT-B blend: The amount of blend of CPLA / CPBAT (total weight 1.2 g) was dissolved in aqueous solution of ammonium bi carbonate (0.3 g NH4HCO3, 5 mL DI water), using different weight ratios of CPLA and CPBAT ranging from 0-100% CPLA and 100-0% CPBAT in 10% increments. After 45 min of constant stirring at 77 °C, the final mixture exhibited a homogeneous milky color, indicating that it had underwent complete ionization and emulsification. The final emulsion had a pH of 7-8.

[0168] Paper coating procedure: A pre starch (5%) coated paper was trimmed to dimension of were trimmed into 18x15cm2and emulsion solution was applied on it. The coated paper was afterward dried in oven at 100 °C for 10 minutes followed by quick drying at 160 °C until a shiny surface appears. After drying at 160 °C samples were kept at kept at room temperature for 24 hours prior to other testing.

[0169] Liquid water resistance: The standard TAPPI protocol, T441 , was used to record water resistance of paper samples against liquid deionized water via Cobb Test for 600 seconds. The weighed paper sample was placed in the Cobb sizing tester (Buchel BV Inc. Utrecht, Netherlands) and 100 mL of deionized water was added to it. The sample was weighed again after the test and difference in weight was related to cobb600 and results were expressed in units of grams per square meter (g / m2). The results show that incorporation of CPBAT decreases the Cobb600 values resulting in increase of water resistance of coated papers. Cobb600 value go down from 62.64±0.43 g / m2for kraft paperto 5.21 ±0.57 g / m2for kraft paper coated with emulsion of a mixture having 10% CPLA and 90% CPBAT. The application of 100% CPBAT emulsion is further down to 3.43±0.46 g / m2. Overall, 85% decrease in Cobb600 values were found for selected samples having 20% CPLA and 80% CPBAT i.e. sample CPLA / CPBAT-20 / 80, having the highest % of CPLA is 20% in the tested series which has practical applications with Cobb600 values less than 10 g / m2.

[0170] The liquid water test was visualized by water droplet test where a droplet of 0.1 mL was placed on the surface of paper sample and results were recorded by capturing images after the interval of 5 minutes and after wiping off. The result showed that the water droplet was quickly taken by kraft paper as well as CPLA (CPLA / CP BAT- 100 / 0) coated paper only suggesting poor water repellency, while selected sample CPLA / CPBAT-20 / 80 showed no dark sign of water absorption suggesting their high-water repellency.

[0171] Oil resistance: The oil resistance of developed coated papers was established by recording their kit tests following a standard TAPPI T 559 method. A series of kit solution 1 - 12 was prepared using different ratios of n-heptane, toluene and castor oil. A drop 0.1 mL of test solution was placed on piece of paper sample for 15 seconds to check appearance of any dark spots which renders failure of that kit solution. If there is no spot appeared for a test solution, it is called passed. The highest number of kit solutions which sample can sustain is called kit number of that specimen. The results are parallel to water resistance, and kit number has been improved with an increasing fraction of CPBAT in the paper coating. The highest kit number 12 was shown in samples having 0-20% CPLA and 100-80% CPBAT.

[0172] An oil droplet test was performed following similar method used for water droplet test described above. All the coated papers showed no dark spot even after the removal of oil droplet with 5 minutes passage of time.

[0173] Table 8 below summarizes the paper coating compositions and results for the Cobb600 values and kit ratings.Table 8. Coating composition and properties using CPBAT / CPLA ionizable polyesters

[0174] Repulpability: The paper samples CPLA / CP BAT- 100 / 0 and CPLA / CPBAT-0 / 100 were selected for the repulpability experiments to check the recyclability of papers coated with neat CPLA and CPBAT. Both papers passed the certified repulpability test as the yields were all above the 85% threshold, including 94.4% for CPLA / CP BAT- 100 / 0 and 86.5% for CPLA / CPBAT-0 / 100.

[0175] Recyclability: The coated paper samples CPLA / CPBAT-100 / 0 and CPLA / CPBAT- 0 / 100 were also tested for recyclability. The recycled paper was converted into sheets and tested for various properties, with the results shown in Table 9. The results indicated that the coated paper is recyclable. All samples met the requirements for burst strength, slide angle, and water penetration. No decrease in burst strength and STFI strength was observed for any of the samples. No significant increase in water penetration was observed for any of the samples.Table 9. Recyclability of coated papers using CPBAT ionizable polyestersExample 6: PBAT-Based Ionizable Polyester / Wax Blends

[0176] This example illustrates the synthesis of ionizable polyesters according to the disclosure including (i) polyester repeat units having either polybutylene adipate terephthalate (PBAT) segments and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. Blends of the ionizable carboxylic acid- functionalized poly(butylene adipate-co-terephthalate) (CPBAT) and a biodegradable synthetic wax were coated on paper substrates and tested for various properties.

[0177] Synthesis of carboxylic acid-functionalized poly(butylene adipate-co- terephthalate) (CPBAT): CPBAT-A and CPBAT-B, along with their intermediate PBAT-diols A and B, respectively, were synthesized as described in Example 4.

[0178] Synthesis of synthetic wax (ODSA-PLA-19-ODSA): PLA (commodity plastic) 100.0 grams were taken in a 250 mL flask. The flask was connected to a mechanical stirrer and was closed with a rubber septum. The flask was then heated to 220 °C for 2 hour. After which 0.5 wt% zinc ethyl hexanoate was added followed by the addition of propylene glycol (2.78 g, 36.5 mmol), stirring, and then cooling to room temperature to obtain PLA-19 (Fig. 12 (top right)). In a subsequent step, PLA-19 (20.0 grams) was heated in a flask (50 mL) at 160 °C until melting. Once melted, 2-(1-octadecenyl)succinic anhydride (ODSA) (4.611 , g, 13.15 mmol, 1 .8 equiv of terminal -OH) was added in a closed system. The reaction mixture was stirred for 1 hour and then cast on a PTFE plate to obtain a ODSA-PLA-19-ODSA film (Fig. 12 (bottom right product)).

[0179] Preparation of blends: 80 to 90 % of ODSA-PLA-19-ODSA were mixed with 10 to 20 % ionizable polyesters CPBAT-A or CPBAT-B in a vial using 3.0 mL chloroform. Once mixed the mixture was cast on 10% starch-coated kraft paper followed by analysis for the water and oil resistance experiments. Table 10 below summarizes the results for the Cobb1800 values and kit ratings.Table 10. Coating compositions and properties using CPBAT / wax blendExample ?: PBAT-Based Ionizable Polyester / Starch Blends

[0180] This example illustrates the synthesis of ionizable polyesters according to the disclosure including (i) polyester repeat units having either polybutylene adipate terephthalate (PBAT) segments and (ii) ring-opened dianhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. Blends of the ionizable carboxylic acid- functionalized poly(butylene adipate-co-terephthalate) (CPBAT) and starch were coated on paper substrates and tested for various properties.

[0181] Paper coating: Blend solutions were prepared using various weight% ratios of a cationic starch and a CPBAT ionic polyester according to the disclosure (collectively “CPBAT-C”). A 10 weight % of starch solution was prepared for each formulation by dissolving the solid starch in water at 90 °C on stirring until a translucent solution was obtained. CPBAT-C was emulsified in water (17% solution in water) using 30 weight % of ammonium bicarbonate with respect to weight of CPBAT-C at 80 °C. The complete emulsification was indicated by the appearance of milky white liquid free of any solid chunks. Kraft paper was trimmed to 20x15cm2and the emulsion solution was applied on it. The coated paper was then dried in oven at 160 °C for 5-10 minutes. After drying, samples were kept at kept at room temperature for 24 hours prior to other testing. The samples were then tested for their Cobb600 values, kit ratings, and thermal sealing properties (sealed at 350°F / 177°C). The results are shown in Table 11 below in which all “SC” samples were coated on kraft paper, except for SC-30 / 70-S, which was coated on a 5%-starch-precoated kraft paper.Table 11. Coating compositions and properties using CPBAT / starch blendExample s: PBAT-Based Ionizable Polyesters

[0182] This example illustrates the synthesis and emulsification of ionizable polyesters according to the disclosure including (i) polyester repeat units having polybutylene adipate terephthalate (PBAT) segments and (ii) ring-opened limonene anhydride linking groups providing pendant carboxylic acid or carboxylate salt groups. The ionizable polyesters were coated on paper substrates and tested for various properties.

[0183] Synthesis Of limonene anhydride: Under nitrogen (N2)atmosphere, 10.0 g (0.07 mol, 1 eq) of limonene (L) are placed in 100 mL sized boiling flask which was heated in oil bath at 160 °C for 10 min. 21 .6 g (0.22 mol, 3 eq) of maleic anhydride (MA) was added to the hot limonene and the reaction mixture was heated for 5 min, the reaction mixture turns to yellow color. 1 .6 g (10 mol%) benzoyl peroxide was added portion wise in the period of 10 min. The reaction mixture was heated at 160 °C for 30 min, and the reaction mixture turns to dark brown color. After cooling down the polyfunctional limonene anhydride (LMA) crude product (30 g) was collected without any further purification (Fig. 13).

[0184] Synthesis of CPBAT-F: CPBAT-F was synthesized in two steps. In the first step, PBAT diol was synthesized via the reaction of commercial PBAT (25 g), 1 ,4-butanediol (0.75 g), and zinc acetate (1 wt%, 0.25g), in a 250 mL round-bottom flask, on heating at 200 °C. The mixture was continuously stirred using a for 4 h to produce PBAT-diol (98% yield). In the second step, the temperature of the same reaction flask containing the PBAT diol, was lowered to 170 °C, then 3.3 g of limonene anhydride was added. Mixture was allowed to react stirring for 30 min to form CPBAT with a yield of 98%.

[0185] Preparation of CPBAT-F emulsion: CPBAT-F (1.3g) was mixed with 0.3 g ammonium bicarbonate and emulsified using 7 ml deionized water at 90°C for 10-15 min until a milky solution was obtained.

[0186] Paper coating: Coated paper samples were prepared by first applying 5wt% starch solution as a base layer onto unmodified kraft paper using a coating machine (K303 Multi Coater) with rod number 8. The resultant 5% starch-coated papers were air dried at ambient temperature for 24 h prior to the application of a waterborne coating as a top layer. The waterborne emulsion solutions were applied onto starch-coated kraft paper via the doctor blade method, using a silicon spatula. The coated paper was subsequently dried in an oven at 160 °C until a shiny surface appeared, approximately 5-10 minutes. Oven dried coated paper samples were further air dried at ambient temperature for 24 h prior to other analysis. The samples were then tested for their Cobb600 values, kit ratings, and thermal sealing properties (sealed at 350°F / 177°C). The results are shown in Table 12 below.Table 12. Coating compositions and properties using CPBAT ionic polyesterExample 9: PBAT-Based Ionizable Polyesters

[0187] This example illustrates the synthesis and emulsification of ionizable polyesters according to the disclosure including (i) polyester repeat units having polybutylene adipate terephthalate (PBAT) segments and (ii) polyacid linking groups providing pendant carboxylic acid or carboxylate salt groups. The ionizable polyesters were coated on paper substrates and tested for various properties.

[0188] Synthesis of Carboxyl functionalized PBAT (CPBAT) (G1): Charged commercial PBAT (10 equiv) in the round bottom flask (RBF) and raised temperature to 200° C to melt it and cooled down to 180° C. Charged 1 ,4 butanediol (1 equiv) and Zinc-2-ethyl hexanoate as a catalyst to the same RBF and heated under stirring for 2 hours (Fig. 17, step 1). To the same RBF, charged citric acid (0.2 equiv), stearic acid (0.2 equiv) and adipic acid (0.8 equiv) with respect to 1 ,4 butanediol and stirred the reaction mixture at 160° C for 6-7 hours by connecting reaction flask with a vacuum pump through a cold trap to ensure the water is being removed throughout the reaction, thereby forming the CPBAT (G1) product (Fig. 17, step 2). Non-sticky solid product was obtained.

[0189] Synthesis of CPBAT (G2): Charged commercial PBAT (10 equiv) in the RBF and raised temperature to 200 ° C to melt it and cooled down to 180 ° C. Charged 1 ,4 butanediol(1 equiv) and Zinc-2-ethyl hexanoate as a catalyst to the same RBF and heated under stirring for 2 hours. To the same RBF, charged citric acid (0.2 equiv), stearic acid (0.1 equiv) and adipic acid (0.8 equiv) with respect to 1 ,4 butanediol and stirred the reaction mixture at 160° C for 6-7 hours by connecting reaction flask with a vacuum pump through a cold trap to ensure the water is being removed throughout the reaction. Non-sticky solid product was obtained.

[0190] Synthesis of CPBAT (G3): In first step, charged dimethyl terephthalate (DMT) (0.475 equiv), 1 ,4-butanediol (1 equiv) into a round-bottom flask equipped with a condenser. Added Ti (OBu)4 (0.1 mol% with respect to DMT) and heated the mixture to 150 ° C for 1 hour. Then, replaced the condenser with a distillation head, and the heating was continued with the removal of methanol for 3-4 hrs. Then added adipic acid (0.475 equiv) and heated the reaction mixture to 180° C and stirred over an hour with the removal of water and methanol. Then, connected the reaction flask with a vacuum pump through a cold trap and heated to 180-190° C at 1-2 Torr over 4-6 hours. In second step, charged citric acid (0.02 equiv), stearic acid (0.01 equiv) and adipic acid (0.08 equiv) with respect to 1 ,4 butanediol into the same RBF and stirred the reaction mixture at 160 ° C for 5-6 hours by connecting reaction flask with a vacuum pump through a cold trap to ensure the water is being removed throughout the reaction. Non-sticky solid product was obtained.

[0191] Synthesis of CPBAT (G4): Charged DMT (0.475 equiv), 1 ,4-butanediol (1 equiv) and Ti (OBu)4 (0.1 mol% with respect to DMT) and heated the mixture to 150° C for 1 hour using condenser. Then, replaced the condenser with a distillation head, and the heating was continued with the removal of methanol for 3-4 hrs. Then, adipic acid (0.475 equiv), citric acid (0.02 equiv), stearic acid (0.01 equiv) and adipic acid (0.08 equiv) with respect to 1 ,4 butanediol into a round-bottom flask. Then, connected the reaction flask with a vacuum pump through a cold trap and heated to 180-190 ° C over 4-6 hours. Non-Sticky solid product was obtained.

[0192] Enhanced Thermal and hydrolytic stability of the CPBAT: Titanium (IV) butoxide was used as a catalyst 0.05 wt% of monomers and optionally adding catalytic deactivators such as phosphoric acid acid 0.02 wt% with respect to solid polymer. Heat and stir for an additional 5 min to ensure the mixing of phosphoric acid with the material.

[0193] Preparation of emulsion from CPBAT: Low-temperature method: The obtained polymer (total weight, 1 .5 g) was emulsified with an aqueous solution of ammonium hydroxide (0.3mL, 5 mL deionized water) at 90°C for 5-10 min until a milky solution was obtained. High-Temperature method: Took CPBAT (20 g) and heat under stirring to 160 °Cuntil it melted. Then, under mechanical stirring, brought the temperature to 110 °C and added hot water (20 ml, dropwise over 2 min). Then, bring temp to 60 and add warm water + ammonium hydroxide (20 ml). Stirred for a few min at this temp, then lowered the temperature to room temp and then (optionally) added thickener at 1-2wt% with respect to PBAT.

[0194] Paper Coating Procedure: Coated paper samples were prepared by applying 5wt% starch solution as a base layer onto unmodified kraft paper using a coating machine (K303 Multi Coater) with rod number 8. The resultant 5% starch-coated papers were air dried at ambient temperature for 24 h before applying a waterborne coating / emulsion of polymers as a top layer. The waterborne emulsion solutions were applied onto starch-coated kraft paper via the doctor blade method using silicon spatula. The coated paper was subsequently dried in an oven at 130 °C until all the moisture was removed followed by rapid drying with hot air to reach shiny surface using heat gun. Hot air -dried coated paper samples were further air-dried at ambient temperature for 24 h before other analyses. The samples were then tested for their Cobbl 800 values and kit ratings. The results are shown in Table 13 below.Table 13. Coating compositions and properties using CPBAT ionic polyesterFurther Aspects

[0195] Further aspects of the disclosure are provided below. While certain properties or features below are described with respect to specific Formulas l-IV, the properties and features can apply to the ionizable polyesters as described more generally herein.

[0196] In an aspect, the disclosure relates to a polymer (or ionizable polymer) according to the following Formula I:-[A-O(O=C)-L-(C=O)O-]n-A- [Formula I]In Formula I: The group A is aromatic, semi-aromatic, or aliphatic polyester or copolyester with Mw 500 to 20,000 g / mol. The group O(O=C) is an ester bond. The group L is anaromatic, aliphatic, semi-aromatic, cyclic, linear, branched, or acyclic structure with carbon numbers 1 -50, preferentially 2-20, and one or more polar functional groups. These functional groups include carboxyl acids and hydroxyl (primary, secondary, tertiary, aromatic), amine groups (primary, secondary, tertiary, quaternary), phosphates, and so on. Optionally, other functional groups such as C=C, acrylic, ketone, halogen, CN, or other organic functional groups can also be part of the L group. The index n denotes the number of repeat units and ranges between 1 and 500, preferentially 2 to 20. Functional groups in Formula I can be ionizable, such as carboxyl acid groups and amine groups. The polymer in Formula I can have a melting temperature in the range of 80-400 °C, 100-300 °C, or 120-200 °C.

[0197] The polymer according to Formula I can be prepared by the reaction of polyesters such as polylactic acid, polyglycolic acid, polybutylene succinate, or copolyesters such as polybutylene adipate terephthalate with C=C bearing COOH, OH, or other functional groups via free radical grafting reaction. More than one type of polyester diols can be used to react with dianhydride. Examples of dianhydride include Pyromellitic dianhydride, Benzophenone- 3,3',4,4'-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. The polyester diols can be prepared by I) diacid / diester reaction with diol polycondensation polymerization; II) ring-opening polymerization of ring monomers such as lactides, glycolides with small diol molecules such as glycols (ethylene glycol, diethylene glycol, butane diols) etc.; and III) partial depolymerization of long chain polyester (virgin or recycled) with diols to produce low Mw polyester diol.

[0198] In an aspect, the disclosure relates to a polymer (or ionizable polymer) according to the following Formula II and / or Formula III:- [RiRna-O(O=C)-R2R22a-(C=O)-O-]n- [Formula II]-[RiRna-O(O=C)-R2R22a-]n- [Formula III]In Formula II and Formula III: The index n denotes the number of repeat units, which ranges between 5 and 1000, preferentially 20 to 1000. The group O(O=C) is an ester bond. The groups Ri and R2are aromatic, semi-aromatic, or aliphatic with carbon numbers 1-20, preferentially carbon number 2-12. The groups Rnaand R22adenote a carbon atom or a carbon-containing group that also includes a polar functional group, such as carboxyl acids and hydroxyl (primary, secondary, tertiary, aromatic) groups, amine groups (primary, secondary, tertiary, quaternary), phosphates, and so on. The ratio of Ri to Rnain formulas II and III can be 1 :1 , 2:1 , 5:1 , 10:1 , 100:1 , or any range between the foregoing. The ratio of R2to R22ain formulas II and III can be 1 :1 , 2:1 , 5:1 , 10:1 , 100:1 , or any range between the foregoing. Polar functional groups in Formulas II and III can be ionizable, such as carboxylacid groups and amine groups. The polymers in Formula II and III can have a melting temperature in the range of 80-400 °C, 100-300 °C, or 120-200 °C.

[0199] Polymers according to Formula II and III can be prepared by the reaction of polyesters such as polylactic acid, polyglycolic, polybutylene succinate, or copolyesters such as polybutylene adipate terephthalate with R1R2CH=CR3R4, where R1is H, and R2is H, or (C=O)O-X, and R3is H or alkyl, R4is (C=O)O-R5X. R5denotes carbon numbers 1 -20 that could be linear, branched, cyclic or acyclic, aromatic, or aliphatic, where X denotes COOH, OH (primary, secondary, tertiary, aromatic), amine (primary, secondary, tertiary, quaternary), etc. The grafting reaction is at temperatures ranging between 50°C-300°C or 100-250 °C by using radical initiator to monomer (R1R2CH=CR3R4) weight ratios such as 1 :1 , 1 :5; 1 :25; 1 :50, or 1 :100.

[0200] In an aspect, the disclosure relates to a polyester (or ionizable polyester) according to the following Formula IV:-A-L-B-L-A-L-A-L-B- [Formula IV]In Formula IV: A can have one or more ester bonds. A can include homopolyesters such as polylactic acid, polyglycolic, polybutylene succinate, or co-polyester such as polybutylene adipate terephthalate (PBAT), poly(butylene adipate succinate), poly(lactic acod-co-glycolic acid), and so on. The Mw of polyester or copolyester A can be Mw 200-100,000 g mol, preferentially 1000-10000 g / mol. B can have one or more ester bonds. B can be the same as / similar to A, or B can be a different polyester / copolyester. For example, B can be polylactic acid, polyglycolic, polybutylene succinate, or co-polyester such as polybutylene adipate terephthalate (PBAT), poly(butylene adipate succinate), poly(lactic acod-co-glycolic acid), and so on. The Mw of polyester or copolyester of B can be Mw 200-100,000 g mol, preferentially 1000-10000 g / mol. In certain cases, B or A could be fully amorphous. Precursors to A and B can be diols, for example bearing two terminal or internal OH groups such as HO-PLA-OHs that react with L precursors. In some cases, the two OH groups can be internal (e.g., a diol made of stearic acid reaction with diepoxy butane). A and / or B can optionally bear additional functionals such as one or more ketone groups, carbon-carbon double bond, acetal bonds, cyano, halogen, long or short alkyl group, etc. (Fig. 15), which functional groups can be used to improve the performance, end of life options and / or further modification. If A and B are different, then A and B distribution in the structure could alternating, blocky, or random. L can be a dianhydride (or multianhydride with three or more anhydride groups) reaction product that couples A and B. This coupling leads to ester bond formation between A and L as well as B and L. In addition, it also creates one, two, or more pendant COOH groups on L as a product of this reaction between A and L and B and L. Forexample, precursors for L that are reactive with diol precursors to A and B can include a dianhydride, for example aromatic such as pyromellitic dianhydride, benzophenone-3,3’,4,4’- tetracarboxylic dianhydride; aliphatic dianhydride such as butane-1 ,2,3,4-tetracarboxylic dianhydride. In the case of a dianhydride, linear polyesters with pendant COOH groups are formed. In certain cases, L is multi-anhydride such as polymer grafted with maleic anhydride. Polymers on which maleic anhydride include carbon-carbon back bone polymer such as polyethylene-g-maleic anhydride, polypropylene-g-maleic anhydride, or polyesters grafted maleic anhydride PBAT-g-maleic anhydride, PBS-g-maleic anhydride, etc. In the case of multi-anhydride, coupling with polyesters yields graft copolymers.

[0201] Polymers having a structure according to any of Formulas l-IV can be used as film, melt, extrusion, or powder coating on paper, for example for use in packaging and nonpackaging applications (e.g., adhesives, 3D printing, automotive components, construction materials). The coated paper has good water and oil resistance and optionally good gas and water vapor barrier. The polymers can be melt-processed via cast-film or blow films into single layer or multilayer materials. These films / coatings can be separated from paper or other substrate by neutralization with a base such as sodium bicarbonate, sodium carbonate, and sodium hydroxide, ammonium bicarbonate, ammonium hydroxide, triethyl amine, etc. The polymers can be used alone or in combination (e.g., as a blend). These films are biodegradable in aquatic environment and / or compost (industry / home) environment. Single layer or multilayer materials films prepared from the polymers are chemically and mechanically recyclable. The structure shown in Formulas l-IV can be emulsified in water in the presence of neutralization with a base such as sodium bicarbonate, sodium carbonate, sodium hydroxide, ammonium bicarbonate, ammonium hydroxide, triethyl amine, etc. The emulsion / latex of the ionic polymers can be used for paper or other article coatings. In the case of paper substrate, it can be coated with another base layer, such as starch, PVOH, etc., prior to applying the emulsion. In the case of ammonium bicarbonate or ammonium hydroxide derived emulsion, heating of the coated paper leads to the removal of ammonia, leaving behind water resistant non-ionic COOH groups. The coated paper is biodegradable under ambient conditions. The coated paper can be recyclable by dipping in basic medium to neutralize the ionizable polyesters chains to wash off wax coatings.

[0202] Because other modifications and changes varied to fit particular operating requirements and environments will be apparent to those skilled in the art, the disclosure is not considered limited to the example chosen for purposes of illustration, and covers allchanges and modifications which do not constitute departures from the true spirit and scope of this disclosure.

[0203] Accordingly, the foregoing description is given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, as modifications within the scope of the disclosure may be apparent to those having ordinary skill in the art.

[0204] All patents, patent applications, government publications, government regulations, and literature references cited in this specification are hereby incorporated herein by reference in their entirety. In case of conflict, the present description, including definitions, will control.

[0205] Throughout the specification, where the compositions, processes, kits, or apparatus are described as including components, steps, or materials, it is contemplated that the compositions, processes, or apparatus can also comprise, consist essentially of, or consist of, any combination of the recited components or materials, unless described otherwise. Component concentrations can be expressed in terms of weight concentrations, unless specifically indicated otherwise. Combinations of components are contemplated to include homogeneous and / or heterogeneous mixtures, as would be understood by a person of ordinary skill in the art in view of the foregoing disclosure.

Claims

What is claimed is:

1. An ionizable polyester comprising: first repeat units according to Formula (1):-[-A-L1-]- (1); optionally, second repeat units according to Formula (2):-[-B-L2-]- (2); optionally, third repeat units according to Formula (3):-[-C-L3-]- (3); wherein:A comprises one or more polyesters selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations thereof;B is different from A, and comprises one or more functional groups selected from the group consisting of ethylen ically unsaturated groups, acetal groups, ketone groups, dicarbonyl groups, cyano groups, halogen groups, and combinations thereof;C is different from A and B, and comprises one or more polyesters selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co- glycolic acid), polyhydroxyalkanoates, and combinations thereof; andL1, L2, and L3are the same or different ring-opening esterification reaction products of a polyanhydride and contain at least two carboxylic groups, salts thereof, and combinations thereof.

2. The ionizable polyester of claim 1 , wherein:A is selected from the group consisting of polybutylene adipate terephthalate and polylactic acid;L1is a ring-opening esterification reaction product of a dianhydride; the second repeat units are not present; and the third repeat units are not present.

3. The ionizable polyester of claim 2, wherein:L1is a ring-opening esterification reaction product of meso-butane-1 ,2,3,4-tetracarboxylic dianhydride and has the following structure:

4. The ionizable polyester of claim 2, wherein L1is present in the first repeat unit in a range of 0.1 wt.% to 25 wt.%.

5. The ionizable polyester of claim 1 , wherein: the second repeat units are present;B contains 1 to 20 repeat units, each repeat unit containing 4 to 20 carbon atoms and comprising the one or more functional groups; and the third repeat units are not present.

6. The ionizable polyester of claim 5, wherein B is an esterification reaction product of one or more of structures (a)-(f):

7. The ionizable polyester of claim 5, wherein: the first repeat units are present in the ionizable polyester in a range of 30 wt.% to 99 wt.%; the second repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; and a weight ratio of first repeat units : second repeat units is in a range of 1 :3 to 100:1 .

8. The ionizable polyester of claim 1 , wherein: the second repeat units are not present;the third repeat units are present; and the ionizable polyester is in the form of a block copolymer between the first repeat units and the third repeat units.

9. The ionizable polyester of claim 8, wherein: the first repeat units are present in the ionizable polyester in a range of 30 wt.% to 99 wt.%; the third repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; and a weight ratio of first repeat units : third repeat units is in a range of 1 :3 to 100:1 .

10. The ionizable polyester of claim 1 , wherein: the second repeat units are present; and the third repeat units are present.

11. The ionizable polyester of claim 10, wherein: the first repeat units are present in the ionizable polyester in a range of 30 wt.% to 99 wt.%; the second repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; the third repeat units are present in the ionizable polyester in a range of 1 wt.% to 70 wt.%; a weight ratio of first repeat units : second repeat units is in a range of 1 :3 to 100:1 ; a weight ratio of first repeat units : third repeat units is in a range of 1 :3 to 100:1 ; and a weight ratio of second repeat units : third repeat units is in a range of 1 :100 to 100:1.

12. The ionizable polyester of claim 1 , wherein:L1, L2, and L3are the same or different ring-opening esterification reaction products of a dianhydride selected from the group consisting of butane-1 ,2,3,4-tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

13. The ionizable polyester of claim 1 , further comprising: ring-opening esterification reaction products of a monoanhydride containing one carboxylic group or a salt thereof.

14. The ionizable polyester of claim 1 , wherein:A has a molecular weight in a range of 200 g / mol to 100,000 g / mol; the ionizable polyester has a molecular weight in a range of 200 g / mol to 100,000 g / mol; and a ratio between the molecular weight of the ionizable polyester to the molecular weight of A is in a range of 1 .02 to 10.

15. The ionizable polyester of claim 1 , wherein:A has a molecular weight in a range of 1 ,000 g / mol to 10,000 g / mol; the ionizable polyester has a molecular weight in a range of 1 ,000 g / mol to 50,000 g / mol; and a ratio between the molecular weight of the ionizable polyester to the molecular weight of A is in a range of 1 .1 to 3.

16. The ionizable polyester of claim 1 , wherein the ionizable polyester has a melting temperature in the range of 80-400 °C.

17. The ionizable polyester of claim 1 , wherein L1, L2, and L3comprise ammonium salts of the ring-opening esterification reaction products.

18. The ionizable polyester of claim 1 , wherein the ionizable polyester is unbranched and not crosslinked.

19. An ionizable polyester comprising: first repeat units according to Formula (1):-[-A-L1-]- (1); wherein:A comprises one or more aromatic, semi-aromatic, or aliphatic polyesters or copolyesters; andL1is an aromatic, aliphatic, semi-aromatic, cyclic, linear, branched, or acyclic hydrocarbon group containing 1 to 50 carbon atoms and comprising one or more polar functional groups.

20. The ionizable polyester of claim 19, wherein:A has a molecular weight in a range of 500 g / mol to 20,000 g / mol; and the polar functional group is selected from group consisting of carboxylic groups, salts thereof, hydroxyl groups, amino groups, ammonium salts thereof, phosphate groups, and combinations thereof.

21. The ionizable polyester of claim 20, wherein each L1contains two carboxylic groups or salts thereof.

22. The ionizable polyester of claim 20, wherein the polyesters A are selected from the group consisting of polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), polybutylene adipate succinate (PBAS), poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, poly(1 ,4-cyclohexanedimethylene succinate) (PCHS), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyethylene succinate) (PES), polybutylene naphthalate (PBN), polybutylene succinate (PBS), polybutylene terephthalate (PBT), polycaprolactone (PCL), polycyclohexylenedimethylene terephthalate (PCT), polyethylene adipate (PEA), polyethylene furanoate (PEF), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyhydroxyalkanoates (PHA), polylactic acid (PLA), polypropylene terephthalate (PPT), polytrimethylene terephthalate (PTT), poly(trimethylene carbonate) (PTMC), poly(glycolide-co-lactide) (PGLA), unsaturated polyesters, alkyd resins; PETG (polyethylene terephthalate glycol- modified), and combinations (e.g., copolymers) thereof.

23. An ionizable polyester comprising: first repeat units according to Formula (1):-[-A-L1-]- (1); optionally, second repeat units according to Formula (2):-[-B-L2-]- (2); optionally, third repeat units according to Formula (3):-[-C-L3-]- (3); wherein:A comprises one or more polyesters selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations thereof;B is different from A, and comprises one or more functional groups selected from the group consisting of ethylen ically unsaturated groups, acetal groups, ketone groups, dicarbonyl groups, cyano groups, halogen groups, and combinations thereof;C is different from A and B, and comprises one or more polyesters selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co- glycolic acid), polyhydroxyalkanoates, and combinations thereof; andL1, L2, and L3are the same or different esterification reaction products of a polycarboxylic acid and contain one or more (pendant) carboxylic groups, salts thereof, and combinations thereof.

24. A method for forming an ionizable polyester, the method comprising: reacting a polyanhydride with a first polyester diol according to Formula (1 A) and, optionally, one or both of a second functional diol according to Formula (2B) and a third polyester diol according to Formula (3A) to form an ionizable polyester product:HO-[-A-]-OH (1A),HO-[-B-]-OH (2A),HO-[-C-]-OH (3A); wherein:A comprises one or more polyesters (or polyester residues) selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations thereof;B is different from A, and comprises one or more functional groups selected from the group consisting of ethylenically unsaturated groups, acetal (or ketal) groups, ketone (or carbonyl) groups, dicarbonyl groups, and combinations thereof;C is different from A and B, and comprises one or more polyesters (or polyester residues) selected from the group consisting of polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene adipate terephthalate, polybutylene adipate succinate, poly(lactic acid-co-glycolic acid), polyhydroxyalkanoates, and combinations (e.g., copolymers) thereof.

25. The method of claim 24, comprising: reacting at a temperature of up to 240 °C; reacting in the presence of 0.01 to 0.1 wt.% catalyst relative to total reactants; and / or adding a catalytic deactivator in an amount of 0.01 to 0.05 wt.% with respect to solid polymer.

26. The method of claim 24, wherein: the first polyester diol has a molecular weight in a range of 200 g / mol to 100,000 g / mol; the ionizable polyester has a molecular weight in a range of 200 g / mol to 100,000 g / mol; anda ratio between the molecular weight of the ionizable polyester to the molecular weight of the first polyester diol is in a range of 1 .02 to 10.

27. The method of claim 24, wherein the ionizable polyester comprises: first repeat units according to Formula (1 ):-[-A-L-]- (1 ); optionally, second repeat units according to Formula (2):-[-B-L-]- (2); optionally, third repeat units according to Formula (3):-[-C-L-]- (3); wherein:L is a ring-opening esterification reaction product of the polyanhydride and contains at least two (pendant) carboxylic groups, salts thereof, and combinations thereof.

28. An ionizable polyester dispersion comprising: an aqueous medium; and an ionizable polyester according to any one of claims 1 to 23 dispersed in the aqueous medium.

29. The ionizable polyester dispersion of claim 28, wherein: water is present in the aqueous medium in an amount of 50 wt.% to 99 wt.% relative to the dispersion; and the ionizable polyester is present in the aqueous medium in an amount of 1 wt.% to 50 wt.% relative to the dispersion.

30. The ionizable polyester dispersion of claim 28, wherein the ionizable polyester is in an ammonium salt form.31 . A coated article comprising: a substrate; and a coating on the substrate, the coating comprising an ionizable polyester according to any one of claims 1 to 23.

32. The coated article of claim 31 , wherein: the substrate is a cellulosic substrate.

33. The coated article of claim 32, further comprising at least one of a cationic starch and polyethylene imine (PEI) present in one or both of a blend with the ionizable polyester in the coating and a separate layer between the cellulosic substrate and the coating.

34. The coated article of claim 31 , wherein: the coated article has a kit rating in a range of 4 to 12; the coated article has a cobb rating of 20 g / m2or less; the coated article has an OTR value between 0.0001 -20 cc*mm / m2»24h at 23 °C and 50% RH; and / or the coated article has a WVTR value between 0.0001 -40 g»mm / m2»24h at 37°C and 90% RH.

35. The coated article of claim 31 , further comprising at least one of a gas barrier layer and an oil-resistant layer.

36. The coated article of claim 31 , further comprising one or more additives.

37. The coated article of claim 31 , further comprising a wax blended with the ionizable polyester.

38. The coated article of 37, wherein the wax comprises a synthetic wax according to Formula I:A-a-B-b-C (I); wherein:A is a hydrocarbon ester group having 12 to 40 carbon atoms;B is an oligomeric residue of (i) n glycolic acid units, (ii) n lactic acid units, or (iii) n glycolic acid units and lactic acid units in total, where n is 4 to 20;C is either OH or a hydrocarbon ester group having 2 to 40 carbon atoms, with the proviso that when C is OH, then A contains at least one of a carboxylic group and an unsaturated carbon-carbon double bond; a is either absent, or present as a linking group between A and B; and b is either absent, or present as a linking group between B and C.

39. The coated article of 37, wherein the wax comprises a synthetic wax according to Formula IA or IB:R1C(=O)O-R2-[-OC(=O)-CHR3-]n-O-R4(IA);R1C(=O)O-[-CHR3-OC(=O)-]n-R2-O-R4(IB); wherein:R1is a hydrocarbon group having 11 to 39 carbon atoms;R2is a hydrocarbon linking group having 2 to 18 carbon atoms; n is 4 to 20;R3is independently H or CH3for each of the n repeat units; andR4is H or hydrocarbon group having 2 to 40 carbon atoms, with the proviso that when R4is H, then R1contains at least one of a carboxylic group and an unsaturated carbon-carbon double bond.

40. The coated article of claim 31 , wherein the ionizable polyester is in an acid form.

41. A method for forming a coated article, the method comprising: applying an aqueous ionizable polyester dispersion to a surface of a substrate, wherein the ionizable polyester dispersion comprises: an aqueous medium; and an ionizable polyester according to claim 17 dispersed in the aqueous medium; removing the aqueous medium from the surface of the substrate, thereby removing an amine from the ionizable polyester and converting the ionizable polyester to an acid form.

42. An ionic polysiloxane comprising: first repeat units according to Formula (1):-[-A-L1-]- (1); optionally, second repeat units according to Formula (2):-[-B-L2-]- (2); optionally, third repeat units according to Formula (3):-[-C-L3-]- (3); wherein:A comprises one or more polysiloxanes;B is different from A, and comprises one or more functional groups selected from the group consisting of ethylen ically unsaturated groups, acetal groups, ketone groups, dicarbonyl groups, cyano groups, halogen groups, and combinations (e.g., oligomers or cooligomers) thereof;C is different from A and B, and comprises one or more polysiloxanes; andL1, L2, and L3are the same or different ring-opening esterification reaction products of a polyanhydride and contain at least two carboxylic groups, and combinations thereof.

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