Synthetic wax materials with degradable linkers

Abstract

The disclosure relates to synthetic wax compositions including at least one long- chain hydrocarbon residue having 4 to 40 carbon atoms, and at least one oligomeric residue containing 4 to 50 ester units such as adipate-co-terephthalate units, alkanoate units, glycolic acid units, and / or lactic acid units. The synthetic wax can include other functional groups such as pendant carboxylic groups to facilitate emulsification and / or metal complexation of the wax, and / or unsaturated carbon-carbon double bonds to facilitate curing or crosslinking of the wax. The synthetic wax can be used as a coating on a variety of substrates, for example paper substrates, to impart water and / or oil resistance to the substrate. The presence of the carboxylic groups and / or oligomeric ester residue in the wax permits chemical degradation under very mild conditions, which in turn facilitates removal, repulping, and / or recycling of the synthetic wax.

Description

SYNTHETIC WAX MATERIALS WITH DEGRADABLE LINKERSCROSS REFERENCE TO RELATED APPLICATION

[0001] Priority is claimed to U.S. Provisional Application No. 63 / 665,034, filed June 27, 2024 and to U.S. Provisional Application No. 63 / 736,861 , filed December 20, 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 2423572 awarded by the National Science Foundation, and under NSF-2208697 awarded by the National Science Foundation. The government has certain rights in the invention.BACKGROUND OF THE DISCLOSUREField of the Disclosure

[0003] The disclosure relates to synthetic wax compositions including at least one or two hydrocarbon residues having 4 to 40 or 12 to 40 carbon atoms, and at least one oligomeric residue containing 4 to 20 or 4 to 50 ester units such as adipate-co-terephthalate units, alkanoate units, glycolic acid units, and / or lactic acid units. One or both of the hydrocarbon residues can include a carboxylic or other ionizable group, which facilitate emulsion and dispersion of the synthetic wax in an aqueous medium. The presence of the ionizable groups and / or oligomeric ester residue in the wax permits chemical degradation under very mild conditions, which in turn facilitates removal, repulping, and / or recycling of the synthetic wax.Background

[0004] Approximately 40% of all plastics produced today are used in the packaging sector. The biggest sustainable packaging hurdle is access to new materials that are universally compostable, repulpable / recyclable available at commodity prices, and have performance matching or exceeding those of the existing polymers.

[0005] Waxes can be used as a paper coating to impart some degree of water and oil resistance to the paper. Petrochemical waxes are difficult to separate from coated paper and thus need alternatives to ensure wax coated paper is recyclable. Natural wax such as beeswax and carnauba wax are good alternatives, but they are expensive and limited in amount.

[0006] The environmental concerns related to plastics have shifted momentum toward paper-based packaging. A major concern with plastics is their potential to formmicroplastics. As an alternative to plastic packaging, paper packaging is in high demand across food and pharmaceutical packaging. This is due to paper’s biodegradability, affordability, lightweight, and biobased nature. However, paper in its uncoated form does not fulfill packaging needs. For example, paper is usually coated with various materials to improve its resistance against water, gas, moisture, and oil, as well as to provide thermal sealing properties. However, the challenges are that the coating materials used today are synthetic, nonbiodegradable, and non-repulpable, thus posing a risk to the environment. For example, polyethylene (PE) is widely used for paper coating to fulfill packaging needs. However, the difficulty in separating the paper from these coated materials causes the paper to lose both its recyclable and biodegradable properties. Consequently, coated or laminated paper often ends up in landfills, where it also leaks into rivers. In the case of plastic leakage into the environment, it eventually turns into microplastics and becomes a high risk for both human and ecological health due to mechanical abrasion brought on by water waves and ultraviolet (UV) exposure.

[0007] Biodegradable polymers offer potential alternatives to plastics or plastic-coated paper as they do not create any persistent microplastics. Starch, cellulose, and some polyesters are examples of biodegradable / compostable polymers due to the presence of hydrolyzable ester bonds in their structures. Some examples of biodegradable or compostable polymers include polyhydroxy hexanoate (PHH), polyhydroxy butyrate (PHB), polyhydroxy valerate (PHV), polylactic acid (PLA), and polycaprolactone (PCL). PLA is an aliphatic polyester that is industrially synthesized via the ring-opening polymerization of lactide especially for obtaining high-molecular-weight PLA. PLA is safe for all food packaging applications and is categorized by the US Food and Drug Administration (FDA) as generally regarded as safe. However, high-molecular-weight PLA is non-biodegradable in soil as it takes 500 and 1000 years to break down, as PLA only degrades in industry compost conditions.

[0008] Wax-coated paper can offer an excellent sustainable alternative to plastics and plastic-coated paper. For example, natural waxes are biodegradable, and thus, they do not generate microplastics. However, waxes are suitable only for low-temperature applications because of their low melting temperature Tm. Also, natural waxes are expensive and insufficiently available for large-scale use in the packaging industry. Also, waxes do not offer good thermal sealing performance because of shorter hydrocarbon chains lacking the necessary polymer chain entanglement.SUMMARY

[0009] In one aspect, the disclosure relates to a synthetic wax according to the following Formula I: A-a-B-b-C (I). In Formula I, 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 (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.

[0010] In one aspect, the disclosure relates to a synthetic wax according to the following Formula II: A(X)-a-B-b-C(Y) (II). In Formula II, A is a hydrocarbon ester group having 4 to 40 carbon atoms; B is an oligomeric residue containing n ester units (e.g., other than glycolic acid units and lactic acid units), where n is 4 to 50 (or 2 to 50, 4 to 20, or 6 to 14); C is either OH or a hydrocarbon ester group having 4 to 40 carbon atoms; a is either absent, or present as a linking group between A and B; b is either absent, or present as a linking group between B and C; X is either absent, or present as one or more (pendant) ionizable groups on A; Y is either absent, or present as one or more (pendant) ionizable groups on C; and at least one of X and Y is present. In embodiments, both X and Y can be present. In embodiments, X and Y independently can be or include carboxylic groups (-COOH), salts thereof (e.g., sodium or alkali metal salts, ammonium salts), amino groups, ammonium salts thereof, phenol groups, phosphate groups (or phosphoric acid groups), sulfonate groups (or sulfonic acid groups), and combinations thereof. In embodiments, X and Y are independently selected from the group consisting of carboxylic groups and salts thereof; and A and C each contain 0, 1 , 2, or 3 (or at least one) unsaturated carbon-carbon double bonds.

[0011] In Formulas I and II, 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 4, 8, 12, 14, 16, 18, 20, or 24 and / or up to 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).

[0012] In Formula I, 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.

[0013] In Formula II, B can include one or more types of ester units. The ester units can include butyl adipate-co-butyl terephthalate units, butyl succinate units, alkanoate units, hydroxyacid units (e.g., from ring-opening of polycaprolactone or other cyclic monomer), glycolic acid units, and / or lactic acid units. In some embodiments, the ester units do not include glycolic and / or lactic units. When B contains multiple units, the units in the oligomeric residue can have a block or random arrangement. The total number n of ester units in B can be at least 2, 3, 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.

[0014] In Formulas I and II, 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 or other ester 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).

[0015] In Formulas I and II, 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 hydroxy functional group the oligomeric B group can react directly with a terminal carboxylic group in precursor reactants forming the A and / or C groups.

[0016] In various refinements of Formulas I and II, 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.

[0017] In another aspect, the disclosure relates to 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-0-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 1 1 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.

[0018] Formulas IA and IB generally represent a more specific structure of Formula I. R1in combination with the adjacent ester group represents specific selections for A. R2represents specific selections for embodiments when linker a is present (Formula IA) or when linker b is present (Formula IB). The n glycolic / lactic repeat units represent the oligomeric residue B, with the orientation / directionality of the repeat units depending on the location / presence of R2linking groups. R4in combination with the adjacent oxygen atom represents specific selections for B (e.g., where R4being H corresponds to C being OH).

[0019] R1can include linear, branched, or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon groups. For example, R1can include linear, branched, or cyclic, substituted or unsubstituted alkyl or alkenyl (e.g., having one or more C=C unsaturated bonds) groups. The R1group 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 R1imparts at least some of the waxy character to the synthetic wax. The R1group can include at least 8, 11 , 13, 15, 17, 19, or 23 and / or up to 15, 19, 23, 27, 31 , 35, or 39 carbon atoms. In embodiments, the R1group can include hydrocarbon groups of multiple different lengths, carbon atoms, etc., such as when the synthetic wax is formed using a mixture or blend of fatty acids, which can be a pre-selected blend or a naturally resulting blend from natural source of fats, oils, fatty acid (tri)glycerides, etc. In embodiments, the R1group can include a C17 alkyl group (e.g., representing a stearic acid residue or stearate ester in combination with the adjacent carboxylate group), a C13 alkyl group (e.g., myristic acid / ester), a C15 alkyl group (e.g., palmitic acid / ester), a C19 alkyl group (e.g., arachidic acid / ester), a C21 alkyl group (e.g., behenic acid / ester), and combinations thereof (e.g., a synthetic wax formed from a mixture or blend of fatty acids).

[0020] R2can include linear, branched, or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon groups. For example, R2can include linear, branched, or cyclic, substituted or unsubstituted alkyl or alkenyl (e.g., having one or more C=C unsaturatedbonds) groups. The R2group generally represents an ester condensation product between a diol or polyol as a linker between a fatty acid, glycolic acid, and / or lactic acid as the corresponding R1 / R4groups (or A / C groups) and the corresponding oligomeric residue (or B group). In embodiments, the R2group can include a C2 to C18 alkylene or hydroxyalkylene group, for example where a C2 alkylene group represents an ethylene glycol residue, a C3 alkylene group represents a propylene glycol residue, a C3 hydroxyalkyl group represents a glycerin residue, etc. The R2group can include at least 2, 3, 4, 5, or 6 and / or up to 3, 4, 5, 6, 8, or 18 carbon atoms.

[0021] As described above for B, the n glycolic / lactic repeat units form an oligomeric residue that facilitates degradation under mild conditions while still providing a thermally stable / thermally processable synthetic wax material. The oligomeric residue can include one or both of glycolic and lactic units. When the oligomeric residue 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. The orientation / direction of the glycolic / lactic repeat units depends on whether a linking group is included in the synthetic wax and / or the time during the synthesis process at which the glycolic / lactic units are reacted with the corresponding reactants forming the R1, R1(when present), and R4groups.

[0022] When R4is not an H atom, R4can generally include the same options as described above for C or as described above for R1when R4includes a carbonyl carbon C(=O), but R4can include comparatively shorter hydrocarbon segments as compared to A or R1(e.g., when A or R1is long enough to substantially provide the desired waxy character). In addition to the carboxylic and unsaturated functional groups that are possible for R4, R4can also include carbonyl carbon (i.e., forming an ester group with the adjacent oxygen atom) and / or an additional oligomeric residue of glycolic / lactic units along its length (i.e., analogous to and in addition to B in Formula I or the n-glycolic / lactic oligomeric segment in Formulas IA / IB). For example, the R4group 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, such where a terminal carbon atom is a carbonyl carbon at the bonding location with the oxygen atom to provide an ester group. In embodiments and similar to R1above, the R4group can include hydrocarbon groups of multiple different lengths, carbon atoms, etc., such as when the synthetic wax is formed using a mixture or blend of fatty acids.

[0023] In a refinement of Formula IA and / or IB, R1is C17H35 (i.e., a stearic fatty acid residue); R2is C2H4 (i.e., an ethylene glycol linker); and / or OR4is OC(=O)-Ci7H35(i.e., a stearic fatty acid residue).

[0024] In a refinement of Formula IA and / or IB, R3is H for all n repeat units (i.e., only glycolic acid residues).

[0025] In a refinement of Formula IA and / or IB, R3is CH3 for all n repeat units (i.e., only lactic acid residues).

[0026] In a refinement of Formula IA and / or IB, R1is selected from the group consisting of: (i) R1A(e.g., saturated or unsaturated fatty acid ester group), and (ii) R1A-d- (e.g., saturated or unsaturated fatty acid ester group with a linker group d containing a pendant carboxylic or carboxylate group in acid or salt form, such as an alkali or other metal salt (e.g., Na, K, Ca, Mg, Zn), ammonium salt, etc.). R1Ais a Cs to C39 alkyl group or unsaturated analog thereof (e.g., an alkenyl group, dienyl group, or trienyl group with 1 , 2, or 3 unsaturated C=C groups along the length of an otherwise saturated alkyl group) More generally, the R1Agroup can include at least 8, 11 , 13, 15, 17, 19, or 23 and / or up to 15, 19, 23, 27, 31 , 35, or 39 carbon atoms, for example with 0, 1 , 2, or 3 unsaturated C=C groups. The d group is a hydrocarbon linking group containing 1 to 4 carbon atoms (e.g., 1 , 2, 3, or 4 carbon atoms) and a pendant carboxylic acid group or salt thereof. For example, the linker d can be represented by *-CH(COOH)-# (1 -carbon linking group with pendant, terminal carboxylic group), *-CH(COOH)-CH2-# (2-carbon linking group with pendant, terminal carboxylic group), *-CH2-CH(COOH)-# (2-carbon linking group with pendant, terminal carboxylic group), or *-CH(CH2COOH)-# (2-carbon linking group with pendant, terminal carboxylic group with an intervening methylene group), where “*” is the point of attachment / bonding to R1A, and “#” is the point of attachment / bonding to the carbonyl carbon / ester group adjacent to R1in Formula IA or IB. The illustrated COOH group in the foregoing structure for the linker d can be in acid form (as shown) or in salt form, such as an alkali or other metal salt (e.g., Na, K, Ca, Mg, Zn), ammonium salt, etc. In some embodiments, R1(or A in Formula I) or its substituents can be substituted with one or more other functional groups such as epoxy groups, halogens, ether groups, acetal groups, etc.

[0027] In a particular refinement, R1is R1A, and R1Ais the Cn to C39 alkyl group (i.e., saturated / not unsaturated). In this case, a saturated fatty acid ester is used to provide the waxy character of the wax via the A or R1group. In an alternative refinement, R1Acan include an unsaturated group, for example to provide a means for curing, such as by addition of a peroxide (e.g., dicumyl peroxide) initiator to the wax. Such curing orcrosslinking can make the resulting wax more difficult to melt, thus increasing its thermal resistance.

[0028] In a particular refinement, R1is R1A-d- or the salt thereof. This represents an alternative embodiment in which a pendant carboxylic / carboxylate group provides some hydrophilic character for improved dispersion and / or dissolution in water, such as when degrading the wax, forming a coating with the wax, etc. More specifically, the carboxylic groups provide several functions. (1 ) The carboxylic groups provide easy removal from coated paper by increasing pH above 7. (2) The carboxylic groups can be used to emulsify the wax in a basic liquid medium (such as ammonia), the wax is then applied as a coating from the basic medium, and then gentle heat is applied to remove the liquid medium (as well as ammonia), leaving the wax as the coating. This provides a water-repellent coating, which can be simply removed from the surface by neutralizing the wax / exposing it to a basic medium again. (3) The carboxylic groups permit complexation with divalent or trivalent metal cations, for example Ca+2. Such complexation can offer better water resistance as it can form synthetic wax dimers (e.g., when using a divalent cation) or trimers (e.g., when using a trivalent cation). As above, the R1Agroup can be saturated to provide a more crystalline solid wax. Alternatively, the R1Agroup can be an unsaturated chain to provide a means for curing as described above, for example when an alkenyl-substituted anhydride, such as a dodecenyl succinic anhydride, is used to provide the waxy character of the wax via the A or R1group.

[0029] In a refinement of Formula IA and / or IB, OR4is selected from the group consisting of: (i) -OC(=O)-R5(e.g., saturated or unsaturated fatty acid ester group), (ii) -OC(=O)-d-R5or a salt thereof (e.g., saturated or unsaturated fatty acid ester group with a linker group d containing a pendant carboxylic or carboxylate group in acid or salt form, such as an alkali metal salt (e.g., Na, K), ammonium salt, etc.), (iii) -OC(=O)-CH=CH2(e.g., acrylate group), (iv) -OC(=O)-C(CH3)=CH2(e.g., methacrylate group), (v) -OC(=O)-C(COOH)=CH2(e.g., itaconic group), (vi) -[-OC(=O)-CHR3-]m-OC(=O)-R5in the synthetic wax according to Formula IB (e.g., saturated or unsaturated fatty acid ester group as above, but attached via a second oligomeric glycolic / lactic residue), (vii) -[-OC(=O)-CHR3-]m-OC(=O)-d-R5or a salt thereof in the synthetic wax according to Formula IB (e.g., saturated or unsaturated fatty acid ester group with a linker group d containing a pendant carboxylic or carboxylate group in acid or salt form as above, but attached via a second oligomeric glycolic / lactic residue), and (viii) combinations thereof (e.g., where different selections for OR4, R5etc. can represent a blend of Formula IA and / or Formula IB synthetic waxes). R5is a Ci to C39 alkyl group or unsaturated analog thereof (e.g., an alkenyl group, dienyl group, or trienyl group with 1 , 2, or3 unsaturated C=C groups along the length of an otherwise saturated alkyl group). More generally, the R5group can include at least 1 , 2, 3, 5, 7, 9, 11 , 13, 15, 17, 19, or 23 and / or up to 3, 5, 7, 11 , 15, 19, 23, 27, 31 , 35, or 39 carbon atoms, for example with 0, 1 , 2, or 3 unsaturated C=C groups. The d group is a hydrocarbon linking group containing 1 to 4 carbon atoms (e.g., 1 , 2, 3, or 4 carbon atoms) and a pendant carboxylic acid group or salt thereof, with the same options as described above (e.g., where “#” is the point of attachment / bonding to R5, and “*” is the point of attachment / bonding to the adjacent carbonyl carbon / ester group). The index m is 4 to 20 or 4 to 50, and it more generally can have the same options for selections and subranges from 4 to 20 or 4 to 50 as described above for the index n. In some embodiments, OR4(or C in Formula I) or its substituents can be substituted with one or more other functional groups such as epoxy groups, halogens, ether groups, acetal groups, etc.

[0030] In a particular refinement, OR4is -OC(=O)-R5, and R5is the Ci to C39 alkyl group (i.e., saturated / not unsaturated). In this case, a saturated fatty acid ester is used to provide additional waxy character of the wax via the C or R5group. In an alternative refinement, R5can include an unsaturated group, for example to provide a means for curing, such as by addition of a peroxide (e.g., dicumyl peroxide) initiator to the wax. Such curing or crosslinking can make the resulting wax more difficult to melt, thus increasing its thermal resistance.

[0031] In a particular refinement, OR4is -OC(=O)-d-R5or a salt thereof. As above, this represents an alternative embodiment in which a pendant carboxylic / carboxylate group provides some hydrophilic character for improved dispersion and / or dissolution in water, such as when degrading the wax, forming a coating with the wax, etc., in particular facilitating coating application / removal in a basic medium and synthetic wax complexation with metal cations.

[0032] In a particular refinement, OR4is -[-OC(=O)-CHR3-]m-OC(=O)-R5or -[-OC(=O)- CHR3-]m-OC(=O)-d-R5or a salt thereof. This represents an embodiment in which an additional oligomeric glycolic / lactic residue is incorporated to provide improved emulsification characteristics, for example for comparatively larger-MW synthetic waxes.

[0033] In a particular refinement, OR4is -OC(=O)-CH=CH2or -OC(=O)-C(CH3)=CH2. This represents an embodiment incorporating a (meth)acrylate group that can be cured in a coating once applied to a substrate or polymerized first in a solvent, water, or melt-phase, and then used for coating. The cured or polymerized waxes offer excellent thermal sealing properties and high melting points (Tm) suitable for hot food / beverage applications.

[0034] In a refinement of Formula IA and / or IB, wherein R2is a glycerin residue comprising a pendant group selected from (i) OH, (ii) -OC(=O)-R6(e.g., saturated or unsaturated fatty acid ester group, such as from original triglyceride), and (iii) -[-OC(=O)- CHR3-]o-OC(=O)-R6(e.g., saturated or unsaturated fatty acid ester group as above, but attached via an additional oligomeric glycolic / lactic residue). R6is a Ci to C39 alkyl group or unsaturated analog thereof (e.g., an alkenyl group, dienyl group, or trienyl group with 1 , 2, or 3 unsaturated C=C groups along the length of an otherwise saturated alkyl group). More generally, the R5group can include at least 1 , 2, 3, 5, 7, 9, 1 1 , 13, 15, 17, 19, or 23 and / or up to 3, 5, 7, 11 , 15, 19, 23, 27, 31 , 35, or 39 carbon atoms, for example with 0, 1 , 2, or 3 unsaturated C=C groups. The index 0 is 4 to 20 or 4 to 50, and it more generally can have the same options for selections and subranges from 4 to 20 or 4 to 50 as described above for the index n. In some embodiments, it is possible to start with a fatty acid triglyceride as a source material for forming the synthetic wax, and then perform one or more transesterification reaction(s) to insert one or more glycolic / lactic oligomeric segments between the glycerin backbone and pendant fatty acid structures to arrive at synthetic wax structures having 1 , 2, or 3 fatty acid segments attached to a glycerin backbone with 1 , 2, or 3 intervening glycolic / lactic oligomeric segments between the fatty acid segments and the glycolic / lactic oligomeric segments. This could be represented, for example, in the context of Formula IA or IB with R2as a glycerin residue with an additional pendant fatty acid ester group, with or without an additional inserted glycolic / lactic oligomeric segment.

[0035] In another aspect, the disclosure relates to a synthetic wax according to the following Formula IIA and / or I IB (e.g., alone or in admixture): R1C(=O)O-R2-[D]n-O(C=O)-R1(HA) ; and R1C(=O)O-[E]m-R2-[D]n-O(C=O)-R1(IIB). In Formulas IIA and I IB, R1is a hydrocarbon group having 4 to 39 carbon atoms having one or more ionizable groups; R2is a hydrocarbon linking group having 2 to 18 carbon atoms; n is 4 to 50; m is 4 to 50; D is an ester unit having 2 to 31 carbon atoms (e.g., with terminal ester links to adjacent groups and optionally one or more internal ester groups, such as from copolyester residues like PBAT, PBS); and E is an ester unit having 2 to 31 carbon atoms (e.g., same or different as D, but reverse orientation). In embodiments, D can be an ester unit represented by -OC(=O)-F-, E can be an ester unit represented by -F-C(=O)O-, and F can be a hydrocarbon group having 1 to 30 carbon atoms. R1, R2, n, and m can generally be selected from the various options described above for Formulas IA and IB.

[0036] In a refinement, D is selected from the group consisting of: (i) -OC(=O)-CeH4- C(=O)O-C4H8-OC(=O)-C4H8-C(=O)O-C4H8- (e.g., PBAT unit); (ii) -OC(=O)-C2H4-C(=O)O- C4H8- (e.g., PBS unit); (iii) -OC(=O)-CH2-CH(CH3)- (e.g., PH3B unit); (iv) -OC(=O)-CH2-CH(C2H5)- (e.g., PHV unit); (v) -OC(=O)-C3H6- (e.g., P4HB unit); (vi) -OC(=O)-CH2- (e.g., PGA unit); (vii) -OC(=O)-CH(CH3)- (e.g., PLA unit); and (viii) -OC(=O)-C5HI0- (e.g., PCL unit).

[0037] In a refinement, E is selected from the group consisting of: (i) -C4H8-OC(=O)-C4H8- C(=O)O-C4H8-OC(=O)-C6H4-C(=O)O- (e.g., PBAT unit); (ii) -C4H8-OC(=O)-C2H4-C(=O)O- (e.g., PBS unit); (iii) -CH(CH3)-CH2-C(=O)O- (e.g., PH3B unit); (iv) -CH(C2H5)-CH2-C(=O)O- (e.g., PHV unit); (v) -C3H6-C(=O)O- (e.g., P4HB unit); (vi) -CH2-C(=O)O- (e.g., PGA unit); (vii) -CH(CH3)-C(=O)O- (e.g., PLA unit); and (viii) -C5HI0-C(=O)O- (e.g., PCL unit).

[0038] In a refinement, R1is selected from the group consisting of: (i) R1A, and (ii) R1A-d-; wherein: R1Ais a C8to C3g alkyl group or unsaturated analog thereof; and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof.

[0039] In a refinement, the synthetic wax according to Formula IIA is present; D is - OC(=O)-C6H4-C(=O)O-C4H8-OC(=O)-C4H8-C(=O)O-C4H8- (e.g., PBAT unit); R1is R1A-d-; R1Ais a C8to C39 hydrocarbon group having one unsaturated carbon-carbon double bond; and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof.

[0040] In a refinement, the synthetic wax comprises at least one synthetic wax according to Formula IA or IIA (e.g., only one or more waxes according to Formula IA or IIA and no waxes according to Formula IB or IIB, such as where there is a blend of Formula IA or IIA waxes with different selections for one or more of R1, R2, R3, R4, and / or n).

[0041] In a refinement, the synthetic wax comprises at least one synthetic wax according to Formula IB or IIB (e.g., only one or more waxes according to Formula IB or IIB and no waxes according to Formula IA or IIA, such as where there is a blend of Formula IB or IIB waxes with different selections for one or more of R1, R2, R3, R4, and / or n).

[0042] In a refinement, the synthetic wax comprises at least one synthetic wax according to Formula IA or IIA; and at least one synthetic wax according to Formula IB or IIB (e.g., a blend of one or more waxes according to Formula IA or IIA and one or more waxes according to Formula IB or IIB, such as with the same or different selections for one or more of R1, R2, R3, R4, and / or n).

[0043] In another aspect, the disclosure relates to a synthetic wax according to the following Formula IIA.1 : R1C(=O)O-R2-[D1]n-O(C=O)-R1(IIA.1 ). In Formula IIA.1 , R1is R1A-d- in which R1Ais a C8to C39 alkyl group or unsaturated analog thereof (e.g., amonounsaturated alkenyl group), and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof; R2is a hydrocarbon linking group having 2 to 18 carbon atoms; n is 4 to 50 or 10 to 50; and D is -OC(=O)-C8H4- C(=O)O-C4H8-OC(=O)-C4H8-C(=O)O-C4H8- (e.g., PBAT residue). In embodiments, R1, R2, and n can generally be selected from the various options described above for Formulas IA and IB.

[0044] In a refinement, the synthetic wax further comprises a wax according to the following Formula IIA.2: R1C(=O)O-R2-[D2]m-O(C=O)-R1(IIA.2) (e.g., as a blend). In Formula IIA.2, R1is R1A-d- in which R1Ais a C8to C39 alkyl group or unsaturated analog thereof (e.g., monounsaturated alkenyl group), and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof; R2is a hydrocarbon linking group having 2 to 18 carbon atoms; m is 4 to 50 or 10 to 50; and D2is -OC(=O)- CH(CH3)- (e.g., PLA residue). In embodiments, R1, R2, and m can generally be selected from the various options described above for Formulas IA and IB for R1, R2, and n, respectively. Selections for components of Formula IIA.2 can be the same or different as the corresponding component in Formula I IA.1 (e.g., R1can be the same or different in the two formulas). In a further refinement, a weight ratio of the Formula I IA.1 wax : the Formula IIA.2 wax is in a range of 70:30 to 90:10, more generally at least and or up to 60:40, 70:30, 75:25, 80:20, 85:15, 90:10, or 95:5.

[0045] In a refinement, the synthetic wax can be a component of a synthetic wax dispersion comprising: an aqueous medium; and a synthetic wax according to the disclosure dispersed in the aqueous medium. The synthetic wax can be in ammonium salt form (e.g., unit d includes -C(=O)ONH4groups).

[0046] In an aspect, the synthetic wax dispersion can be used in methods for sizing fiberbased materials. In a refinement, the method can include mixing (i) the synthetic wax dispersion with (ii) cellulosic fibers and (iii) optionally a sizing agent and / or a size retention aid to form sized cellulosic fibers, and then forming the sized cellulosic fibers into a two- dimensional cellulosic structure (e.g., paper or other thin, flat structure) or a three- dimensional cellulosic structure (e.g., paper or cardboard container). A weight ratio of cellulosic fiber:synthetic wax can be 100:0.1 to 100:15 (e.g., 100:0.1 , 100:1 , 100:2, 100:3, 100:5, 100:8, 100:10, 100:15 and ranges therebetween). In a refinement, the method can include applying the synthetic wax dispersion as a surface treatment (e.g., surface sizing) to a two-dimensional cellulosic structure or a three-dimensional cellulosic structure.

[0047] Various refinements of the disclosed synthetic wax compositions in any of their aspects are possible (e.g., according to any of Formulas I, II, IA, IIA, IIA.1 , II.A.2, IB, or IIB).

[0048] In a refinement, the synthetic wax is a reaction product between (i) a polyester diol and (ii) an anhydride comprising a saturated or unsaturated pendant hydrocarbon group having 4 to 30 carbon atoms (e.g., a PBAT-diol, PBS-diol, PHA-diol reacted with ODSA (octadecenyl succinic anhydride). A polyester diol can be formed by reaction of the polyester-forming monomers with a diol (e.g., an excess diol monomer for PBAT or PBS, an additional diol terminator for PHA, etc.). A polyester diol can be formed by ring opening polymerization of cyclic esters (cyclic diesters) with a polymerization initiator, such as a diol ring opening of caprolactone, lactide, glycolide. A polyester diol alternatively can be formed by partial depolymerization of the polyester in the presence of a diol.

[0049] In a refinement, the synthetic wax can have a melting temperature in a range of 30°C to 160°C or 30°C to 90°C. Generally, lower melting temperatures are characteristic of unpolymerized, uncrosslinked, uncured, and / or uncomplexed embodiments as described above. Similarly, higher melting temperatures are characteristic of polymerized, crosslinked, cured, and / or complexed (e.g., with metal divalent or trivalent cations) embodiments as described herein. For example, the melting temperature can be at least 30, 40, 50, 60, 70, 80, 90, 100, or 110°C and / or up to 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, or 160°C.

[0050] In a refinement, the synthetic wax can have a molecular weight in a range of 2000- 100000 g / mol, 2000-20000 g / mol or 300-5000 g / mol. Generally, lower molecular weights are characteristic of unpolymerized, uncrosslinked, uncured, and / or uncomplexed embodiments as described above. Similarly, higher molecular weights are characteristic of polymerized, crosslinked, cured, and / or complexed (e.g., with metal divalent or trivalent cations) embodiments as described above. For example, the molecular weight can be at least 300, 500, 700, 1000, 2000, 3000, 5000, 10000, 20000, 30000, or 50000 g / mol and / or up to 800, 1000, 2000, 3000, 5000, 10000, 20000, 30000, 50000, or 100000 g / mol. The foregoing weights can represent the molecular weights of specific synthetic wax molecules or an average (e.g., number- or weight-average) molecular weight for a polymeric, cured, crosslinked, or complexed wax containing a distribution of different sizes / molecular weights.

[0051] In another aspect, the disclosure relates to a high-melting synthetic wax comprising a polymerized and / or a metal-complexed synthetic wax according to the disclosure. For example, a high-melting synthetic wax can comprise a polymerization reaction product of a synthetic wax according to Formula I or II in which at least one (or onlyone) of A and C contains at least one (or only one) unsaturated carbon-carbon (polymerizable) double bond. Alternatively, a high-melting synthetic wax can comprise a polymerization reaction product of a synthetic wax according to Formula IA, IIA, IB, and / or 11 B in which at least one (or only one) of R1and R4contains at least one (or only one) carbon-carbon (polymerizable) double bond. Alternatively, a high-melting synthetic wax can comprise a complex between a polyvalent metal cation (e.g., divalent or trivalent) and a synthetic wax according to Formula I or II in which at least one (or only one) of A and C contains at least one (or only one) carboxylic group. Alternatively, a high-melting synthetic wax can comprise a complex between a polyvalent metal cation (e.g., divalent or trivalent) and a synthetic wax according to Formula IA, IIA, IB, and / or 11 B in which at least one (or only one) of R1and R4contains at least one (or only one) carboxylic group.

[0052] In another aspect, the disclosure relates to a synthetic wax composition comprising the synthetic wax according to any of the variously disclosed aspects, refinements, embodiments, etc.; and one or more additives blended with the synthetic wax (e.g., organic additives and / or inorganic additives). In a refinement, the additives are selected from the group consisting of inorganic fillers, organic additives, polymeric fillers, nanoparticles, natural waxes, ionizable polymers, non-ionizable hydrophilic polymers, and combinations thereof.

[0053] In a refinement, the additives are present in an amount of 0.5 wt.% to 50 wt.%, 1 wt.% to 50 wt.%, or 5 wt.% to 20 wt.% relative to the synthetic wax composition. More generally, the additives can be present in an amount of at least 0.1 , 0.5, 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, titanium dioxide), polymeric fillers (e.g., polyvinyl acetate and copolymers thereof, polymerized waxes, biodegradable polymers, such as biodegradable polymers including carboxylic and / or hydroxyl functional groups), nanoparticles / nanocrystals (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.

[0054] In a refinement, the inorganic filler is present and is selected from the group consisting of modified or unmodified titanium dioxide, modified or unmodified silica, modified or unmodified clay, calcium carbonate, aluminum oxide, zinc oxide, talc, mica, bariumsulfate, iron oxides, and combinations thereof. The fillers can be used as their hydrolyzed forms or their salt form (such as alum). The fillers can have various roles, such as thickeners, surface energy modifiers, sealing properties, etc.

[0055] In a refinement, the organic additive is present and is selected from the group consisting of acrylics, polyurethane, epoxy, alkyds, functional polyester (e.g., ionizable polyesters), natural waxes, petroleum waxes, polyhydrocarbons, silicone, vinylic, vinylic- acrylics, polyamide, modified or unmodified carbohydrates (starch, cellulose, chitosan, alginates), polyvinyl alcohol, polyethylene vinyl alcohols acrylic acid, polyethylene vinyl alcohol, proteins, lignin (such as kraft lignin predispered in water using a base), polyethers, polyether-polyesters, amine / imine containing polymers such as polyethylene imine, and combinations thereof. The various organic additives can be anionic, cationic, or neutral, such as cationic acrylics, anionic acrylics, cationic starches, neutral / cationic / an ionic starches, etc.

[0056] In another aspect, the disclosure relates to a synthetic wax dispersion or emulsion comprising an aqueous medium (e.g., water alone or in combination with other solvents or solutes); and a synthetic wax according to any of the variously disclosed aspects, refinements, embodiments, etc. dispersed in the aqueous medium. The synthetic waxes can be emulsified or dispersed after ionizing the carboxylic or other ionizable groups present in the structure. In the case of carboxylic group, the waxes can be emulsified in water in the presence of neutralization with a base such as sodium bicarbonate, sodium carbonate, sodium hydroxide, ammonium bicarbonate, ammonia, ammonium hydroxide, triethyltrialkyl amine, polyethylene imines, etc. Such waterborne or other aqueous emulsion / latex or dispersions can be used to apply a coating on a paper or other substrate. For example, the synthetic wax can be dispersed in hot water, and then the hot water dispersion can be applied onto paper or other another substrate to form the wax coating (e.g., after drying / water evaporation). In certain cases, wax can be melted before adding water and neutralizer (base for acid functional waxes and vice versa) to provide stable emulsions. In other cases, emulsions can be stabilized with thickeners such as polyacid or their salts, polybasic (cationic starch) and their salts or combination of heat and thickeners.

[0057] In a refinement of the dispersion or emulsion, the synthetic wax is in ammonium salt form.

[0058] In another aspect, the disclosure relates to a coated article comprising: a substrate; and a coating on the substrate, the coating comprising the synthetic wax or the synthetic wax composition according to any of the variously disclosed aspects, refinements,embodiments, etc. As described above, the coating can be applied from an aqueous dispersion or emulsion of the synthetic wax. In other embodiments, the coating can be applied in the form of a melt coating of the synthetic wax (e.g., extrusion and non-extrusion melt-coating). In other embodiments, the coating can be applied via rod coating, spray coating, knife coating, roll coating, curtain coating, or dip coating. The substrate is suitably a cellulosic substrate such as a paper substrate. These synthetic wax 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 synthetic wax). The synthetic wax 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 thicknesses can be 1 pm to 1000 pm or 20 pm to 50 pm.

[0059] In a refinement, the substrate is a cellulosic substrate (e.g., paper, wood, molded fiber, etc.). The substrate, such as paper, Kraft paper (bleached and unbleached), corrugated paper, paperboard, and molded pulp paper, can be modified or unmodified before coating with the synthetic wax. For example, the substrate can be treated with acrylics, polyurethane, epoxy, alkyds, functional polyester, natural waxes, petroleum waxes, polyhydrocarbons, silicone, vinylic, vinylic-acrylics, polyamide, carbohydrates (starch, cellulose, chitosan, alginates), polyvinyl alcohol, polyethylene imines, cationic starches, polyethylene vinyl alcohols acrylic acid, polyethylene vinyl alcohol, proteins, lignin, polyethers, polyether-polyesters, or a combination thereof. These organic additives can be anionic, cationic, or neutral; inorganic fillers (such as TiO2, Silica, clay, alum, calcium carbonate, etc.; nano- or micro-sized) before applying a wax coating layer. Thermal treatment can also be applied before applying the coating. For example, briefly heating paper before coating is applied. In other embodiments, the waxes (and their blends with organic / inorganic additives) can be used for internal sizing where fiber and waxes (optionally additives) are mixed and molded or handsheets are formed. Alum or other retention aids are added to improve the retention of wax(and their blends) onto the fiber.

[0060] In a refinement, the synthetic wax coating is applied as a second layer on top of a pre-coated paper. The pre-coated paper is obtained by coating a paper substrate with one or more of a hydrophilic polymer, an oxygen- and / or oil-barrier polymer or additive, or a blend including a hydrophilic polymer, for example including (i) a hydrophilic polymer (e.g., 50, 80 or 90 to 95, 98, or 99.8 wt.% hydrophilic polymer relative to blend), (ii) 0.1-10 wt.% polyethylene imine or other amine / imine polymer different from the hydrophilic polymer, and / or (iii) 0.1-10 wt.% carbonate salt (e.g., sodium carbonate, calcium carbonate, etc.).Once the hydrophilic polymer or blend thereof is coated on paper as first layer via meltcoating, solvent coating, aqueous coating, or other suitable method, then the synthetic wax coating can be applied as a second layer thereon. The pre-coating can improve recycling during paper repulping by more rapidly degrading the waxes, and / or improve barrier performance.

[0061] In a refinement, the coated article has a kit rating in a range of 1 to 12 or 4 to 12; and / or the coated article has a cobb (or cobb1800) rating of 20 g / m2or less. For example, the kit rating can be at least 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11 and / or up to 4, 6, 8, 9, 10, 11 , or 12. Alternatively or additionally, the cobb rating (or cobbl 800 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. Alternatively or additionally, the cobb600 rating can be 70 g / m2or less, for example at least and / or up to 5, 10, 15, 20, 30, 40, 50, 60, or 70 g / m2. Suitable methods for determining the ratings include TAPPI methods T599 pm-96 (kit), UM 557 (kit), and T441 om-09 (cobb).

[0062] In a refinement, the coated article has a water vapor transmission rate (WVTR in a range of 0.0001 to 1000 g»mm / m2»24h at 37°C and 90% RH (e.g., 0.01 to 20 g»mm / m2»24h), for example at least and / or up to 0.0001 , 0.001 , 0.01 , 0.1 , 1 , 2, 5, 10, 20, 50, 100, 200, 500, or 1000 g*mm / m2*24h at 37°C and 90% RH.

[0063] In a refinement, the coating on the coated article has at least one of properties (I), (II), and (III): (I) the coated article has a relative permeability for water vapor of 0.5 or less, relative to a corresponding substrate without the synthetic wax coating thereon; (II) the coated article has a water contact angle in a range of 80° to 120° or 70° to 150° for a 10 pl- deionized water droplet measured 30 sec after application of the droplet; and (III) the coated article has an oil contact angle in a range of 40° to 75° or 20° to 75° for a 10 pL castor oil droplet measured 30 sec after application of the droplet.

[0064] In a refinement, the coated article is thermally sealable at a dwell time of 5 seconds or less and at a temperature of up to 200°C (e.g., dwell time of 0.5 or 1 second or less and at a temperature of up to 160°C).

[0065] In a refinement, the coated article is biodegradable.

[0066] In a refinement, the coated article is repulpable and / or recyclable.

[0067] In another aspect, the disclosure relates to a method for degrading or emulsifying a synthetic wax, the method comprising: contacting the synthetic wax or synthetic wax composition according to any of the variously disclosed aspects, refinements, embodiments,etc. with at least one of a carbonate salt, a bicarbonate salt, and an aqueous solution thereof at a temperature and for a time sufficient to degrade or emulsify the synthetic wax.

[0068] The synthetic wax is degradable and / or emulsifiable under mild conditions, in particular for PLA / PGA-based waxes or waxes including at least some LA or GA ester units (e.g., in combination with other ester units). Degradation and / or emulsification can be performed, for example, by contact with carbonate / bicarbonate salts or immersion in aqueous carbonate / bicarbonate solutions (e.g., 5-50 wt.% or 1-50 wt.% (bi)carbonate or (bi)carbonate salt in water, such as about 1 , 2, 3, 5, 10, 15, 20, 30, 40, or 50 wt.%. Suitable (bi)carbonate salts usable as is or to form corresponding carbonate ions in solution (CO32) can include alkali metal carbonates (e.g., sodium carbonate, sodium bicarbonate), ammonium carbonate, ammonium bicarbonate, etc. Degradation also can be effected in a mild acidic medium (e.g., pH 4-6 aqueous medium) or a mild basic medium (e.g., pH 8-10 aqueous medium). Degradation generally includes cleaving one or more glycolic / lactic ester bonds in the glycolic / lactic oligomeric residue in the original synthetic wax molecule, breaking it into smaller fragments, which can facilitate removal and / or separation of a wax coating from its substrate. Degradation temperatures are suitably elevated related to ambient conditions, but need not be excessively high. For example, degradation temperature can be in a range of 20-95°C, 40-95°C, 40-80°C, or 60-80°C. Degradation times can range from about 0.1-5 hr (or 0.2-2 hr).

[0069] The synthetic wax can also be in the form of synthetic wax composition blended with other additives, for example a coating on a substrate in a method for removing / degrading the coating. For example, when the coating is on a paper substrate, the method for degrading the synthetic wax can be part of a recycling method to remove the wax coating, followed by repulping and recycling the paper. Typically, the degraded wax is in the form of smaller hydrocarbons relative to the original synthetic wax, often with carboxylic groups such as from stearic acid or pendant carboxylic groups, which in a basic medium makes the degraded wax water soluble and / or water-emulsifiable, which in turn facilitates removal, separation, and / or recovery of the wax material from the substrate. In some cases, emulsification can occur upon neutralization of a synthetic wax containing a carboxylic group in its normal form (e.g., prior to degradation).

[0070] In some embodiments, the synthetic wax can be recovered either in addition or as an alternative to the degradation described above. For example, when the synthetic wax includes pendant carboxylic groups (e.g., an emulsifiable synthetic wax), removal of the synthetic wax coating is possible by neutralization in an aqueous medium to emulsify andremove the synthetic wax from its substrate. Such an emulsified wax can be recovered and reverted back to a solid by changing pH, for example for use in subsequent coating step (e.g., in an overall recycling process).

[0071] 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

[0072] For a more complete understanding of the disclosure, reference should be made to the following detailed description and accompanying drawings wherein:

[0073] Figure 1 is a schematic of a coated article including a synthetic wax coating according to the disclosure.

[0074] Figure 2 is a diagram illustrating measurement of a contact angle for a liquid droplet on a surface.

[0075] Figure 3 is a scheme illustrating steps for forming a synthetic PBAT-wax via PBAT depolymerization according to an embodiment of the disclosure.

[0076] Figure 4 is a scheme illustrating steps for forming a synthetic PBAT-wax from PBAT monomers according to an embodiment of the disclosure.

[0077] Figure 5 is a scheme illustrating steps for forming a synthetic PLA-wax from lactide monomers according to an embodiment of the disclosure.

[0078] Figure 6 is a scheme illustrating steps for forming an emulsion from a synthetic PLA-wax according to an embodiment of the disclosure.DETAILED DESCRIPTION

[0079] The disclosure relates to synthetic wax compositions including at least one long- chain hydrocarbon residue having 4 to 40 or 12 to 40 carbon atoms, and at least one oligomeric residue containing 4 to 20 or 4 to 50 ester units such as adipate-co-terephthalate units, alkanoate units, glycolic acid units, and / or lactic acid units. One or both of the hydrocarbon residues can include a carboxylic or other ionizable group, which facilitate emulsion and dispersion of the synthetic wax in an aqueous medium. More generally, the synthetic wax can include other functional groups such as pendant carboxylic groups to facilitate emulsification and / or metal complexation of the wax, and / or unsaturated carbon-carbon double bonds to facilitate curing or crosslinking of the wax. The synthetic wax can be used as a coating on a variety of substrates, for example paper substrates, to impart water and / or oil resistance to the substrate. The presence of the ionizable groups and / or oligomeric ester residue in the wax permits chemical degradation under very mild conditions, which in turn facilitates removal, repulping, and / or recycling of the synthetic wax.

[0080] The disclosed synthetic, biodegradable wax is an alternative to natural wax. The synthetic wax has performance characteristics, such as water and oil resistance, matching that of a natural wax like beeswax and carnauba wax. Natural waxes such as beeswax and carnauba consist of ester linkages that make them readily biodegradable. Natural waxes have general structures of RI(CO)-OR2 where R2 represents a long alkyl groups, such as a C30 chain, which provide properties such as water repellency and high melting points. The synthetic wax developed can include degradable links, for example glycolic acid units and / or lactic acid units, that impart to the waxes universal compostabilty (e.g., biodegrade in the ocean, lake, or other water environment, soil, and industrial compost environment), as well as on-demand degradability during repulping (e.g., washing or otherwise being easily removed from paper, etc.). The biodegradability aspect of the synthetic wax mitigates the accumulation of microplastics that are otherwise building up in the ocean and soil, while repulping enables the synthetic wax-coated paper to stay in use for repetitive use. The synthetic wax can provide excellent water resistance to a coated paper substrate (e.g., Cobb1800 value of 10 g / m2or less, or 15 g / m2or less). The synthetic wax can be formulated with a desired melting point based on its intended application. For low- temperature applications, the synthetic wax can be formulated with a melting temperature (Tm) of about 70°C or less. For high-temperature applications, the synthetic wax can be formulated with a melting temperature (Tm) up to about 140°C.Synthetic Wax

[0081] The synthetic wax according to the disclosure can be represented by the following Formula I or Formula II:A-a-B-b-C (I)A(X)-a-B-b-C(Y) (II)

[0082] In Formulas I and II, A can be a hydrocarbon ester group having 4 to 40 or 12 to 40 carbon atoms. 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 esterfunctional 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 4, 8, 12, 14, 16, 18, 20, or 24 and / or up to 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).

[0083] In Formula I, B can be 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 50, 4 to 20, or 6 to 14. 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.

[0084] In Formula II, B can be an oligomeric residue of n ester units, where n is 4 to 50, 4 to 20, or 6 to 14. The ester units can include diacid-diol units, butyl adipate-co-butyl terephthalate units, butyl succinate units, alkanoate units, hydroxyacid units (e.g., from ringopening of polycaprolactone or other cyclic monomer), glycolic acid units, and / or lactic acid units. In some embodiments, the ester units do not include glycolic and / or lactic units. When B contains multiple units, the units in the oligomeric residue can have a block or random arrangement. The total number n of ester 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.

[0085] In Formulas I and II, C can be 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. 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).

[0086] In Formulas I and II, a and b are linking groups that can be either present or absent (e.g., only a present, only b present, both a and b present). When present, a is a linkinggroup between A and B. When present, and b is a linking group between B and C. Each of 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 hydroxy functional group the oligomeric B group can react directly with a terminal carboxylic group in precursor reactants forming the A and / or C groups. 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.

[0087] The synthetic wax according to the disclosure additionally or alternatively can be represented by the following Formula IA and / or IB, for example alone (e.g., only wax(es) of Formula IA) or in admixture (e.g., wax(es) of Formula IA and wax(es) of Formula IB):R1C(=O)O-R2-[-OC(=O)-CHR3-]n-O-R4(IA)R1C(=O)O-[-CHR3-OC(=O)-]n-R2-O-R4(IB)

[0088] Formulas IA and IB generally represent a more specific structure of Formula I. R1in combination with the adjacent ester group represents specific selections for A. R2represents specific selections for embodiments when linker a is present (Formula IA) or when linker b is present (Formula IB). The n glycolic / lactic repeat units represent the oligomeric residue B, with the orientation / directionality of the repeat units depending on the location / presence of R2linking groups. R4in combination with the adjacent oxygen atom represents specific selections for B (e.g., where R4being H corresponds to C being OH).

[0089] In Formulas IA and IB, R1can be a hydrocarbon group having 4 to 39 or 11 to 39 carbon atoms. R1can include linear, branched, or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon groups. For example, R1can include linear, branched, or cyclic, substituted or unsubstituted alkyl or alkenyl (e.g., having one or more C=C unsaturated bonds) groups. The R1group can be substituted with or otherwise include a (pendant) carboxylic group (e.g., in acid or salt form) or other ionizable group, and / or an unsaturated (polymerizable) C=C unsaturated bond. In embodiments, the 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), for example a carboxylic group (-COOH), a salt thereof (e.g., sodium or alkali metal salt, ammonium salt), an amino group, an ammonium salt thereof, a phenol group, a phosphate group (or phosphoric acid group), or a sulfonate group (or sulfonic acid group). In embodiments, the R1C(=O)O- unit can be a ring-opening reaction product of analkyl- or alkenyl-substituted cyclic anhydride (e.g., succinic anhydride). The ring-opened reaction product provide an ester link and a pendant carboxylic group between the R1group and the oligomeric ester residues of the synthetic wax. The relatively long hydrocarbon character of R1imparts at least some of the waxy character to the synthetic wax. The R1group can include at least 4, 8, 11 , 13, 15, 17, 19, or 23 and / or up to 12, 15, 19, 23, 27, 31 , 35, or 39 carbon atoms. In embodiments, the R1group can include hydrocarbon groups of multiple different lengths, carbon atoms, etc., such as when the synthetic wax is formed using a mixture or blend of fatty acids, which can be a pre-selected blend or a naturally resulting blend from natural source of fats, oils, fatty acid (tri)g lycerides, etc. In embodiments, the R1group can include a C17 alkyl group (e.g., representing a stearic acid residue or stearate ester in combination with the adjacent carboxylate group), a C13 alkyl group (e.g., myristic acid / ester), a C15 alkyl group (e.g., palmitic acid / ester), a C19 alkyl group (e.g., arachidic acid / ester), a C21 alkyl group (e.g., behenic acid / ester), and combinations thereof (e.g., a synthetic wax formed from a mixture or blend of fatty acids).

[0090] In Formulas IA and IB, R2can be a hydrocarbon linking group having 2 to 18 carbon atoms. R2can include linear, branched, or cyclic, saturated or unsaturated, substituted or unsubstituted hydrocarbon groups. For example, R2can include linear, branched, or cyclic, substituted or unsubstituted alkyl or alkenyl (e.g., having one or more C=C unsaturated bonds) groups. The R2group generally represents an ester condensation product between a diol or polyol as a linker between a fatty acid, glycolic acid, and / or lactic acid as the corresponding R1 / R4groups (or A / C groups) and the corresponding oligomeric residue (or B group). In embodiments, the R2group can include a C2 to C18 alkylene or hydroxyalkylene group, for example where a C2 alkylene group represents an ethylene glycol residue, a C3 alkylene group represents a propylene glycol residue, a C3 hydroxyalkyl group represents a glycerin residue, etc. The R2group can include at least 2, 3, 4, 5, or 6 and / or up to 3, 4, 5, 6, 8, or 18 carbon atoms.

[0091] In Formulas IA and IB, n can be 4 to 50, 4 to 20, or 6 to 14. R3can be independently H (i.e., glycolic acid residue) or CH3(i.e., lactic acid residue) for each of the n repeat units, such that one or both of glycolic acid and lactic acid units can be included in the n repeat units. The n glycolic / lactic repeat units form an oligomeric residue that facilitates degradation under mild condition while still providing a thermally stable / thermally processable synthetic wax material. The oligomeric residue can include one or both of glycolic and lactic units. When the oligomeric residue 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 Formulas IA and IB 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. The orientation / direction of the glycolic / lactic repeat units depends on whether a linking group is included in the synthetic wax and / or the time during the synthesis process at which the glycolic / lactic units are reacted with the corresponding reactants forming the R1, R2, and R4groups.

[0092] In Formulas IA and IB, R4can be 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. When R4is not an H atom, R4can generally include the same options as described above for C or as described above for R1when R4includes a carbonyl carbon C(=O), but R4can include comparatively shorter hydrocarbon segments as compared to A or R1(e.g., when A or R1is long enough to substantially provide the desired waxy character). In addition to the carboxylic and unsaturated functional groups that are possible for R4, R4can also include carbonyl carbon (i.e., forming an ester group with the adjacent oxygen atom) and / or an additional oligomeric residue of glycolic / lactic units along its length (i.e., analogous to and in addition to B in Formula I or the n-glycolic / lactic oligomeric segment in Formulas IA / IB). For example, the R4group 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, such where a terminal carbon atom is a carbonyl carbon at the bonding location with the oxygen atom to provide an ester group. In embodiments and similar to R1above, the R4group can include hydrocarbon groups of multiple different lengths, carbon atoms, etc., such as when the synthetic wax is formed using a mixture or blend of fatty acids.

[0093] The synthetic wax according to the disclosure additionally or alternatively can be represented by the following Formula IIA and / or 11 B, for example alone (e.g., only wax(es) of Formula IIA or I IB) or in admixture (e.g., wax(es) of Formula IIA and wax(es) of Formula I IB) : R1C(=O)O-R2-[D]n-O(C=O)-R1(IIA)R1C(=O)O-[E]m-R2-[D]n-O(C=O)-R1(IIB)

[0094] Formulas IIA and IIB generally represent a more specific structure of Formula II. R1in combination with the adjacent ester group represents specific selections for A and C, with or without linkers a and / or b. R2can represent selections for embodiments when linker a is present or when linker b is present. The n ester repeat units D, alone or in combination with the m ester repeat units E, can represent the oligomeric residue B, with the orientation / directionality of the repeat units depending on the location / presence of R2linking groups. In Formulas IIA and IIB, R1and R1can be selected from the various options described above for Formulas IA and IB. Similarly, n and m can be independent selectedfrom the various options for n described above for Formulas IA and IB, for example with n and m independently being 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.

[0095] In Formulas 11 A and 11 B, D and E can be the same or different ester units having 2 to 31 carbon atoms, for example at least and / or up to 2, 3, 4, 5, 6, 7, 9, 11 , 13, 16, 21 , 26, or 31 carbon atoms. D and E can have a terminal carboxylate group (e.g., -OC(=O) or C(=O)O-) for forming an ester link to an adjacent group and an opposing terminal carbon atom (e.g., as part of a methylene group -CH2-) also for forming an ester link to an adjacent group. In embodiments, D can be an ester unit represented by -OC(=O)-F-, E can be an ester unit represented by -F-C(=O)O-, and F can be a hydrocarbon group having 1 to 30 carbon atoms, for example at least and / or up to 1 , 2, 3, 4, 5, 6, 8, 10, 12, 15, 20, 25, or 30 carbon atoms. D, E, and F can have one or more internal ester groups, such as from copolyester residues like PBAT, PBS. The hydrocarbon groups forming D, E, and F can contain linear or branched alkyl groups, aromatic groups (e.g., -CeH4- groups), heteroatom- substituted analogs of the foregoing, and combinations of the foregoing, for example for ester units that are from copolyester residues. The hydrocarbon groups forming D, E, and F can correspond to polyester units such as those from polyglycolic acid (PGA), polylactic acid (PLA), polybutylene adipate-co-terephthalate (PBAT), polybutylene succinate (PBS), a polyhydroxyalkanoate (PHA) (e.g., poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly-3-hydroxybutyrate (PHB), poly-3-hydroxybutyrate-co-4-hydroxybutyrate (P(3-HB-co-4- HB)), poly-hydroxyvalerate (PHV), and polyhydroxybutyrate-co-hydroxyhexanoate (PHBH)), a polylactone (e.g., ring-opening polymerization product of a cyclic ester like polycaprolactone (PCL)). Representative selections for D include (i) -OC(=O)-C6H4-C(=O)O- C4H8-OC(=O)-C4H8-C(=O)O-C4H8- (e.g., PBAT unit); (ii) -OC(=O)-C2H4-C(=O)O-C4H8- (e.g., PBS unit); (iii) -OC(=O)-CH2-CH(CH3)- (e.g., PH3B unit); (iv) -OC(=O)-CH2-CH(C2H5)- (e.g., PHV unit); (v) -OC(=O)-C3H6- (e.g., P4HB unit); (vi) -OC(=O)-CH2- (e.g., PGA unit); (vii) - OC(=O)-CH(CH3)- (e.g., PLA unit); and (viii) -OC(=0)-C5HIO- (e.g., PCL unit).Representative selections for E include (i) -C4H8-OC(=O)-C4H8-C(=O)O-C4H8-OC(=O)-C6H4- C(=O)O- (e.g., PBAT unit); (ii) -C4H8-OC(=O)-C2H4-C(=O)O- (e.g., PBS unit); (iii) -CH(CH3)- CH2-C(=O)O- (e.g., PH3B unit); (iv) -CH(C2H5)-CH2-C(=O)O- (e.g., PHV unit); (v) -C3H6- C(=O)O- (e.g., P4HB unit); (vi) -CH2-C(=O)O- (e.g., PGA unit); (vii) -CH(CH3)-C(=O)O- (e.g., PLA unit); and (viii) -C5HI0-C(=O)O- (e.g., PCL unit). Representative selections for F include those for D and E, but without the terminal carboxylate group.

[0096] In general, waxes according to Formulas I, II, IA, IIA, IIA.1 , II.A.2, IB, and IIB can be synthesized using precursors that provide the structural units in the formulas afterreaction (e.g., condensation reaction, ring-opening reaction). Suitable precursors for providing the A unit of Formula I can include carboxylic acids having a hydrocarbon chain having from 12 to 40 carbon atoms and esters of such acids. In particular, hydroxycontaining esters of such acids, such as hydroxyethyl esters. Similarly, precursors for providing the R1C(=O)O- unit of Formula IA and Formula IB can include carboxylic acids having the formula R1C(=O)OH and esters of such acids. Other suitable precursors for the A unit or the R1C(=O)O- unit include succinic acid anhydrides having a hydrocarbon chain according to the definitions of A and R1in the respective formulas. As noted above, including an anhydride such as a succinic anhydride in the synthesis of the wax can introduce a pendant carboxylic or carboxylate group to the resulting wax. As described above, pendant carboxylic or carboxylate groups on the wax can provide several functions, including providing easy removal of the wax from coated paper by increasing pH above 7; enabling the wax to be emulsified in a basic medium and applied as a water-repellent coating which can be easily removed by re-exposure to a basic medium; and providing improved water resistance via complexation with multivalent cations.

[0097] In embodiments, the synthetic wax can be formed as a reaction product between a polyester diol and an anhydride containing a saturated or unsaturated pendant hydrocarbon group having 4 to 30 carbon atoms (e.g., a hydrocarbon group as generally described above for R1). For example, a PBAT-diol, PBS-diol, PLA-diol, PHA-diol, or other polyester diol can be reacted with ODSA (octadecenyl succinic anhydride). A polyester diol can be formed by partial depolymerization of the polyester in the presence of a diol, such as a diol analog of the R1group described above, thus forming a polyester diol having a relatively lower molecular weight as compared to that of the initial polyester. 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 anhydride ring-opening and polyester diol reaction, but without substantial degradation of the polyester portion of the polyester diol reactants. The reaction can be performed in the presence of 0.01 to 0.5 wt.% catalyst relative to total reactants (e.g., all diols and anhydrides combined), for example Zn-, Ti-, or Sn-based catalyst, or other known condensation / esterification / transesterification catalyst. A polyester diol also can be formed by reaction of the polyester-forming monomers with a diol (e.g., an excess diol monomer for PBAT or PBS, an additional diol terminator for PHA, etc.). A polyester diol also can be formed by ring opening polymerization of cyclic esters (e.g., cyclic monoesters such as caprolactone, cyclic diesters such as lactide, glycolide, etc.) with a polymerization initiator, such as a diol ring opening of caprolactone, lactide, glycolide.

[0098] The A unit of Formula I, and the R1C(=O)O- unit of Formula IA and Formula IB, can be provided by a carboxylic acid having a hydrocarbon group corresponding to R1.

[0099] Glycolide, lactide (e.g., L-lactide, DL-lactide, D-lactide, or blends thereof), or a mixture thereof can be the precursor for glycolic and / or lactic units comprising the synthetic wax, i.e., unit B of Formula I, the OC(=O)-CHR3unit of Formula IA, and the CHR3-OC(=O) unit of Formula IB.

[0100] In embodiments, blends of synthetic waxes according to the disclosure can be used as coating materials, with or without additional additives, fillers, etc. For example, a blends of synthetic waxes can include a first synthetic wax, a second synthetic wax, optionally a third synthetic wax, optionally a fourth synthetic wax, etc. Each individual synthetic wax independently can be present in an amount of 1 wt.% to 99 wt.% relative to total synthetic waxes in the blend, for example at least and / or up to 1 , 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99 wt.% for an individual wax relative to total wax. Blends can be selected based on a desired combination of favorable resistance or barrier properties, favorable recycling or repulping properties, etc.

[0101] The synthetic waxes according to the disclosure can be provided in the form of a synthetic wax dispersion (or emulsion). 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 synthetic wax (or multiple synthetic waxes) 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 synthetic wax 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+(e.g., where R1, R2, and R3independently can be H or an alkyl group, such as with 1 , 2, 3, or 4 carbon atoms), 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. The synthetic wax dispersion can be applied to a substrate to form a coating thereon as described below. After application, the aqueous medium can be removed from the surface of the substrate (e.g., via applied heat or other drying step), thereby removing an amine from the synthetic wax (NR1R2R3) and converting the ionizable group of the synthetic wax to an acid form in the dried coating. 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).Coated Article

[0102] As illustrated in Figure 1 , the disclosure provides a coated article 300 including a substrate 310 and a coating 320 on or adjacent to the substrate. The coating 320 can include the synthetic wax or the synthetic wax composition according to any of the variously disclosed embodiments. The coating can be applied by any suitable method, for example from an aqueous dispersion or emulsion of the synthetic wax (e.g., solvent casting). In other embodiments, the coating can be applied in the form of a melt coating of the synthetic wax (e.g., extrusion and non-extrusion melt-coating). In other embodiments, the coating can be applied by compression molding the synthetic wax (e.g., application of heat and pressure to a synthetic wax in contact with a substrate to be coated). The substrate 310 is suitably a cellulosic substrate such as a paper substrate. These synthetic wax 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 synthetic wax). The synthetic wax 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 320 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 310 to form even thicker layers of the coating 320 (e.g., above 1000 pm, 2000 pm, or otherwise) if desired.

[0103] The coated article 300 of the disclosure includes a substrate 310. 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 synthetic wax 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 310 is a porous substrate, the coating 320 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).

[0104] 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 a synthetic wax 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 include any cellulosic materials commonly used in garments or otherwise, such as cotton, jute, flax, hemp, etc.

[0105] 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).

[0106] In embodiments (not shown), the substrate 310 has opposing first and second surfaces, and both surfaces of the substrate are coated with a synthetic wax coating 320 as described herein. The coatings 320 on opposing surfaces can be the same as or different from each other.

[0107] In other embodiments (not shown), two opposing substrates 310 can be adhered to or otherwise joined together by an intervening synthetic wax coating 320, for example where the synthetic wax serves as an adhesive. The substrates 310 can be the same as or different from each other.

[0108] The coating 320 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 synthetic wax coating asapplied to the (porous and / or cellulosic) substrate. For example, the additives can be included in a solution or mixture containing the synthetic wax 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, 5, 7, 10, 12, 15, or 20 wt.% and / or up to 0.1 , 0.2, 0.3, 0.5, 1 , 2, 3, 4, 5, 6, 8, 10, 12, 15, 16, 20, 25, 30, 40, or 50 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.

[0109] In embodiments, the synthetic wax coating 320 is applied as a second layer on top of a pre-coated paper or substrate 310. The pre-coated paper or substrate 310 can include an additional, intervening layer (not shown) between the coating 320 and the substrate 310. The pre-coating or intervening layer can improve recycling during paper repulping by more rapidly degrading the waxes, and / or improve barrier performance. In embodiments, the pre-coating can include one or more of a hydrophilic polymer, an oxygen- and / or oil-barrier polymer or additive, or a blend including a hydrophilic polymer. For example, the pre-coating can include one or more of a hydrophilic polymer (e.g., 50, 80 or 90 to 95, 98, or 99.8 wt.% hydrophilic polymer relative to blend), 0.1-10 wt.% polyethylene imine or other amine / imine polymer different from the hydrophilic polymer, and / or 0.1-10 wt.% carbonate salt (e.g., sodium carbonate, calcium carbonate, etc.). Examples of suitable hydrophilic polymers include PVOH and starch, for example alone or as a blend with each other. The pre-coating can also include any of the various additives and amounts described above, for example with fillers such as cellulose nanocrystals, clays, etc. to improve oil resistance and oxygen barrier property. Once the hydrophilic polymer or blend thereof iscoated on paper as first layer via melt-coating, solvent coating, aqueous coating, or other suitable method, then the synthetic wax coating can be applied as a second layer thereon.

[0110] In embodiments, the coated article 300 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, 11 , or 12. Suitable methods for determining the kit rating include TAPPI methods T599 pm-96 and UM 557.

[0111] In embodiments, the coated article 300 can have a cobb (or cobbl 800) rating of 20 g / m2or less. For example, the cobb rating (or cobbl 800 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. A suitable methods for determining the cobb rating includes TAPPI method T441 om-09.

[0112] In embodiments, the coated article 300 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 300 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.

[0113] The water- and oil-resistance properties of the coated article 300 or corresponding coating 320 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 320. Figure 2 illustrates a contact angle for test droplet (e.g., water or oil droplet) on a generic substrate, which could be the coating 320 on an underlying substrate 310.

[0114] 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.

[0115] 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.

[0116] 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 a corresponding 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

[0117] Water Resistance: The water resistance of a wax can be measured as a cobbl 800 value that represents grams of water per square meter that a wax 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 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 1800 values are expressed herein in grams per square meter (g / m2) unless otherwise indicated. Analogous methods and measurements can be made for a cobb600 value that represents grams of water per square meter that a wax absorbs in 600 seconds when brought in contact with water.

[0118] 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 and viscosities (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 0.5 inches 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 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.

[0119] Preparation of coated paper: 1 .0 g of the polymeric wax was introduced into a 20 ml vial followed by the addition of 2ml chloroform. The mixture was kept on stirring to obtain a clear solution. The obtained clear mixture was cast onto kraft paper (pre-coated with 5% starch) using a silicon spatula to get a smooth and uniform coating. The coated paper was subsequently dried in oven at 60°C for 30 minutes, followed by drying at room temperature for 24 hrs. The coatings generally had a coating loading of about 40-60 g / m2or about SO- 55 g / m2.

[0120] Nuclear Magnetic Resonance (NMR) Analysis:1H-NMR spectra for all samples were recorded using 500 MHz NMR spectrometer. Deuterated chloroform (CDCI3) and water (D2O) were used as solvents for all samples. Chemical shift values for all the spectrums were recorded in ppm.

[0121] Fourier-transform Infrared (FTIR) analysis: FTIR analysis for all the samples was done using FT / IR-6600 spectrometer designed by JASCO (Easton, Maryland, USA). The FTIR spectra were recorded using 32 scans in the range of 500-4000 cm-1at room temperature using resolution of 4cm-1.

[0122] Differential scanning calorimetry analysis (DSC): Differential scanning calorimetry analysis was done using DSC Q100 model instrument 10-15 mg of the sample was taken for each polymeric wax under the nitrogen flow of 100 ml / min. The three cycles method was used, and temperature was kept in between the range of 0°C to 200°C at a rate of 10°C / min for all samples.

[0123] Thermogravimetric analysis (TGA): Thermogravimetric analysis of all the samples were recorded using thermogravimetric analyzer (Q 50). 8-12 mg of the sample was taken ina platinum pan using nitrogen flow of 40 ml / min. The temperature was kept from 25°C to 600°C using a heating rate of 10°C / min.

[0124] 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 as well as at 90% RH and 38°C. Water vapor permeation was calculated by multiplying thickness of paper samples with water vapor transmission values.

[0125] 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.

[0126] Thermal sealing: The ASTM F88-21 standard protocol was adopted for recording thermal seal strength. The sealed samples were prepared using a bar thermal sealer (SENCORP, MA, USA). The 4-inch-long (about 10 cm) and 1 -inch-wide (about 2.5 cm) sample stripes were taken for preparing sealed samples at 121 °C (250°F) keeping sealing time at 5 second and sealing width of 0.4 inches (about 1 cm). The sealed samples were stored at 50% relative humidity and room temperature for 24 hours prior testing their seal strength. The maximum seal strength was recorded by measuring the force (N) required to break the seal and tensile strength (MPa) at maximum load and break point using 5565 Universal Instron Testing Machine (Instron, MA, USA). The grip separation rate was maintained to 10 inches / minute and grip separation of one inch. The samples were produced in triplicate.

[0127] Chemical degradation: 250 mg of each polymeric wax was taken in a 10 ml vial followed by the addition of 2 ml of 5 weight % of Na2COs solution. It was noted when the polymer's particles started to scatter in an alkaline medium. For each sample, the moment when it entirely disperses was the time for its degradation.

[0128] Recyclability: 2 g of a selected wax-coated paper was cut into small pieces and soaked into 50 mL of 3% Na2COs solution and was kept at 75°C for 10 minutes. The soaked coated paper was then kept at room temperature for 1 hr. The liquid was decanted followed by washing paper with deionized water three times to remove any suspended coatingmaterial left behind. The recovered paper was then dried in a vacuum oven for 24 hrs. at 70°C. FTIR analysis of the recovered paper can be used to confirm the separation of the coating material from the paper substrate (i.e., and thus the recyclability of the coated paper), for example when the recovered paper’s FTIR spectrum closely matches the original paper substrate (e.g., uncoated commercial Kraft paper).

[0129] Recyclability: An alternate lab-scale recyclability test can be used. The test procedure is modified according to 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. Briefly, 20% coated sample and 80% uncoated base paper is mixed and repulped in a lab-scale pulper at pH 7 and 125°F (about 52°C). The pulped suspension is passed through a vibration flat screen with 0.010 inch (about 0.0254 cm) slots. Handsheets are made from screen accepts. Properties including Coefficient of Friction (Slide Angle), Short Span Compression Strength (STFI), Burst Strength, Water-Drop Penetration, and Stickies are investigated following TAPPI standards. The results are compared to a control sample, which is a 100% base paper pulped and screened using identical conditions. In certain cases, removing any coating flakes from pulp during the recyclability is further assisted with a) use of bubble flotation with and without emulsifiers; b) use of screens sizes such as between 50-254 micron slit size or a combination of both a and b. Also, the stickies count can be done for a hand sheet prepared at different temperatures such as 120°C-180°C.

[0130] Repulpability: Repulpability can be evaluated using the FBA Voluntary Standard for Repulping and Recycling Corrugated Fiberboard Treated to Improve Its Performance in the Presence of Water and Water Vapor - Part I Repulpability. Briefly, paper samples are repulped in a Modified Waring Blender and a British Disintegrator in water at a pH of 7 (+ / - 0.5 pH units) that is maintained at 125°F (+ / - 10°F; about 52°C + / - 6°C). The pulped material is separated in a screen with 0.010 inch (about 0.0254 cm) slots to determine fiber recovery as a percentage of the amount of fiber charged. 85% repulping yield is required to pass this test. The yield of repulping is calculated as the fraction of fiber accepted (or recovered on screen) relative to total fiber accepted (or recovered on screen) plus fiber rejected (or passing through screen).

[0131] 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.

[0132] Compression Molding: 5 g of polymeric wax sample was spread on 5% starch- coated paper sample and was pressed using PHI Manual Hydraulic Compression Press (California, USA) at 70°C for 4 minutes to obtain a coated paper sample.

[0133] Gel permeation chromatography (GPC) analysis: Gel permeation chromatography (GPC) analysis was performed using refractive index detector (Waters 2414) and Isocratic HPLC pump (Waters 1515) connected to plus Autosampler (Waters 717). The polymeric wax sample (P-W-LA3) was dissolved in tetrahydrofuran (2 mg / mL). Approximately 100 pL of the solutions (filtered) were injected and adjusted the run time = 50 min and flow rate = 1 .0 mL / min. The instrument was calibrated using PS (polystyrene) standards. A Waters BREEZE Software was used for the molecular weight distribution (MWD) curves.Examples

[0134] The following examples illustrate the disclosed synthetic waxes 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 : Synthesis of Synthetic PBAT-Wax from PBAT Polymer

[0135] This example illustrates a generic synthesis of a synthetic wax including butylene adipate-co-butylene terephthalate ester units derived from a PBAT polymer (Fig. 3, top). A 500 mL flask was charged with commercial PBAT (polybutylene adipate terephthalate) (plates) 250.0 grams (0.595 moles) and zinc ethyl hexanoate catalyst (0.1 wt%, 0.5 g). The flask was closed via rubber septum to block any air movement and was heated to 220 °C for 2 hours using a mechanical stirrer. Once the PBAT was melted, 1 ,4-butanediol (99%) (0.059 mole, 5.418 g) was injected (with vigorous stirring for quick mixing). The reaction mixture was further heated at 220 °C for 1 hour using mechanical stirrer to partially depolymerize the PBAT polymer to form a lower molecular weight PBAT-diol (Fig. 3, middle) having two terminal hydroxyl groups and lower number of PBAT ester linking units (average of ten) relative to the original PBAT polymer. For the subsequent step of the addition of 2-(1 - octadecenyl) succinic anhydride (ODSA), the temperature of the reaction mixture was decreased to 160 °C and ODSA (0.107 mole, 37.5 g) was added. The reaction mixture was stirred for 1 hour and then cast on a TEFLON (PTFE) plate to form sheet (or film) of the synthetic wax ODSA-PBAT 10-ODSA (Fig. 3, bottom). The ODSA-PBAT 10-ODSA wax has terminal two anhydride ring-opened analogs of ODSA, each with a pendant carboxylic group (see Fig. 6 top for ring-opened ODSA units in a PLA-based synthetic wax), a butylene linker, and an average of ten PBAT ester units. The foregoing method can be generalized to theformation of other synthetic waxes. For example, the ratio of diols with respect to starting polyester polymer (e.g., PBAT) can be selected based on the targeted units in the polyester diols. The amount of ODSA to OH groups in the prepared polyester diol can be selected within the range of 1 :0.8 to 0.8:1 molar equivalents. Also, the catalyst can be Zn, Ti, Sn, or other known condensation / esterification / transesterification catalysts, which can be used in amounts ranging from 0.01 -0.5wt%.Example 2: Synthesis of Synthetic PBAT -Wax from PBAT Monomers

[0136] This example illustrates a generic synthesis of a synthetic wax including butylene adipate-co-butylene terephthalate ester units derived from a PBAT monomers (Fig. 4, top and middle). A 250 mL three-necked flask was charged with dimethylterephthalate (DMT) monomer (100 mmole, 19.419 grams), 1 ,4-butanediol monomer (99%) (110 mmole, 10.013) and Ti(OBu)4 (0.1 mol% with respect to DMT). The flask was equipped with a condenser followed by heating the mixture to 150eC for 2 hrs (Fig. 4, top). Next, the condenser was replaced with a distillation head, and the heating was continued at 160eC with the removal of methanol for 3-4 hrs (Fig. 4, middle). Adipic acid monomer (100 mmole, 14.616 grams) was added to the reaction mixture, and the reaction mixture was at 180eC for an hour with the removal of methanol and water. Subsequently, the flask was connected with a vacuum pump through a cold trap and heated to 180-190eC at 4 hours to form a lower molecular weight PBAT -diol having two terminal hydroxyl groups and an average of ten PBAT ester linking units (Fig. 4, bottom). For the subsequent step of the addition of 2-(1 -octadecenyl) succinic anhydride (ODSA), the temperature of the reaction mixture was decreased to 160 °C and ODSA (19.8 mmole, 6.930 g) was added. The reaction mixture was stirred for 1 hour and then cast on a TEFLON (PTFE) plate to form sheet (or film) of the synthetic wax ODSA- PBAT10-ODSA (Fig. 4, bottom). The foregoing method can be generalized to the formation of other synthetic waxes. For example, the ratio of diols with respect to 1 mol equivalent of diester / diacid can be selected in the range of 1 .02-1 .6 molar equivalents as this helps to tailor the degree of polymerization in the polyester diol. The amount of ODSA to OH groups in the prepared polyester diol can be selected within the range of 1 :0.8 to 0.8:1 molar equivalents.Example 3: Synthesis of Synthetic PLA-Wax from PLA Polymer

[0137] This example illustrates a generic synthesis of a synthetic wax including lactic acid ester units derived from a PLA polymer. The synthesis is analogous to that shown in Fig. 3 (Example 1), but using a PLA polymer as starting material instead of a PBAT polymer. A 500 mL flask was charged with commercial PLA (polylactic acid) 250.0 grams (1 .736moles) and zinc ethyl hexanoate catalyst (0.1 wt%, 0.5 g). The flask was closed via septum to block any air movement and was heated to 200 °C for 2 hours using mechanical stirrer. Once the PLA was melted, 1 ,4-butanediol (99%) (0.868 mole, 7.901 g) was injected (with vigorous stirring for quick mixing). The reaction mixture was further heated at 200 °C for 1 hour using mechanical stirrer to partially depolymerize the PLA polymer to form a lower molecular weight PLA-diol having two terminal hydroxyl groups, a butylene linker, and a lower number of PLA ester linking units (average of 20) relative to the original PLA polymer. For the subsequent step of the addition of 2-(1 -octadecenyl) succinic anhydride (ODSA), the temperature of the reaction mixture was decreased to 160 °C and ODSA (1 .562 mole, 54.687 g) was added. The reaction mixture was stirred for 1 hour and then cast on a TEFLON (PTFE) plate to form sheet (or film) of the synthetic wax ODSA-PLA20-ODSA. The ODSA-PLA20-ODSA wax has terminal two anhydride ring-opened analogs of ODSA, each with a pendant carboxylic group, a butylene linker, and an average of 20 PLA ester units. The foregoing method can be generalized to the formation of other synthetic waxes. For example, the ratio of diols with respect to starting polyester polymer (e.g., PLA) can be selected based on the targeted units in the polyester diols. The amount of ODSA to OH groups in the prepared polyester diol can be selected within the range of 1 :0.8 to 0.8:1 molar equivalents. Also, the catalyst can be Zn, Ti, Sn, or other known condensation / esterification / transesterification catalysts, which can be used in amounts ranging from 0.01-0.5wt%.Example 4: Synthesis of Synthetic PLA-Wax from PLA Monomer

[0138] This example illustrates a generic synthesis of a synthetic wax including lactic acid ester units derived from PLA monomer (lactide) (Fig. 5, top). A 100 mL flask was charged with vacuumed dried lactide monomer 40.0 grams (0.277 moles), 1 ,4-butanediol monomer (99%) (0.014 mole, 1.264 g), and zinc ethyl hexanoate catalyst(0.5 wt%, 0.200 g). The flask was closed via rubber septum and was heated to 160 °C for 7 hours to form a PLA diol including two oligomeric PLA segments (20 PLA units each) joined by a butylene linker (BD) and having two terminal hydroxyl groups (HO-PLA20-BD-PLD20-OH) (Fig. 5, bottom). For the subsequent step of the addition of 2-(1 -octadecenyl) succinic anhydride (ODSA), the temperature of the reaction mixture was maintained at 160 °C and ODSA (0.025 mole, 8.750 g) was added. The reaction mixture was stirred for 1 hour and then cast on a TEFLON (PTFE) plate to form sheet (or film) of the synthetic wax ODSA-PLA20-BD-PLD20-ODSA material. (Fig. 6, top). The ODSA-PLA20-BD-PLD20-ODSA wax has terminal two anhydride ring-opened analogs of ODSA, each with a pendant carboxylic group, two segments of an average of 20 PLA ester units, and central butylene linker. The foregoingmethod can be generalized to the formation of other synthetic waxes. For example, the ratio of diol as ring-opening initiator with respect monomer (e.g., lactide) can be based on the targeted units in the polyester diols. The amount of ODSA to OH groups in the prepared PLA diol can be selected within the range of 1 :0.8 to 0.8:1 molar equivalent. This approach is extendable to other polyesters that are prepared from their monomers, such as polylactones, polylactides, polyglycolides, and their combinations. Also, the catalyst can be Zn, Ti, Sn, or other known condensation / esterification / transesterification catalysts, which can be used in amounts ranging from 0.01 -0.5wt%.Example 5: Synthetic Wax Emulsions and Paper Coatings

[0139] This example illustrates the formation of synthetic wax emulsions by forming an ionized form of the synthetic wax, which can then be used to form paper coatings, both as single waxes and as wax blends. Coated paper materials were tested for their water resistance (cobb600 value) and oil / grease resistance (kit rating). To make an emulsion of the PLA-wax (ODSA-PLA20-ODSA), 1 .0 gram of the wax (ground) was combined with 3-4 drops of NH4OH in total of 3 ml of deionized water. The mixture was stirred for 2-3 hours at 70eC to get fine emulsion before their use to form a coating on kraft paper (KP) or starch coated kraft paper (KP / S). To make the emulsion of the PBAT-wax (ODSA-PBAT10-ODSA), 1 .0 gram of the wax (ground), was added 5-6 drops of NH4OH in total of 3 ml of deionized water. The mixture was stirred for 1 hour at 70eC to get fine emulsion before their use to form a coating on kraft paper (KP) or starch coated kraft paper (KP / S). Fig. 6 (bottom) illustrates an ionized form of the ODSA-PLA20-BD-PLD20-ODSA wax in an emulsion. For starch coated kraft paper, a 10 wt.% starch solution in water was prepared and used to precoat the paper before coating with the emulsified waxes. The resistance properties for Example 5 are shown in Table 1 .Table 1 . Resistance values and for wax-coated paper

[0140] As shown in Table 1 , blends of PBAT-wax and PLA-wax enhance the water barrier properties on uncoated paper (i.e., no starch coating). In particular, blends with about 10-30 wt.% PLA-wax and about 70-90 wt.% PBAT-wax provided improved water resistance (Cobb600 rating) relative to both PBAT-wax alone and PLA-wax alone.Example 6: Synthetic PLA-Wax Additive Blends

[0141] This example illustrates the use of PLA-wax (ODSA-PLA20-ODSA) blends with various plasticizer and other additives as coatings on uncoated kraft paper. Qualitative observations were made after spraying coated papers with water. Tables 2 and 3 below show the results as well as the additive amount (wt.%), with the balance of the coating being PLA-wax.Table 2. Water-resistance properties of PLA-wax / plasticizer coatings on paperTable 3. Water-resistance properties of PLA-wax / additive coatings on paperExample 7: Synthetic PLA-Wax / PBAT-Wax Additive Blends

[0142] This example illustrates the use of PLA-wax (ODSA-PLA20-ODSA) and PBAT- wax (ODSA-PBAT10-ODSA) blends (10:90 w / w PLA-wax :PBAT-wax) with various additives as coatings on paper. The additives were selected to advance the barrier properties of the coating, ensuring that the paper could withstand exposure to water without compromising its functionality, biodegradability, and recyclability. The additives interact to create a stronger protective layer on the paper surface to prevent water or moisture penetration. The additives extend the potential applications of the coated paper and also contribute to its performance in demanding environments, such as packaging for food or moisture-sensitive products. Additives include a butyl distearate (distearate ester of 1 ,4-butanediol), sodium stearate, polyvinyl acetate (PVA), and a carboxylated PBAT (CPBAT) as disclosed in PCT / US25 / 26354. Qualitative observations were made after spraying coated papers with water, and quantitative Cobb600 and kit measurements were made. Table 4 below shows the results as well as the additive amount (wt.%), with the balance of the coating being PLA- wax / PBAT-wax (10 / 90 w / w).Table 4. Water-resistance properties of PLA-wax / PBAT-wax / additive coatings on paperExample 8: Synthetic PLA-Wax / PBAT-Wax Blends with Variable Ester Content

[0143] This example illustrates the use of PLA-waxes and PBAT-waxes having variable ester in terms of number of ester residues in the wax between terminal ODSA units. Waxes were synthesized as generally described in Examples 1-4, including ODSA-PLA5-ODSA, ODSA-PLA7-ODSA, ODSA-PLA10-ODSA, ODSA-PLA20-ODSA, ODSA-PBAT5-ODSA, ODSA-PBAT7-ODSA, and ODSA-PBAT10-ODSA, with the number in the name indicating the number of ester residues in the wax. Wax blends, with and without commercial acrylates additives, were applied as coatings on paper, and Cobb600 and recyclability measurements were made. Table 5 below shows the results.Table 5. Water-resistance properties of PLA-wax / PBAT-wax / additive coatings on paperExample 9: Synthetic PLA-Wax / PBAT-Wax Emulsions with Additives

[0144] This example illustrates the use of PLA-wax (ODSA-PLA20-ODSA) and PBAT- wax (ODSA-PBAT10-ODSA) emulsions with various thickeners or additives to evaluate emulsion stability. A stable emulsion ensures a uniform distribution of particles, improves its viscosity, prevents phase separation, which ensures the coating's homogeneity and improves its functional / barrier properties. Qualitative observations were for emulsion stability, and quantitative Cobb600 measurements were made after coating on a paper substrate. Table 6 below shows the results.Table 6. Stability of PLA-wax / PBAT-wax / additive emulsionsExample 10: Synthetic PBAT-Wax Coatings with Variable Paper Treatment

[0145] This example illustrates the use of PBAT-wax (ODSA-PBAT10-ODSA) with various paper treatments before application of PBAT-wax coating. Four different paper (kraft paper) pretreatments were used, including: (1) applying 5% starch as base layer, (2) washing the kraft paper surface with 2% alum solution, (3) washing kraft paper surface with 10% acetic acid solution, or (4) heating kraft paper for 2 min at 120°C. Next, a PBAT-wax emulsion was applied to paper followed by drying at room temperature to form a coated paper. The coated kraft paper was passed with hot air (170°C) for 2-3 seconds. Next the coated paper samples were tested for their water (Cobb600) and oil resistance test (kit rating). All coated samples were repulpable as well as recyclable. Table 7 below shows the results.Table 7. Water-resistance properties of PBAT-wax coatings on pretreated paperExample 11 : Synthetic PLA-Wax Coatings with Biodegradable Polymer

[0146] This example illustrates the use of PLA-wax blended with a biodegradable polymer (PBS-graft-maleic anhydride) as a coating, for example in sustainable packaging applications. Recyclable waxes were synthesized from commercial polylactic acid (PLA) and 2-(1 -octadecanyl)succinic anhydride (ODSA-PLAn-ODSA or Pn, where the ‘n’ in PLAn denotes the number of lactide units) as described in Example 3 above. The PLA-waxes were blended with the graft copolymer polybutylene succinate-graft-maleic anhydride (PBS- g-MA or PMAn, where the ‘n’ in MAn denotes the wt% of MA that had been grafted onto the PBS backbone), and the blends were used for paper coating applications. PBS-g-MAn was used to improve the strength, toughness, and flexibility of the wax-coated paper, thusreducing its brittleness and tendency to form cracks. ODSA-PLAn-ODSA waxes and PBS-g- MAn were dissolved in a solvent and applied onto starch pre-coated paper substrates. Subsequently, the water resistance of these blend-coated paper samples was determined via Cobb1800 measurements. Paper coated with PLA-wax alone was found to have a Cobbl 800 value of 28.3 ± 3.4 g / m2, while the wax / graft copolymer blend-coated paper (coated with ODSA-PLA15-ODSA / PBS-g-MA5, with a 75:25 wax:graft copolymer weight ratio) exhibited a much lower Cobbl 800 value of 3.7± 1 .3 g / m2. Similarly, kit rating measurements were performed to evaluate the oil resistance, and all the coated paper samples were found to have excellent oil resistance (with the maximum possible kit rating of 12 / 12). In addition, the wax-blend coated paper successfully passed repulpability and recyclability tests. The thermal sealing strength of the wax blend-coated paper was comparable to that of commercial acrylic-coated paper. Table 8 below shows the compositions and results for the tested coatings.Table 8. Composition and properties of Pn:PMn coatings on pretreated paperFurther Aspects

[0147] Further aspects of the disclosure are provided below. Synthetic waxes and their blends can include at least one long-chain hydrocarbon residue having 4 to 40 or 12 to 40 carbon atoms, and at least one oligomeric ester residue containing 4 to 50 ester units such as adipate units, adipate-co-terephthalate units, alkanoates units, glycolic acid units, lactic acid units, and / or other ester units. The hydrocarbon residues include at least one ionizable functional group such as carboxylic groups (-COOH), amines (-NH2, -NHR, -NR2), phenols,phosphoric acids, sulfonic acids, or a combination thereof. The wax can be used in waterborne emulsions and wax blends, for example in paper coatings, such that, at the end of life, the paper is recyclable / repulpable and biodegradable. While certain properties or features below are described with respect to specific Formulas III and 11 IA-I I IB, the properties and features can apply to the synthetic waxes and related compositions as described more generally herein.

[0148] In an aspect, the disclosure relates to a synthetic wax according to the following Formula III:A(X)-a-B-b-(Y)C [Formula III]In Formula III: A is a hydrocarbon (linear, cyclic, branched, saturated, unsaturated, with or without additional non-hydrogen and non-carbon atoms) having 4 to 40 carbon atoms. B is an oligomeric residue of n ester linkers such as (i) n glycolic acid units, (ii) n lactic acid units, (iii) n glycolic acid units and lactic acid units in total, (iv) n alkylene succinate unit, (v) n alkylene adipate units, and / or (vi) n copolyester units. The index “n” can be in a range of 4 to 50 ester linker units. C is either OH or a hydrocarbon (linear, cyclic, branched, saturated, unsaturated, with or without additional non-hydrogen and non-carbon atoms) having 4 to 40 carbon atoms. Linker a can be an ester linking group between A and B. Linker b, if present, can be an ester linking group between B and C. X and Y denote one of the more ionizable groups (e.g., which can be pendant from A and C, respectively) such as COOH, amines (- NH2, -NHR, -NR2); phenols, phosphoric acids, sulfonic acids, or a combination and optionally have 1 -6 carbon atoms. In embodiments, one or both of X and Y are present.

[0149] In an aspect, the disclosure relates to a synthetic wax according to the following FormulaIn Formulas 11 IA, IIIB, and IIIC: R1is a hydrocarbon group having 4 to 39 carbon atoms with one or more COOH group or other ionizable groups. The R1hydrocarbon group can be on one end, both ends, and / or non-terminal (e.g., attached to the backbone). R2is a hydrocarbon linking group having 2 to 18 carbon atoms. The index n is 4 to 50, and the index m is 0 to 16. R3is independently H or CH3 for each of the n repeat units. The synthetic wax can include a blend of at least one synthetic wax according to Formula 11 IA, at least one synthetic wax according to Formula IIIB, and / or at least one synthetic wax according to Formula IIIC.

[0150] The synthetic wax of Formula I IIA can be prepared by reacting PLA-diol and then reacting with ODSA / octadecenylsuccinic anhydride. PLA diols are prepared from PLA partial depolymerization with diols such as ethylene glycol or ring opening of lactide with diol such as ethylene glycol. PLA stands for polylactic acid. The synthetic wax of Formula I IIA also can be prepared by reacting PGA-diol and then reacting with ODSA / octadecenylsuccinic anhydride. PGA diols are prepared from PGA partial depolymerization with diols such as ethylene glycol or ring opening of glycolide with diol such as ethylene glycol. PGA stands for polyglycolic acid.

[0151] The synthetic wax of Formula 11 IB can be prepared by reacting PBAT-diol or PBS- diol and then reacting with ODSA / octadecenylsuccinic anhydride. PBAT and PBS diols are prepared from PBAT and PBS partial depolymerization, respectively. Alternatively, oligomeric PBAT and PBS diols are prepared via a reaction of monomers in stoichiometric imbalance where diols are present in excess relative to diacids / diesters. PBS stands for polybutylene succinate, and PBAT for polybutylene adipate-co-terephthalate.

[0152] The synthetic wax of Formula 11 IC can be prepared by reacting diols of polyhydroxy alkanoates (PHAs) with octadecenylsuccinic anhydride. Diols of polyhydroxy alkanoates are prepared by i) partial depolymerization of polyhydroxy alkanoates; or ii) oligomerization of hydroxy alkanoates.

[0153] In Formulas 11 IA, 11 IB, and II IC: R1can be selected from the group consisting of (i) R1A, and (ii) R1A-d-; wherein: R1A is a C8 to C39 alkyl group or unsaturated analog thereof; and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group (or other ionizable groups) or a salt thereof. In embodiments, R1is R1A, and R1Ais a C1 1 to C39 alkyl group. In embodiments, R1is R1A-d- or the salt thereof.

[0154] In embodiments, the synthetic wax has a melting temperature in a range of 30°C to 90°C; and / or the synthetic wax has a molecular weight in a range of 300-5000 g / mol.

[0155] In embodiments, the synthetic wax has a melting temperature in a range of 30°C to 160°C; and / or the synthetic wax has a molecular weight in a range of 500-100000 g / mol.

[0156] In an aspect, the disclosure relates to a high-melting synthetic wax comprising: a polymerization reaction product of a synthetic wax according to Formula III in which at least one of A and C contains at least one unsaturated carbon-carbon double bond; a polymerization reaction product of a synthetic wax according to Formulas 11 IA, 111 B, and / or IIIC in which R1contains at least one carbon-carbon double bond; a complex between a polyvalent metal cation and a synthetic wax according to Formula III in which at least one ofA and C contains at least one carboxylic group or other ionizable groups; or a complex between a polyvalent metal cation (Ca+2, Mg+2, Al+3, etc.) and a synthetic wax according to Formulas IIIA, I IIB, and / or I IIC in which R1contains at least one carboxylic group.

[0157] In an aspect, the disclosure relates to a synthetic wax composition comprising: a synthetic wax according to Formulas III, IIIA, 111 B, and / or 11 IC; and one or more additives (organic, inorganic, and both organic-inorganic).

[0158] In embodiments, the additives are selected from inorganic fillers such as modified / unmodified titanium dioxide, modified / unmodified silica, modified / unmodified clay, calcium carbonate, aluminum oxide, zinc oxide, talc, mica, barium sulfate, and iron oxides. Some of these fillers can be used as their hydrolyzed forms or their salt form (such as alum). These additives are present in an amount of 0.5 wt.% to 50 wt.% relative to the synthetic wax composition. These additives have various roles, such as thickeners, surface energy modifiers, sealing properties, etc.

[0159] In embodiments, organic additives include polymers / oligomers such as acrylics, polyurethane, epoxy, alkyds, functional polyester, natural waxes, petroleum waxes, polyhydrocarbons, silicone, vinylic, vinylic-acrylics, polyamide, carbohydrates (starch, cellulose, chitosan, alginates), polyvinyl alcohol, polyethylene vinyl alcohols acrylic acid, polyethylene vinyl alcohol, proteins, lignin (such as kraft lignin predispered in water using a base), polyethers, polyether-polyesters, or a combination thereof. These organic additives can be anionic, cationic, or neutral. For example, cationic acrylics, anionic acrylics, cationic starches, neutral / cationic / an ionic starches, etc. These additives are present in an amount of 0.5 wt.% to 50 wt.% relative to the synthetic wax composition. These additives have various roles, such as thickeners, surface energy modifiers, sealing properties, etc.

[0160] In embodiments, organic additives can also include low molecular weight (MW below 1000 g / mol) substances with functional groups such as esters (mono, diester, triester), mono-, di-, tri-, and poly-alcohol bearing additives (primary, secondary, tertiary); and amide bearing additives (mono, di-, tri-amides). These additives are present in an amount of 0.5 wt.% to 50 wt.% relative to the synthetic wax composition. These additives have various roles such as thickeners, surface energy modifiers, etc.

[0161] In an aspect, the disclosure relates to a synthetic wax dispersion comprising: an aqueous medium; and a synthetic wax according to Formulas III, IIIA, IIIB, and / or IIIC dispersed in the aqueous medium after ionizing the COOH or other ionizable groups present in the structure. In the case of COOH group, waxes are emulsified in water in the presence of neutralization with a base such as sodium bicarbonate, sodium carbonate, sodiumhydroxide, ammonium bicarbonate, ammonia, ammonium hydroxide, trialkyl amine, polyethylene imines, etc. The emulsion / latex of the waxes can be used for paper or other article coatings. In certain cases, wax was melted before adding water and neutralizer (base for acid functional waxes and vice versa) which gave stable emulsions. In other cases, emulsions were stabilized with thickeners such as polyacid or their salts, polybasic (cationic starch) and their salts or combination of heat and thickeners.

[0162] In an aspect, the disclosure relates to a coated article comprising: a substrate; and a synthetic wax according to Formulas III, 11 IA, 111 B, and / or 11 IC, a high-melting synthetic wax formed therefrom, with and without organic / inorganic additives / f illers.

[0163] In embodiments, the coating can be applied via rod coating, spray coating, knife coating, roll coating, curtain coating, and dip coating.

[0164] In embodiments, the substrate is a primarily cellulosic substrate (such as paper, wood, molded fiber, etc.).

[0165] In embodiments, the coating can be applied as thin coating (less than 1wt% of the cellulose article such as paper) or applied as thick coating 1 -20 wt% of the cellulose article

[0166] In embodiments, the substrate, such as paper, Kraft paper, corrugated paper, paperboard, and molded pulp paper, can be modified or unmodified before coating. For example, the substrate can be treated with acrylics, polyurethane, epoxy, alkyds, functional polyester, natural waxes, petroleum waxes, polyhydrocarbons, silicone, vinylic, vinylic- acrylics, polyamide, carbohydrates (starch, cellulose, chitosan, alginates), polyvinyl alcohol, polyethylene vinyl alcohols acrylic acid, polyethylene vinyl alcohol, proteins, lignin, polyethers, polyether-polyesters, or a combination thereof. These organic additives can be anionic, cationic, or neutral; inorganic fillers (such as TiO2, Silica, clay, alum, calcium carbonate, etc.) before applying a wax coating layer. Thermal treatment can also be applied before applying the coating. For example, briefly heating paper before coating is applied.

[0167] In embodiments, the waxes (and their blends with organic / inorganic additives) can be used for internal sizing where fiber and waxes (optionally additives) are mixed and molded or handsheets are formed. Alum or other retention aids are added to improve the retention of wax(and their blends) onto the fiber.

[0168] In embodiments, the coated article has a kit rating in a range of 1 to 12; and / or the coated article has a cobb600 rating of 70 g / m2 or less.

[0169] In embodiments, the coated articles with waxes or their blends have WVTR values between 0.0001- 1000 g*mm / m2*24h at 37°C and 90% RH. Preferentially, WVTR is between 0.01-20 g*mm / m2*24h.

[0170] In embodiments, the coated articles with waxes (or their blends) have Cobb600 <60 g / m2 (preferentially 10-30) and kit rating between 1-12 (preferably 3-12).

[0171] In embodiments, the articles coated with these waxes (or their blends) are thermally sealable with dwell time <5 sec, temperature <200°C, preferentially, 1 sec and <160°C.

[0172] In embodiments, the articles with waxes (or their blends) are thermally sealable with dwell time <5 sec, temperature <200°C, preferentially, 1 sec and <160°C.

[0173] In embodiments, paper, molded fiber containers, and paper board coated with waxes (or their blends) are biodegradable.

[0174] In embodiments, paper, molded fiber containers, and paper board coated with waxes (or their blends) are reputable / recyclable. Optionally, waxes and their blends can also be applied to paper, fiber, and paper board that already has some 0.1-5wt% of organic / inorganic materials such as sodium carbonate, sodium bicarbonate, sodium silicate, polyethylene imine, cationic starches prior to applying wax (or wax blends coating) to further facilitate repulping / recycling of the coated paper.

[0175] International Publication No. WO 2024 / 215970 (PCT Application No. PCT / US24 / 24191) contains additional disclosure related to synthetic waxes and is incorporated herein by reference in its entirety.

[0176] 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 all changes and modifications which do not constitute departures from the true spirit and scope of this disclosure.

[0177] 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.

[0178] All patents, patent applications, government publications, government regulations, and literature references cited in this specification are hereby incorporatedherein by reference in their entirety. In case of conflict, the present description, including definitions, will control.

[0179] 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. A synthetic wax according to the following Formula IIA.1 :R1C(=O)O-R2-[D1]n-O(C=O)-R1(IIA.1 ); wherein:R1is R1A-d- in which R1Ais a Cs to C39 monounsaturated alkenyl group, and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof;R2is a hydrocarbon linking group having 2 to 18 carbon atoms; n is 10 to 50; andD is -OC(=O)-C6H4-C(=O)O-C4H8-OC(=O)-C4H8-C(=O)O-C4H8-.

2. The synthetic wax of claim 1 , further comprising a wax according to the following Formula IIA.2:R1C(=O)O-R2-[D2]m-O(C=O)-R1(IIA.2); wherein:R1is R1A-d- in which R1Ais a Cs to C39 monounsaturated alkenyl group, and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof;R2is a hydrocarbon linking group having 2 to 18 carbon atoms; m is 10 to 50; andD2is -OC(=O)-CH(CH3)-.

3. The synthetic wax of claim 2, wherein a weight ratio of the Formula IIA.1 wax : the Formula IIA.2 wax is in a range of 70:30 to 90:10.

4. A synthetic wax dispersion comprising: an aqueous medium; and a synthetic wax according to claim 1 dispersed in the aqueous medium.

5. The synthetic wax dispersion of claim 4, wherein the synthetic wax is in ammonium salt form.

6. A coated article comprising: a cellulosic substrate; and a coating on the substrate, the coating comprising the synthetic wax of claim 1 .

7. A synthetic wax according to the following Formula II:A(X)-a-B-b-C(Y) (II); wherein:A is a hydrocarbon ester group having 4 to 40 carbon atoms;B is an oligomeric residue containing n ester units (e.g., other than glycolic acid units and lactic acid units), where n is 4 to 50;C is either OH or a hydrocarbon ester group having 4 to 40 carbon atoms; a is either absent, or present as a linking group between A and B; b is either absent, or present as a linking group between B and C;X is either absent, or present as one or more (pendant) ionizable groups on A;Y is either absent, or present as one or more (pendant) ionizable groups on C; and at least one of X and Y is present.

8. The synthetic wax of claim 7, wherein at least one of a and b is present.

9. The synthetic wax of claim 7, wherein both a and b are absent.

10. The synthetic wax of claim 7, wherein both X and Y are present.

11. The synthetic wax of claim 10, wherein X and Y are independently selected from the group consisting of carboxylic groups, salts thereof, amino groups, ammonium salts thereof, phenol groups, phosphate groups (or phosphoric acid groups), sulfonate groups (or sulfonic acid groups), and combinations thereof.

12. The synthetic wax of claim 10, wherein:X and Y are independently selected from the group consisting of carboxylic groups and salts thereof; andA and C each contain 0, 1 , 2, or 3 unsaturated carbon-carbon double bonds.

13. A synthetic wax according to the following Formula 11 A or 11 B:R1C(=O)O-R2-[D]n-O(C=O)-R1(HA);R1C(=O)O-[E]m-R2-[D]n-O(C=O)-R1(IIB); wherein:R1is a hydrocarbon group having 4 to 39 carbon atoms having one or more ionizable groups;R2is a hydrocarbon linking group having 2 to 18 carbon atoms; n is 4 to 50; m is 4 to 50;D is an ester unit represented by -OC(=O)-F-;E is an ester unit represented by -F-C(=O)O-;F is a hydrocarbon group having 1 to 30 carbon atoms.

14. The synthetic wax of claim 13, wherein D is selected from the group consisting of:(i) -OC(=O)-C6H4-C(=O)O-C4H8-OC(=O)-C4H8-C(=O)O-C4H8-;(ii) -OC(=O)-C2H4-C(=O)O-C4H8-;(iii) -OC(=O)-CH2-CH(CH3)-;(iv) -OC(=O)-CH2-CH(C2H5)-;(v) -OC(=O)-C3H6-;(vi) -OC(=O)-CH2-;(vii) -OC(=O)-CH(CH3)-; and(viii) -OC(=O)-C5HI0-.

15. The synthetic wax of claim 14, wherein the synthetic wax according to FormulaI IB is present and E is selected from the group consisting of:(i) -C4H8-OC(=O)-C4H8-C(=O)O-C4H8-OC(=O)-C6H4-C(=O)O-;(ii) -C4H8-OC(=O)-C2H4-C(=O)O-;(iii) -CH(CH3)-CH2-C(=O)O-;(iv) -CH(C2H5)-CH2-C(=O)O-;(v) -C3H6-C(=O)O-;(vi) -CH2-C(=O)O-;(vii) -CH(CH3)-C(=O)O-; and(viii) -C5HI0-C(=O)O-.

16. The synthetic wax of claim 13, wherein R1is selected from the group consisting of:(i) R1A, and(ii) R1A-d-; wherein:R1Ais a Cs to C39 alkyl group or unsaturated analog thereof; and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof.

17. The synthetic wax of claim 13, wherein: the synthetic wax according to Formula 11 A is present;D is -OC(=O)-C6H4-C(=O)O-C4H8-OC(=O)-C4H8-C(=O)O-C4H8-;R1is R1A-d-;R1Ais a Cs to C39 hydrocarbon group having one unsaturated carbon-carbon double bond; and d is a hydrocarbon linking group containing 1 to 6 carbon atoms and a pendant carboxylic acid group or salt thereof.

18. The synthetic wax of claim 13, comprising at least one synthetic wax according to Formula IIA.

19. The synthetic wax of claim 13, comprising at least one synthetic wax according to Formula I IB.

20. The synthetic wax of claim 13, comprising: at least one synthetic wax according to Formula IIA; and at least one synthetic wax according to Formula 11 B.

21. The synthetic wax of claim 7 or claim 13, wherein the synthetic wax is a reaction product between (i) a polyester diol and (ii) an anhydride comprising a saturated or unsaturated pendant hydrocarbon group having 4 to 30 carbon atoms.

22. The synthetic wax of claim 7 or claim 13, wherein: the synthetic wax has a melting temperature in a range of 30°C to 90°C; and / or the synthetic wax has a molecular weight in a range of 300-5000 g / mol.

23. The synthetic wax of claim 7 or claim 13, wherein: the synthetic wax has a melting temperature in a range of 30°C to 160°C; and / or the synthetic wax has a molecular weight in a range of 2000-20000 g / mol.

24. A high-melting synthetic wax comprising: a polymerization reaction product of a synthetic wax according to claim 7 in which at least one of A and C contains at least one unsaturated carbon-carbon double bond.

25. A high-melting synthetic wax comprising: a polymerization reaction product of a synthetic wax according to claim 13 in which R1contains at least one carbon-carbon double bond.

26. A high-melting synthetic wax comprising: a complex between a polyvalent metal cation and a synthetic wax according to claim 7 in which at least one of A and C contains at least one carboxylic group.

27. A high-melting synthetic wax comprising: a complex between a polyvalent metal cation and a synthetic wax according to claim 13 in which R1contains at least one carboxylic group.

28. A synthetic wax composition comprising: a synthetic wax according to claim 7 or claim 13; and one or more additives blended with the synthetic wax.

29. The synthetic wax composition of claim 28, wherein: the additives are present in an amount of 0.5 wt.% to 50 wt.% relative to the synthetic wax composition; and the additives are selected from the group consisting of inorganic fillers, organic additives, polymeric fillers, nanoparticles, natural waxes, ionizable polymers, non-ionizable hydrophilic polymers, and combinations thereof.

30. The synthetic wax composition of claim 29, wherein the inorganic filler is present and is selected from the group consisting of modified or unmodified titanium dioxide, modified or unmodified silica, modified or unmodified clay, calcium carbonate, aluminum oxide, zinc oxide, talc, mica, barium sulfate, iron oxides, and combinations thereof.

31. The synthetic wax composition of claim 29, wherein the organic additive is present and is selected from the group consisting of acrylics, polyurethane, epoxy, alkyds, functional polyesters, natural waxes, petroleum waxes, polyhydrocarbons, silicone, vinylic, vinylic-acrylics, polyamide, modified or unmodified carbohydrates, polyvinyl alcohol, polyethylene vinyl alcohols acrylic acid, polyethylene vinyl alcohol, proteins, lignin, polyethers, polyether-polyesters, amine / imine containing polymers, and combinations thereof.

32. A synthetic wax dispersion comprising: an aqueous medium; and a synthetic wax according to claim 7 or claim 13 dispersed in the aqueous medium.

33. The synthetic wax dispersion of claim 32, wherein the synthetic wax is in ammonium salt form.

34. A coated article comprising: a substrate; and a coating on the substrate, the coating comprising the synthetic wax of claim 7 orclaim 13, the high-melting synthetic wax of one of claims 24 to 27, or the synthetic wax composition of claim 28.

35. The coated article of claim 34, wherein: the substrate is a cellulosic substrate.

36. The coated article of claim 34, wherein: the coated article has a kit rating in a range of 1 to 12; the coated article has a cobb600 rating of 70 g / m2or less; and / or the coated article has a WVTR in a range of 0.0001 to 1000 g»mm / m2»24h at 37°C and 90% RH.

37. The coated article of claim 34, wherein the coating has at least one of properties(I), (II), and (III):(I) the coated article has a relative permeability for water vapor of 0.5 or less, relative to a corresponding substrate without the coating thereon;(II) the coated article has a water contact angle in a range of 70° to 150° for a 10 pl- deionized water droplet measured 30 sec after application of the droplet; and(III) the coated article has an oil contact angle in a range of 20° to 75° for a 10 plcastor oil droplet measured 30 sec after application of the droplet.

38. The coated article of claim 34, wherein the coated article is thermally sealable at a dwell time of 5 seconds or less and at a temperature of up to 200°C.

39. The coated article of claim 34, wherein the coated article is biodegradable.

40. The coated article of claim 34, wherein the coated article is repulpable and / or recyclable.

41. A method for degrading or emulsifying a synthetic wax, the method comprising: contacting the synthetic wax according to claim 7 or claim 13 with at least one of a carbonate salt, a bicarbonate salt, and an aqueous solution thereof at a temperature and for a time sufficient to degrade or emulsify the synthetic wax.

42. A method for sizing fiber-based materials, the method comprising performing one or both of (a) and (b):(a) mixing (i) a synthetic wax dispersion according to claim 32 with (ii) cellulosic fibers and (iii) optionally a sizing agent and / or a size retention aid to form sized cellulosic fibers, and then forming the sized cellulosic fibers into a two-dimensional cellulosic structure or athree-dimensional cellulosic structure; and(b) applying the synthetic wax dispersion as a surface treatment to a two-dimensional cellulosic structure or a three-dimensional cellulosic structure.

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