A biodegradable, repulpable, compostable and recyclable composition comprising a modified polyester for a barrier coating for packaging, articles including the barrier coating, and methods thereof

Abstract

A composition is described, which when applied to paper, cardboard or other cellulose based composites used in packaging, provides a layer that is oil resistant, moisture resistant and provides an effective oxygen barrier layer. The composition is comprised of a modified polyester polymer and may be applied as an aqueous emulsion or out of a solvent system. The coated substrate after being used is compostable, repulpable, recyclable and biodegradable.

Description

[0001] Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO A BIODEGRADABLE, REPULPABLE, COMPOSTABLE AND RECYCLABLE COMPOSITION COMPRISING A MODIFIED POLYESTER FOR A BARRIER COATING FOR PACKAGING, ARTICLES INCLUDING THE BARRIER COATING, AND METHODS THEREOF FIELD

[0001] The present invention relates to modified polyester polymers, coating compositions including a modified polyester polymer, and coating comprising the coating composition or the modified polyester polymer. The coating composition and / or coating may optionally contain other additives (i.e., addenda) used to enhance the coating uniformity, adhesion, chemical and mechanical resistance, and performance. The coating has a composition that can be appropriately tailored for having a rheology, dispersibility, and / or other properties such that it may be sprayed, brushed, dipped, roller coated, curtain coated, extrusion coated or coated with a wire rod of knife. The composition and coating realized from it is primarily intended for deposition onto to paper, cardboard and cellulosic based materials, but may be used on other substrates such as textiles and wood. BACKGROUND

[0002] The use of paper and cardboard has presented a challenge for years to improve various characteristics of performance for numerous applications. Whether for food, household products, personal care products, industrial, chemical and other uses there is a need to reduce or eliminate permeability. For example, there is also a need for better barrier properties (e.g., improved resistance to the transmission of oil, water, oxygen, or any combination thereof). At the same time environmental and sustainability concerns have also created new performance requirements with respect to repulpability, compostability and biodegradability. At the same time, there is also a need for materials having good mechanical and adhesion properties. The present technology has been able to achieve one or two of the desired properties (e.g., one or two of: transmission resistance, environmental / sustainability Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO performance (e.g., repulpability, compostability, biodegradability, or a combination thereof), but no coating composition exists that offers all the delineated desired attributes.

[0003] Various polymers and polymer compositions are taught as possible approaches for attempting to solve one of the above requirements, such as polylactide polymer compositions, polymers prepared with recycled polyethylene terephthalate, starch modified with an anhydride of a polyacid having pH below 4.5, aqueous dispersions of biopolymer blends including polycaprolactone and at least one additional biopolymer, lactide polymer coatings, coatings including polylactic acid, articles including multiple coating layers including a layer of a polylactic acid polymer, coating compositions including a polyvinyl alcohol polymer, copolymers of polylactic acid, polymers including residual lactic acid monomer, coatings including modified starch esters (e.g., C2-C8 esters), compositions including hydrogenated triglycerides and emulsion of hydrogenated triglyceride and styrene acrylic, compositions including biodegradable plastics, compositions including multiple synthetic polymers and phyllosilicate particles, compositions including a fatty acid modified polyethyleneterephthalate, coatings having an emulsion of an ethylene copolymer or polyvinyl alcohol and a volatile antimicrobial agent., barrier coatings including a prolamin and a polyol fatty acid ester, substrate treatments including a saccharide fatty acid esters (SFAE) and an inorganic particle, compositions including wax and polyvinyl alcohol, paper coating compositions including a polysaccharide, a solvent, and a base, a barrier coating comprising at least two polyol and / or saccharide fatty acid ester, a coating comprising a tackifier and a polymer selected from natural rubber, polyacrylate, polystyrene butadiene, polybutene, polyisobutene, and polyisoprene, a liner composition including a biopolymer and graphene nanoplatelets, an adhesive including a latex-base modifier copolymer, a modified Loctite, or a styrene ester copolymer, a composition including a reaction product of a biodegradable polyester and a siloxane, articles having multiple coatings layers that are different, and coating compositions requiring high temperatures for sealing. See for example United States (US) Patent Numbers 6,183,814, 5,475,080, 6,001,473, 6,007,614, 6,187,389, 6,066,368, 11,345,831, and 11,530,517; United States (US) Patent Application Numbers 2003 / 0127210, 2021 / 0155776, Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO 2024 / 0101816, 2014 / 0239052, 2016 / 0340833, 2024 / 0093023, 20070092718, 20150119505, 2020 / 0095731, 2020 / 0255676, 2023 / 0182980, and 2023 / 0220627; Australia (AU) Patent Application Number 200165455, 202 / 30357991; Canada (CA) Patent Application Numbers 2124845, 2428035, 2428320, and 2327478; New Zealand (NZ) Patent Number 501695; and International (WO) Patent Application Number 2022 / 226053, 2007 / 113121, 2013 / 101778, 2018 / 031388, and 2023 / 049120; each incorporated herein by reference in its entirety).

[0004] There are a myriad of problems and shortcomings in current products and present technologies as it relates barrier efficacy and the reuse of discarded product. Much of the prior art focuses on improving the strength of the paper, cardboard or cellulosic substrate by increasing the tensile strength and shear modulus. Other prior art centers on improving the resistance to oil, water, moisture, and oxygen transmission. Other prior art centers on environment, sustainability, composting, biodegradability, repulpability and recyclability. No prior art has been detected that describes a composition or method to solve more than one, or even all three of these issues in one composition or method, or with one polymer. It is the intention of the present invention to unite all performance features into one approach that satisfies requirements for at least two or more of (or all of) strength, resistance barrier and environmental concerns. SUMMARY

[0005] One aspect of the teachings herein is directed to a modified polyester comprising a polymerization product of: (i) an aliphatic polyol having a functionality of 2 or more; (ii) an aliphatic carboxylic acid having two or more carboxyl groups or an aliphatic anhydride having a functionality of two or more, and (iii) a modified aliphatic polyol, a modifiedaliphatic carboxylic acid having a functionality of two or more, and / or a modified aliphatic anhydride having a functionality of two or more, wherein the modified aliphatic polyol, the modified aliphatic carboxylic acid, or the modified aliphatic anhydride includes a pendant group. Preferably the aliphatic polyol, the aliphatic carboxylic acid, and the aliphatic anhydride are free of pendant groups including two or more, or three or more atoms having an atomic number of 6 or more. Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO

[0006] Another aspect of the teachings herein is directed to a modified polyester comprising (i) repeat units having the structure: -( C(O)O – R1– C(O)O – R2-), where R1and R2are linear alkyl groups; and (ii) repeat units having the structure: -( C(O)O – R1– C(O)O – R3(R4)-) or -( C(O)O – R2– C(O)O – R3R4-); where R1, R2, and R3are linear alkyl groups, and R4is a pendant group attached to R3; optionally, wherein the modified polyester is formed from an aliphatic polyol including R1, an aliphatic carboxylic acid or an aliphatic anhydride include R2, and a modified aliphatic polyol or a modified aliphatic carboxylic acid or a modified aliphatic anhydride including R3R4; optionally wherein R3is the same as R1or R2.

[0007] Another aspect of the teachings herein is directed at a polymeric composition (e.g., a coating composition) including a modified polyester. The polymeric composition may be a solution (e.g., including a solvent), an emulsion (e.g., including an aqueous phase), or may be substantially or entirely free of solvent and / or water.

[0008] Another aspect of the teachings herein is directed at packaging including a substrate coated with a layer of material including, consisting essentially of, or consisting entirely the modified polyester. For example, the packaging material may include the polymeric composition coated on a substrate, or the product of such composition after heating and / or drying.

[0009] Another aspect of the teachings herein is directed at a method of preparing a modified polyester.

[0010] Another aspect of the teachings herein is directed at a method of coating a substrate with a material or polymeric composition comprising a modified polyester.

[0011] Preferably the modified polyester, the polymeric composition, the coating composition, or the coating layer provide a combination of two or all of barrier properties, mechanical properties, and environmental properties. DETAILED DESCRIPTION

[0012] As discussed, the prior art is replete with examples teaching the use of polyhydroxyalkanoates, polylactic acid, starch, esters of starch, polyvinyl alcohol, hydrogenated triglycerides, saccharide fatty acid esters, polystyrene acrylates, sulfopolyester, Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO polybutylene succinate, polybutylene succinate adipate, and iterations thereof in addition to other common polymers. Although some have one or more of the desired features, none can adequately resolve all the issues of strength, environment, and barrier protection.

[0013] A very specific family of polyester polymers has been found to meet at least two if not all required features. The polyester polymers of the present teachings may be applied to a substrate (alone or in a composition formulated with other ingredients) to form a layer possessing the previously stated attributes (e.g., strength, environment, and barrier protection). The polyester polymers of the present teachings may be used in a polymeric composition including one or more addenda to form a layer possessing the previously stated attributes. The polymeric composition preferably is a coating composition. For example, the polymeric composition may be an aqueous emulsion or a solvent system for coating a substrate. Depending on the substrate to be coated and / or requirements of a packaging, other additives may be advantageously employed. For example, the polymeric composition may include a surfactant or other additive for reducing surface tension, better leveling, improving flow (such as for smooth compatibility), or any combination thereof. The surfactant may be an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant. Nonionic surfactants are preferred. Nonionic surfactants with an HLB (i.e., hydrophilic- lipophilic balance) of between 7 and 14 are more preferred. Nonionic surfactants with an HLB of between 10 and 12 are most preferred.

[0014] Additionally, other addenda (e.g., additives) may be added to improve the performance of the composition and / or to reduce the cost of the composition. Examples of addenda that may be used in the composition include organic fillers, inorganic fillers, stabilizers, process aids. A particularly preferred addenda is starch. The starch may be a natural starch or a modified starch. The starch may be hydrolyzed chemically or enzymatically to change one or more of its characteristics. Both natural and modified starch have been found to improve one or more properties of the coating composition, such as heat sealing, tensile strength, shear strength. Typically, the starch does not increase costs and often results in reduced cost of the Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO composition. Another addenda that may be employed in the composition is a polyol, particularly for improving heat sealing and other characteristics.

[0015] The preferred polyester is prepared using an aliphatic diol, an aliphatic dioic acid or anhydride and an aliphatic diol or dioic acid or anhydride that is modified with a pendant group. The pendant group may include or consist essentially of an alkane or alkene. The most preferred pendant group is an alkene. Preferred aliphatic diols have 3 or more carbon atoms and more preferably 4 or more carbon atoms. Preferred aliphatic diols have 40 or less carbon atoms, more preferably 30 or less carbon atoms, even more preferably 10 or less carbon atoms, and most preferably 8 or less carbon atoms. Examples of useful diols are ethylene glycol, propylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol and so on to dodecane diol, caprolactone diol, polyethylene glycol, and neopentyl glycol.

[0016] In various aspects, vicinal diols are preferred over geminal diols.

[0017] More preferred diols have at least one of the hydroxyl groups on the first or last carbon in the alkyl chain. Most preferred diols have hydroxyl groups is on the first and last carbon in the alkyl chain.

[0018] It will be appreciated that some or all of the diols may be replaced by a polyol having three, four, or more hydroxyl groups. If present the amount of polyol having a functionality greater than two preferably is about 75 weight percent or less, about 25 weight percent or less, about 10 weight percent or less, about 3 weight percent or less, about 1 weight percent or less, or about 0.5 weight percent or less, based on the total weight of the polyols (including diols). The amount of polyol having a functionality greater than two may be about 0 weight percent or more, about 0.2 weight percent or more, or about 0.4 weight percent or more.

[0019] Examples of useful dioic acid or anhydrides include but are not limited to oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, itaconic acid, pimelic acid, suberic acid, and so on up to dodecanedioic acid. Each of the specified dioic acids may be used as an anhydride. Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO

[0020] The number of atoms in the pendant group having an atomic number of 6 or more preferably is about 2 or more, about 4 or more, about 6 or more, about 8 or more, or about 10 or more. The pendant groups may include one or more unsaturated groups or may be entirely saturated. The pendant group may be a functional pendant group. The pendant group (e.g., the functional pendant group) may be attached to either the polyol (e.g., the diol), the dioic acid, the anhydride, or any combination thereof. The pendant groups may include a mono-, di-, or tri- alkene. The unsaturated groups are advantageously added to increase molecular weight, improve the self-alignment of a coating that is dried, increase abrasion resistance, to increase scratch resistance, to increase chemical resistance, to increase molecular weight, or any combination thereof. Without being bound by theory, the improvements in self-alignment is believed to be due to the angularity introduced. Examples of useful pendant alkenes include but are not limited to 2-butene adipic anhydride, and 4-hexene succinic anhydride. The pendant group may reduce the crystallinity of the polyester and / or reduce the melting temperature of the polyester. The pendant group may be used for reacting the modified polyester with itself, with another component of the coating composition, to a substrate, or to a component on a surface of the substrate.

[0021] By achieving the desired performance properties (e.g., with a single polymer), it may be possible to apply a single coating or a coating including a single polymer to achieve the desired strength, environment, and barrier protection properties.

[0022] The thickness of the coating layer may be characterized by the coating weight (in units of g / m²). Preferably the coating weight of the layer including (or consisting substantially of, or consisting entirely of) the modified polyester is about 1 g / m² or more, about 3 g / m² or more, about 5 g / m² or more, about 8 g / m² or more, about 12 g / m² or more, or about 20 g / m² or more. Preferably the coating weight of the layer is about 100 g / m² or less, about 75 g / m² or less, about 50 g / m² or less, about 35 g / m² or less, or about 25 g / m² or less.

[0023] The modified polyester and / or composition including the modified polyester may be deposited as one or more layers on a substrate. It will be appreciated that one or more additional functional layers may also be deposited. For example, an article including a layer Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO comprising the modified polyester may include a functional layer that is interposed between a substrate and the modified polyester, or where the modified polyester is interposed between the functional layer and the substrate. The functional layer may be printed or printable (such as a photo-activated or thermal activated printable layer that undergoes a color transformation upon application of energy).

[0024] The total mole percentage of the modified aliphatic polyol (if any), the modified aliphatic carboxylic acid (if any) and the modified aliphatic anhydride (if any) in the polyester polymer may be about 3 % or more, about 5% or more, about 7% or more, about 10% or more, about 20% or more, or about 29% or more. The total mole percentage of the modified aliphatic polyol (if any), the modified aliphatic carboxylic acid (if any) and the modified aliphatic anhydride (if any) in the polyester polymer may be about to 50 % or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, or about 20% or less.

[0025] The modified polyester preferably is characterized by a tensile strength of 0.5 Pa or more, more preferably about 1 Pa or more, even more preferably about 2 Pa or more, even more preferably about 4 Pa or more, and most preferably about 7 Pa or more. The tensile strength may be 100 Pa or less, although higher values are also possible. The modified polyester preferably is characterized by a shear strength (adhesion) of about 0.5 Pa or more, about 1.0 Pa or more, about 1.5 Pa or more, about 5 Pa or more, about 10 Pa or more, or about 20 Pa or more. The shear strength (adhesion) of the modified polyester may be about 100 Pa or less, although higher values are also possible. The modified polyester preferably is characterized by a KIT value of about 6 or more, more preferably about 8 or more, even more preferably about 10 or more, and most preferably about 12 or more, as measured according to ASTM TAPPI Test Method T559. The modified polyester is preferably characterized by a COBB 180 value measured on untreated and uncoated 15-lb brown kraft paper (water absorption test) of about 20 g / m² or less, preferably about 8 g / m² or less, more preferably about 3 g / m² or less and most preferably about 2 g / m² or less.

[0026] The modified polyester may provide good barrier properties. For example, the modified polyester may have improved resistance to the transmission of oil, water, oxygen, or any Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO combination thereof. Preferably the modified polyester is characterized by a water vapor transmission rate (WVTR) of about 100 g / m2 / day or less, more preferably about 20 g / m2 / day or less, and most preferably about 8 g / m2 / day or less. The modified polyester preferably is characterized by an oxygen transmission rate (OTR) of about 150 cc / m2 / 24 hours or less, more preferably about 45 (cc / m2) / 24 hours or less and most preferably about 15 (cc / m2) / 24 hours or less.

[0027] The modified polyester preferably is characterized by a weight average or number average molecular weight of about 3,000 g / mole or more, about 5,000 g / mole or more, or about 7,000 g / mole or more. The molecular weight preferably is measured by gel permeation chromatography.

[0028] The pendant groups on the modified polyester are preferably present in a concentration of about 0.01% or more, about 0.03% or more, about 0.1% or more, about 0.3% or more, about 1.0% or more, or about 3.0% or more, wherein the concentration is the ratio of the number of pendant groups attached to a backbone of the modified polyester to the number of carbon atoms in the modified polyester. The concentration of the pendant groups preferably is about 10% or less, about 8% or less, about 6% or less, about 4% or less, or about 3.2% or less.

[0029] For some applications, it is preferred that the modified polyester is substantially free of or entirely free of long chain branching. As used herein, long chain branching refers to a branch having a total of 100 or more carbon and / or oxygen atoms. The amount of long chain branching preferably is about 5 or less, about 4 or less, about 3 or less, about 2 or less, about 1 or less, or zero long chain branches.

[0030] The aliphatic polyol having a functionality of two or more, preferably includes, consists substantially of, or consists entirely of one or more aliphatic diols. If present, the aliphatic carboxylic acid having two or more carboxyl groups preferably includes, consists substantially of, or consists entirely of one or more aliphatic dioic acids. If present, the aliphatic anhydride having a functionality or two or more preferably includes, consists substantially of, or consists entirely of one or more aliphatic anhydrides having a functionality of 2. If present, the modified Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO aliphatic polyol preferably includes, consists substantially of, or consists entirely of one or more aliphatic diols. If present, the modified aliphatic carboxylic acid preferably includes, consists substantially of, or consists entirely of one or more modified aliphatic dioic acids. If present, the modified aliphatic anhydride preferably includes, consists substantially of, or consists entirely of one or more modified aliphatic anhydrides having a functionality of 2.

[0031] The total concentration of the aliphatic polyol having functionality of two or more, the aliphatic anhydride, and the aliphatic carboxylic acid having two or more carboxyl groups preferably is about 60 weight percent or more, more preferably about 80 weight percent or more, even more preferably about 85 weight percent or more, and most preferably about 90 weight percent or more, based on the total weight of the modified polyester. The total concentration of the aliphatic polyol having functionality of two or more, the aliphatic anhydride, and the aliphatic carboxylic acid having two or more carboxyl groups may be about 100 wt% or less, or about 97 weight percent or less, or about 94 weight percent or less, or about 91 weight percent or less.

[0032] It has been found that it may be possible to improve and or tailor properties of the modified polyester, such as shown in the examples, by using additional monomers. For example, the modified polyester may include two or more different aliphatic polyols (optionally diols), two or more different aliphatic carboxylic acids having two or more carboxyl groups (optionally dioic acids), two or more aliphatic anhydrides having a functionality of tow or more (optionally having a functionality of two), two or more different modified aliphatic polyols, two or more different modified aliphatic carboxylic acids, or any combination thereof. The modified polyester may include both an aliphatic carboxylic acid (having a functionality of two or more) and an aliphatic anhydride (having a functionality of two or more). The modified polyester may also include one or more additional monomers that are not aliphatic. For example, the modified polyester may include one or more non-aliphatic diols, one or more non-aliphatic dioic acids, a monomeric ester, a fumarate, a malonate, an aziridine, an epoxidized soyabean oil, or a polycaprolactone. If present, the total amount of any non-aliphatic components (e.g., monomers or oligomers) may be about 45 weight percent or less, about 30 weight percent or Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO less, about 20 weight percent or less, about 10 weight percent or less, about 5 weight percent or less, or about 2 weight percent or less. It has been found that properties of the modified polyester may be improved or modified by end capping one or more of the ends of the polymer. For example, one or more (e.g., all) ends of the modified polyester may be capped by reacting with an aliphatic monoacid. Preferred aliphatic acids are monoacids having 2 to 50 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 3 to 14 carbon atoms.

[0033] The concentrations of the monomers (having functionality of two or more) in the modified polyester may be chosen to approach or achieve stoichiometry of the reactive groups. Preferably the amount of the hydroxyl groups (No), the amount of the carboxyl groups (Nc) and the amount of the anhydride groups (Na) is selected so that No= (Nc+ 2Na) + / - 5%. The molar ratio of the hydroxyl groups to the total of the carboxyl groups and twice the anhydride groups for the multifunctional monomers preferably is about 0.95 or more, more preferably about 0.97 or more, even more preferably about 0.98 or more, and most preferably about 0.99 or more. The molar ratio of hydroxyl groups to the total of the carboxyl groups and twice the anhydride groups for the multifunctional monomers preferably is about 1.05 or less, more preferably about 1.03 or less, even more preferably about 1.02 or less, and most preferably about 1.01 or less.

[0034] The modified polyester preferably has a majority of aliphatic groups. The concentration of the aliphatic groups in the modified polyester preferably is about 60 weight percent or more, more preferably about 70 weight percent or more, and most preferably about 80 weight percent or more, based on the total weight of the modified polyester. Preferably, 60 weight percent or more of the backbone of the modified polyester is aliphatic, more preferably 70 weight percent or more of the backbone of the modified polyester is aliphatic, and most preferably 80 weight percent or more of the backbone of the modified polyester is aliphatic. Preferably, 60 weight percent or more of the pendant group of the modified polyester is aliphatic, more preferably 70 weight percent or more of the pendant group of the modified polyester is aliphatic, and most preferably 80 weight percent or more of the pendant group of the modified polyester is aliphatic. Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO

[0035] The concentration of ester groups, -C(O)O-, in the modified polyester preferably is about 3 weight percent or more, about 5 weight percent or more, or about 7 weight percent or more. The concentration of ester groups, -C(O)O-, in the modified polyester preferably is about 30 weight percent or less, about 25 weight percent or less, about 20 weight percent or less, or about 15 weight percent or less.

[0036] Test Methods

[0037] Unless otherwise specified, all testing is performed at or about room temperature (e.g., about 20 °C) and / or at or about standard pressure (e.g., about 1 atmosphere).

[0038] COBB TESTING

[0039] The ability of a hygroscopic material to resist the penetration of water may be measured with Cobb test. Specifically, this test permits the determination of the quantity of water that can be absorbed by the surface of paper or board in a given time. Water absorption is a function of various paper and board characteristics such as sizing, porosity, etc. The Cobb test determines the amount of water absorbed into the surface by a sized (non-bibulous) paper, paperboard, and corrugated fiberboard paper or paperboard sample in a set period, usually 60 or 180 seconds (Cobb60 or Cobb180). Unless otherwise specified, the Cobb test was at 180 seconds on a standard 15-pound brown kraft paper. Water absorbency is quoted in g / m². A standard volume of water is dropped onto the paper surface and the amount of water absorbed after 180 seconds is measured. The water absorbency rate is used as a measure of the acceptability of tissue, toweling and blotter papers in absorptive tasks.

[0040] Preferred the modified polyester and / or the coating composition has a water absorbancy of about 15.9 g / cm² or less, more preferably about 10 g / cm² or less, even more preferably about 5 g / cm² or less, even more preferably about 3 g / cm² or less, and most preferably about 2 g / cm² or less, as measured by Cobb180 on brown kraft paper substrate having a coating weight of 15 pounds.

[0041] KIT TESTING

[0042] The KIT method describes a procedure for testing the degree of repellency and / or the anti-wicking characteristics of paper or paperboard treated with fluorochemical sizing Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO agents. The test is run according to TAPPI Test Method T559. Fluorochemical agents may impart both oleophobic and hydrophobic characteristics to paper through a reduction in the surface energy of the sheet. This is often done by a surface treatment of the fibers without the formation of continuous films. Testing involves placing a series of numbered reagents (varying in surface tension and viscosity or “aggressiveness”) onto the surface of the sample. The solutions are numbered from 1 (the least aggressive) to 12 (the most aggressive). The highest numbered solution that does not stain the surface is reported as the “kit rating.”

[0043] SHEAR TESTING: A shear test is a strength test conducted on test samples to identify their reaction to shear stress, modulus, and strain. Shear testing shows how well parts will glue together after adhesive use. The purpose of this test is to compare the performance of an adhesive in a joint and to determine its mechanical response. The shear test measures the force required to pull a defined area from the test panels when the substrates on the test panels are being pulled at a constant rate. Shear strength is the internal or cohesive strength of the adhesive mass. The strength is measured in Pascals (Pa). Unless otherwise specified, the shear testing is measured according to TAPPI T837, with a joint width of 1 cm x 2 cm, on substrates of a standard 15 pound brown kraft paper. The figure below shows a test sample with the composition between the substrate, where the substrate provides tabs for pulling the sample in a shear

[0044] TENSILE TESTING: Tensile testing is a destructive test process that provides information about the tensile strength, yield strength, and ductility of the substrate material. It measures the force required to break a test sample and the extent to which the sample stretches or elongates to that breaking point. Tensile testing of composites is generally in the form of basic tension or flat-sandwich tension testing. The strength is measured in Pascals (Pa).

[0045] COMPOSTABILITY: Compostability is the evaluation of the ability of materials to break down into natural elements in a composting environment. The purpose and importance are 1) Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO compostable materials can be diverted from landfills, contributing to environmental sustainability, 2) consumers are increasingly aware of environmental impacts, and companies can gain market share by addressing these concerns, 3) regulatory changes, such as bans on single-use food packaging in some communities, drive demand for biodegradable packaging. The Testing Protocol has three stages: 1) Disintegration: Measures how well the material breaks down in a stable environment, 2) Plant Seed Germination: Assesses the impact of the material on seed germination, and 3) Biodegradability: Determines the extent to which the material biodegrades.

[0046] BIODEGRADABILITY: Biodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. It is generally assumed to be a natural process, which differentiates it from composting. Composting is a human-driven process in which biodegradation occurs under a specific set of circumstances.

[0047] The process of biodegradation is threefold: first an object undergoes biodeterioration, which is the mechanical weakening of its structure; then follows bio-fragmentation, which is the breakdown of materials by microorganisms; and assimilation. In practice, almost all chemical compounds and materials are subject to biodegradation, the key element being time. Things like vegetables may degrade within days, while glass and some plastics take many millennia to decompose. A standard for biodegradability is that greater than 90% of the original material must be converted into CO2, water and minerals by biological processes within 6 months.

[0048] EXAMPLES

[0049] Comparative Example 1.

[0050] Polyester A is DAN-04071 is a commercially available polymer from DANIMER SCIENTIFIC (Brainbridge, Georgia) sold as DAN-04071. This polyester is a polyhydroxy alkanoate (aka PHA). DAN-04071 is a linear polyester and is free of pendant groups. Comparative example 1 is prepared from Polyester A as a coating material without any addenda being added. Comparative Example 1 has a coating weight of 25 g / m². Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO

[0051] POLYESTER B is a POLY(BUTYL SUCCINATE) polyester polymer of succinic acid and 1,4-butane diol commercially available from UNILONG INDUSTRY CO. LTD. (Jinan City, Shandong Province, China). This polyester is a linear polyester and is free of pendant groups. Comparative Examples 2, 3, and 4 are prepared from POLYESTER B as a coating material without any addenda being added. Comparative Examples 2, 3, and 4 have coating weights of 37 g / m², 54 g / m², and 69 g / m², respectively.

[0052] Example 5 is a modified polyester having pendant groups. Example 5 is a copolymer where 1,4-butanediol and succinic acid are polymerized with (2-dodecen-1-yl) succinic anhydride to form a copolymer including two types of repeating groups: A) 1,4-butanediol + succinic acid, and B) 1,4-butanediol + (2-dodecen-1-yl) succinic anhydride. The copolymer is prepared by adding 27.46 g of 1,4-butanediol, 19.60 g of succinic acid, and 29.57 g of (2- dodecen-1-yl) succinic anhydride into a 500 ml 3-neck round-bottom flask to form a reaction mixture. A glass gas inlet is connected to a first neck of the flask, the middle neck is used for an overhead stirrer that stirs the reaction mixture, and the other neck is connected to a collecting flask.71 mg of titanium (IV) isopropoxide catalyst is added to the round bottom flask before the reaction is started. The round-bottom flask is heated to 120°C in an oil bath. The overhead stirrer is turned on to 230 RPM while nitrogen is flushed through the round bottom flask to a condenser and the collecting flask. The reaction is carried out isothermally for 6 hours. The nitrogen is turned off and the oil bath is gradually heated to 160°C. An additional 79 mg of titanium (IV) isopropoxide is added. The reaction continues under vacuum until the polymer becomes a highly viscous material and the overhead stirrer stops. The polymer is then isolated.

[0053] Example 6 is a modified polyester having pendant groups. Example 6 is a copolymer prepared using the same method as Example 5, except the amounts of the 1,4 butane diol, the (2-dodecen-1-yl) succinic anhydride, and the titanium catalyst are increased. In preparing example 6, 19.60 g of succinic acid, 29.96 g of butanediol, 29.97 g of (2-dodecen-1-yl) succinic anhydride are added to the round bottom flask and 167 mg of the titanium catalyst. The times, Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO temperatures and conditions are the same as Example 5, except all of the catalyst is added in the earlier step.

[0054] Example 7 is a modified polyester having pendant groups. Example 7 is a copolymer prepared using the same method as Example 5, except the amounts of the 1,4-butanediol and succinic acid, and catalyst are increased, the 2-dodecen-1-yl) succinic anhydride is eliminated and diethyl fumarate and dihydro-3-(tetrapropenyl) furan 2,5-dione are added. The amount of each monomer is: 37.60 g of 1,4-butanediol, 33.29 g of succinic acid, 20.01 g of dihydro-3- (tetrapropenyl) furan 2,5-dione, and 3.23 g of diethyl fumarate. The times, temperatures and conditions are the same as Example 5, except all of the catalyst is added in the earlier step.

[0055] Example 8 is a modified polyester having pendant groups. Example 8 is a copolymer prepared using the same method as Example 5, except the monomers and amount of catalyst are changed and BHT is added. Example 8 is prepared using 120.00 g of succinic acid, 126.43 g of butanediol, 40.604 g of (2-dodecen-1-yl) succinic anhydride, 8.74 g of diethyl fumarate, 0.30 g of BHT, 0.60 g of titanium catalyst. The times, temperatures and conditions are the same.

[0056] Example 9 is a modified polyester having pendant groups. Example 9 is a copolymer prepared using the same method as Example 5, except the monomers and amount of catalyst are changed and BHT is added. Example 9 is prepared using 33.29 g of succinic acid, 37.60 g butanediol, 20.01 g (2-dodecen-1-yl) succinic anhydride, 3.23 g diethyl fumarate, 0.10 g of BHT, 0.20 g of titanium (IV) isopropoxide catalyst. The times, temperatures and conditions are the same, except all of the catalyst is added in the earlier step.

[0057] Example 10 is a polyester having pendant groups. Example 10 is a polymer prepared using the same method as Example 5, except the monomers are succinic acid, alkylsuccinic acid, 1,4-butane diol, and diethyl fumarate, and a different amount of the titanium (IV) isopropoxide catalyst is used. The times, temperatures and conditions are the same, except all of the catalyst is added in the earlier step.

[0058] Example 11 is a modified polyester having pendant groups. Example 11 is a copolymer prepared using the same method as Example 5, except the monomers and amount of catalyst Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO are changed and BHT is added. Example 11 is prepared using 40.01 g of adipic acid, 45.01 g of hexanediol, 14.59 g of (2-dodecen-1-yl) succinic anhydride, 0.24 g of titanium (IV) isopropoxide catalyst and 0.10 g of BHT. The times, temperatures and conditions are the same, except all of the catalyst is added in the earlier step.

[0059] Example 12 is a polyester without pendant groups. Example 12 is a polymer prepared using the same method as Example 5, except the monomers and amount of catalyst are changed. Example 12 is prepared using 40.00 g of oxalic acid, 56.85 g of ethylene glycol, and 0.21 g of titanium (IV) isopropoxide catalyst. The times, temperatures and conditions are the same, except all of the catalyst is added in the earlier step. TABLE 1 Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Polyester A 100 Polyester B 100 100 100 Coating structure Coating Weight, g / m² 25 37 54 69 Substrate (paper) 15-lb brown 15-lb brown 15-lb brown 15-lb brown Kraft Kraft Kraft Kraft Test results Does polymer have no no no no pendant groups? COBB 180 (g / m²) <3 145 53 16 KIT (rating) 3-5 3 6 11 Tensile (Pa) Not Tested Not Tested Not Tested Not Tested Cure Temperature (°C) 120 + 120 + 120 + 120 +

[0060] Example 13 is a modified polyester having pendant groups. Example 13 is a copolymer prepared using the same method as Example 5, except the monomers and amount of catalyst are changed and BHT is added. Example 13 is prepared using 50.01 g of oxalic acid, 93.80 g of ethylene glycol, 29.61 g of (2-dodecen-1-yl) succinic anhydride, 0.35 g of titanium (IV) isopropoxide catalyst, and 0.01 g of BHT. The times, temperatures and conditions are the same, except all of the catalyst is added in the earlier step.

[0061] Example 14 is a modified polyester having pendant groups. Example 14 is a copolymer prepared using the same method as Example 5, except the monomers and amount of catalyst are changed and BHT is added. Example 14 is prepared using 49.99 g of oxalic acid, 72.33 g of 1,4-butanediol, 29.60 g of (2-dodecen-1-yl) succinic anhydride, 0.23 g of titanium (IV) Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO isopropoxide catalyst, and 0.01 g of BHT. The times, temperatures and conditions are the same, except all of the catalyst is added in the earlier step.

[0062] Example 15 is prepared by first preparing a polyester having pendant groups. The polyester is prepared by reacting alkyl ketene dimer and glycerol (1:1 mole ratio) in a one- neck round bottom flask at 110oC for 4 hours. The product is an emulsion including a polyester having pendant groups and is cooled down to room temperature. The polyester is then used to prepare a coating solution by adding additives. The first additive is a starch solution. The starch solution is prepared as follows: starch (10 weight percent) is added to deionized water (90 weight percent) and stirred at room temperature, and then heated to 80oC and maintained at this temp for 30 minutes. The emulsion of alkyl ketene dimer and modified glycerol is added in an amount of 10 percent of the weight of the starch. The blend is stirred at 80oC for 60 minutes.

[0063] Polyester / starch product is made using the solution of polyester which is added and vigorously stirred at 70oC for 30 minutes. The mixture is diluted with DI water to reduce the viscosity.

[0064] In preparing the coating composition of Example 15, 8.0 grams of corn starch is mixed with: 0.8 grams of the polyester, 3 grams of sorbitol, 4.5 grams of glycerin, 0.5 grams of calcium carbonate and 83.2 grams of water.

[0065] In preparing test specimens of the examples and competitive examples, a standard 15-pound brown kraft paper which is uncoated and otherwise untreated is used. A sheet of the paper (10 inches x 16 inches) is placed on a flat glass surface. A small amount of coating is placed in front of the rod. Using uniform pressure, the rod is drawn down over the surface of the pater. The coating is uniformaly coated on the paper. TABLE 2 Example Example Example Example Example Example 5 6 7 8 9 10 Monomers (g) 1,4-butanediol 27.46 29.96 37.60 126.43 37.60 45.05 1,6-hexanediol succinic acid 19.60 19.60 33.29 120.00 33.29 40.00 adipic acid Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO (2-dodecen-1-yl) 29.57 29.97 40.604 20.01 succinic anhydride dihydro-3- 20.01 (tetrapropenyl) furan 2,5-dione diethyl fumarate 8.74 3.23 3.75 alkylsuccinic anhydride 14.62 Catalyst (mg) titanium (IV) 150 167 167 600 200 yes isopropoxide Other Addenda (g) BHT 0.60 0.10 Coating structure Coating Weight, g / m² 25 15 22 12.2 16.6 16.6 Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb brown brown brown brown brown brown Kraft Kraft Kraft Kraft Kraft Kraft Test results Does polymer have yes yes yes yes yes yes pendant groups? COBB 180 (g / m²) <2 <2 <2 <2 1.3 1.4 KIT (rating) 12 12 12 12 8 8 Tensile (Pa) 11 14 2 5.9 Not Not tested tested Cure Temperature (°C) 25 25 25 25 25 25 TABLE 3 Example Example Example Example Example 11 12 13 14 15 Monomers (g) 1,4-butanediol 72.33 1,6-hexanediol 45.01 ethylene glycol 56.85 93.80 succinic acid adipic acid 40.01 oxalic acid 40.00 50.01 49.99 (2-dodecen-1-yl) succinic 14.59 29.61 29.60 anhydride alkyl ketene dimer / glycerol 0.80 polyester (1:1) Catalyst (mg) titanium (IV) isopropoxide 240 210 350 230 Other Addenda (g) BHT 0.10 0.01 0.01 Corn starch 8.0 Sorbitol 3 Glycerin 4.5 Calcium carbonate 0.5 Water 83.2 Coating structure Coating Weight, g / m² 35 47 35 30 36 Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb brown brown brown brown brown Kraft Kraft Kraft Kraft Kraft Test results Does polymer have yes no yes yes yes pendant groups? COBB 180 (g / m²) 15.7 <2 2 7 2.5 KIT (rating) 12 12 12 10 12 Tensile (Pa) 3.1 1.2 Not Not tested 4.1 Tested Cure Temperature (°C) 25 120 25 25 25

[0066] The monomers, catalyst and addenda used in Examples 16-22 are shown in Table 4. The times, temperatures and conditions are the same as in example 5 with the following exception(s): in Example 16-22, all of the catalyst is added in the earlier step.

[0067] The monomers, catalyst and addenda used in Examples 23-29 are shown in Table 5. The times, temperatures and conditions are the same as in example 5 with the following exception(s): in Example 23-29, all of the catalyst is added in the earlier step, and in Examples 24-26, stearic acid is added for end capping.

[0068] The monomers, catalyst and addenda used in Examples 30-36 are shown in Table 6. The times, temperatures and conditions are the same as in example 5 with the following exception(s): in Example 30-36, all of the catalyst is added in the earlier step, and in Example 36, stearic acid is added for end capping. TABLE 4 Example Example Example Example Example Example Example 16 17 18 19 20 21 22 Mononmers (g) 1,4-butanediol 72.33 69.19 107.99 103.72 103.71 1,6-Hexanediol 45 Ethylene glycol 93.8 Succinic acid 58.97 15.08 47.23 Itaconic Acid 13.01 13.02 Adipic acid 40 29.20 Oxalic acid 50.01 49.99 50 13.50 18.04 27.03 (2-dodecen—1-yl) 14.58 29.61 29.6 39.93 53.28 53.27 succinic anhydride Catalyst and Other Addenda Titanium 200 330 123 240 500 500 500 (IV)isopropoxide (mg) Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO BHT (mg) 100 100 10 20 Coating Structure Coating weight, (g / m2) 11.1 35 33 35.3 20 35 Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb brown brown brown brown brown brown brown Kraft Kraft Kraft Kraft Kraft Kraft Kraft Test results Does polymer have yes yes yes yes yes yes yes pendant groups? Cobb 180 (g / m2) 5.9 34.8 31 5 KIT (ratting) 12 8 8 3 8 Tensile (Pa) 5.9 6.3 Sheer (Pa) 92 Cure Temperature (^C) 25 25 25 25 25 25 25

[0069] The monomers, catalyst and addenda used in Examples 37-41 are shown in Table 7. The times, temperatures and conditions are the same as in example 5 with the following exception(s): in Example 37-41, all of the catalyst is added in the earlier step, and in Example 37, stearic acid and calcium stearate are added for end capping. TABLE 5 Mononmers (g) Example Example Example Example Example Example Example 23 24 25 26 27 28 29 1,4-butanediol 103.64 100.61 100.59 101.57 51.89 75.52 103.16 Succinic acid 23.68 14.63 45.81 23.14 29.57 59.06 29.58 Itaconic Acid 13.02 12.62 12.63 12.75 13.05 Adipic acid 14.62 Oxalic acid 45.03 17.50 26.22 44.13 9.03 Stearic acid 4.04 4.04 4.04 Aziridine 2.02 2.02 2.38 Dimethyl Malonate 19.87 39.65 13.3 polycaprolactones 14.02 Glycolic acid 7.67 (2-dodecen—1-yl) 53.30 51.68 51.67 52.23 26.72 53.3 64.68 succinic anhydride Catalyst and Other Addenda Titanium (IV) 200 500 500 500 600 600 300 isopropoxide (mg) BHT (mg) 100 100 20 20 20 20 Coating Structure Coating weight, 11.1 35 (g / m2) Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb brown brown brown brown brown brown brown Kraft Kraft Kraft Kraft Kraft Kraft Kraft Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO Test results Does polymer have yes yes yes yes yes yes yes pendant groups? Cobb 180 (g / m2) 5.4 KIT (ratting) Tensile (Pa) 5.9 5.4 Cure Temperature 25 25 25 25 25 25 25 (^C) TABLE 6 Example Example Example Example Example Example Example 30 31 32 33 34 35 36 Mononmers (g) 1,4-butanediol 67.81 99.56 51.05 51.08 51.03 76.77 104.42 Ethylene glycol 93.8 Succinic acid 45.34 22.46 22.29 22.28 59.05 59.09 Oxalic acid 49 25.95 11.35 11.1 16.9 Stearic Acid 7.32 Itaconic acid 12.5 8.11 8.1 1.96 Aziridine 2.44 polycaprolactones 20.13 20.19 20.29 Stearic acid 5.87 Poly(ethyleneoxide) 1.96 MW-4,000,000 (2-dodecen—1-yl) 51.14 33.05 33.05 33.14 53.32 79.96 succinic anhydride Diethyl malonate 59.70 10.93 Catalyst and Other Addenda Titanium (IV) 235 500 500 500 500 500 500 isopropoxide (mg) BHT (mg) 10 100 Coating Structure Coating weight, (g / m2) Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb brown brown brown brown brown brown brown Kraft Kraft Kraft Kraft Kraft Kraft Kraft Test results Does polymer have yes yes yes yes yes yes yes pendant groups? Tensile (Pa) 5.9 Cure Temperature 25 25 25 25 25 25 25 (^C) Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO TABLE 7 Mononmers (g) Example Example Example Example Example 37 38 39 40 41 1,4-butanediol 104.42 51.53 54.01 54.1 Succinic acid 59.04 22.44 29.52 29.53 23.6 Adipic acid 21.47 21.92 21.92 Oxalic acid 11.29 Itaconic acid 8.21 Polycaprolactones 3.92 20.15 Dihydro-2- 26.64 40.03 (tetrapropenyl)furan-2,5- dione Diethylmalonate 10.93 Calcium Stearate 1.96 Stearic acid 5.87 (2-dodecen—1-yl) 79.96 35.50 26.60 succinic anhydride Catalyst (mg) and Other Addenda Titanium 500 500 250 500 500 (IV)isopropoxide (mg) BHT (mg) 100 10 20 20 Coating Structure Coating weight, (g / m2) 19.1 25 35 21.5 Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb Brown Brown Brown Brown Brown kraft kraft kraft kraft kraft Test results Does polymer have yes yes yes yes yes pendant groups? Cobb 180 (g / m2) 6 2.2 56 KIT (ratting) 6 12 6 Cure Temperature (^C) 25 25 25 25 25

[0070] The monomers, catalyst and addenda used in Examples 42-27 are shown in Table 8. The times, temperatures and conditions are the same as in example 5 with the following exception(s): in Example 42-47, all of the catalyst is added in the earlier step. Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO TABLE 8 Mononmers (g) Example Example Example Example Example Example 42 43 44 45 46 47 1,4-butanediol 54.1 54.08 54.08 54.09 54.09 51.5 Succinic acid 23.6 23.65 23.65 23.64 23.64 22.27 Adipic acid 21.92 21.95 21.95 14.62 14.62 Oxalic acid 11.29 Polycaprolactone 9250 20.07 Dihydro-2- 40.03 (tetrapropenyl)furan- 2,5-dione Itaconic acid 6.51 6.51 8.11 Epoxy soyabean oil 2.8 2.8 Sodium silicate 3.1 *2-dodecen—1-yl) 14.58 39.97 39.97 39.95 39.95 33 succinic anhydride Catalyst and Other Addenda Titanium (IV) 500 500 500 555 555 500 isopropoxide (mg) BHT (mg) 20 10 10 20 20 20 Coating Structure Coating weight, (g / m2) 25 30 30.5 21.6 25.6 23 Substrate (paper) 15-lb 15-lb 15-lb 15-lb 15-lb 15-lb Brown Brown Brown Brown Brown Brown kraft kraft kraft kraft kraft kraft Test results Does polymer have yes yes yes yes yes yes pendant groups? Cobb 180 (g / m2) 6 1.8 3.2 4.8 KIT (ratting) 12 12 12 12 Cure Temperature (^C) 25 25 25 25 25 25

[0071] The monomers, catalyst and addenda used in Examples 48-51 are shown in Table 9. The times, temperatures and conditions are the same as in example 5 with the following exception(s): in Example 48-51, all of the catalyst is added in the earlier step. Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO TABLE 9 Mononmers (g) Example Example Example Example 48 49 50 51 1,4-butanediol 50.08 51.78 54.01 1,6-Hexanediol Ethylene glycol Succinic acid 22.62 22.11 29.53 Adipic acid 11.27 22.01 21.97 Oxalic acid 11.53 13.51 Maleic anhydride 4.90 Itaconic acid 8.18 8.09 Polycaprolactone 9250 30.01 40.03 Dihydro-2- 26.7 (tetrapropenyl)furan- 2,5-dione (2-dodecen—1-yl) 33.33 33.4 10.04 succinic anhydride Catalyst and Other Addenda Titanium 500 500 500 500 (IV)isopropoxide (mg) BHT (mg) 20 20 20 20 Coating Structure Coating weight, (g / m2) 33 24 47 35 Substrate (paper) 15-lb 15-lb 15-lb 15-lb Brown Brown Brown Brown kraft kraft kraft kraft Test results Does polymer have yes yes yes yes pendant groups? Cobb 180 (g / m2) 62 KIT (ratting) 12 10 12 12 Tensile (Pa) Cure Temperature (^C) 25 25 25 25

[0072] TEST RESULTS

[0073] The Cobb test is useful for measuring the absorbency of water. It is used most widely for assessing the resistance of water absorption by paper. The lower the number, the better the treated substrate is in repelling water or avoiding water absorption. It is seen that with examples 2-4, wherein the polymer does not have a pendent group (e.g., a pendant alkene or alkane group), the measured values are all above 10. All examples wherein the polymer had an pendant alkane or alkene group built into the backbone typically exhibited single digit Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO values, most being under 4. One exception to this is the comparative Example 1 which had a Cobb value of < 3.

[0074] The KIT test is based on TAPPI Test Method T559. It measures the degree of repellency and / or the antiwicking characteristics of paper or paperboard to grease and oil. The test uses a series of reagents with increasing oleophilic characteristics. The rating is 1 to 12 with 12 being the most oleophilic. When absorbency by the substrate is not seen, that is the value assigned for the KIT rating. The data show that all competitive products had values less than 12. The closest was Example 4 which chemically is the same as Examples 2 and 3 but has a coating weight of 69 grams / M2to achieve such performance. Examples 9 and 10 had KIT values of 8 but had coating weights of < 20 g / M2which is a typically lower coating weight than would typically be desired. In general, all the examples with an alkene group built into the backbone of the polyester polymer have the best performance.

[0075] Cure temperature is the temperature at which the coating is dried after the coating is applied. In many coating compositions, such as in Examples 1-4, there is a final in situ reaction as the coating is drying. In contrast, the modified polyesters and coating compositions of the present invention are typically fully reacted and / or fully cured and do not require further heating after being applied to a substrated. The low cure temperature used in the coating process of the inventive examples is an indicator of an advantageous feature that minimizes energy consumption while delivery and fully acceptable product coating. Without being bound by theory, it is believed that the pendant alkyl group eliminates the need for aggressive thermal treatment during or after applying the coating composition to a substrate. All four competitive products (i.e., Competitive Examples 1-4) require 120° C or greater to achieve full performance capability. Example 12 also requires elevated temperatures of greater than 120° C. It is also noted that the polyesters in Example 12 does not benefit from the pendant group.

[0076] Any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. As can be seen, the teaching of amounts expressed as “parts by weight” herein also contemplates the same ranges expressed in terms of percent by weight. Thus, an expression in the Detailed Description of a range in terms of at “x parts by weight of the composition” also contemplates a teaching of ranges of same recited amount of “x in percent by weight of the composition.”

[0077] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of “about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30”, inclusive of at least the specified endpoints.

[0078] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The term “consisting essentially of” to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist essentially of, or even consists of, the elements, ingredients, components or steps. By use of the term “may” herein, it is intended that any described attributes that “may” be included are optional.

[0079] Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of “a” or “one” to describe an element, ingredient, Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO component or step is not intended to foreclose additional elements, ingredients, components or steps. All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.

[0080] It will be appreciated that concentrates or dilutions of the amounts recited herein may be employed. In general, the relative proportions of the ingredients recited will remain the same. Thus, by way of example, if the teachings call for 30 parts by weight of a Component A, and 10 parts by weight of a Component B, the skilled artisan will recognize that such teachings also constitute a teaching of the use of Component A and Component B in a relative ratio of 3:1. Teachings of concentrations in the examples may be varied within about 25% (or higher) of the stated values and similar results are expected. Moreover, such compositions of the examples may be employed successfully in the present methods.

[0081] It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as well as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor should it be regarded that the inventors did not It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as well as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description.

[0082] The scope of the teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

Claims

Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO CLAIMS What is claimed is:

1. A modified polyester comprising a polymerization product of: (i) an aliphatic polyol having a functionality of 2 or more; (ii) an aliphatic carboxylic acid having two or more carboxyl groups or an aliphatic anhydride having a functionality of two or more, and (iii) a modified aliphatic polyol, a modified aliphatic carboxylic acid having a functionality of two or more, and / or a modified aliphatic anhydride having a functionality of two or more, wherein the modified aliphatic polyol, the modified aliphatic carboxylic acid, or the modified aliphatic anhydride includes a pendant group, optionally wherein the aliphatic polyol, the aliphatic carboxylic acid, and the aliphatic anhydride are free of pendant groups including two or more, or three or more atoms having an atomic number of 6 or more.

2. A modified polyester comprising: (i) repeat units having the structure: -( C(O)O – R1– C(O)O – R2-), where R1and R2are linear alkyl groups; and (ii) repeat units having the structure: -( C(O)O – R1– C(O)O – R3(R4)-) or -( C(O)O – R2– C(O)O – R3R4-); where R1, R2, and R3are linear alkyl groups, and R4is a pendant group attached to R3; optionally, wherein the modified polyester is formed from an aliphatic polyol including R1, an aliphatic carboxylic acid or an aliphatic anhydride include R2, and a modified aliphatic polyol or a modified aliphatic carboxylic acid or a modified aliphatic anhydride including R3R4;Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO optionally wherein R3is the same as R1or R2.

3. The modified polyester of claim 1 or 2, wherein the modified polyester has an amorphous phase and a crystalline phase, wherein the crystallinity of the modified polyester is reduced by at least 5% relative to a polyester that is free of the pendant group, wherein the crystallinity is measured using differential scanning calorimetry at a heating rate of 10 C / min.

4. The modified polyester of any of claims 1 through 3, wherein the aliphatic polyol includes a linear alkane with C2– C12.

5. The modified polyester of claim 4, wherein the aliphatic polyol is an aliphatic diol having a structure: OH – R1– OH, where R1is a linear alkane having 2 to 12 carbon atoms.

6. The modified polyester of any of claims 1 through 5, wherein the aliphatic carboxylic acid or the aliphatic anhydride includes a linear alkane with C2– C12.

7. The modified polyester of claim 6, wherein the aliphatic carboxylic acid is a dioic acid having a structure: O=CH-O-(R2)-O-CH=O, where R2is a linear alkane having 2 to 12 carbon atoms.

8. The modified polyester of any of claims 1 through 7, wherein the modified aliphatic carboxylic acid, the modified aliphatic polyol or the modified aliphatic anhydride includes a linear alkane with C2– C12.

9. The modified polyester of any of claims 1 through 8, wherein the pendant group affects the crystallinity of the polyester; preferably wherein the pendant group includes at least two carbon atoms or at least five atoms.

10. The modified polyester of any of claims 1 through 9, wherein the pendant group includes or consists of a linear aliphatic alkane and / or a linear aliphatic alkene.

11. The modified polyester of Claim 10, wherein the pendant group is linear aliphatic alkane having 3 to 16 carbon atoms and / or a linear aliphatic alkene having 3 to 16 carbon atoms.Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO 12. The modified polyester of any of claims 1 through 11, wherein the modified polyester consists essentially of (e.g., at least 98%, at least 99%, at least 99.8%, or at least 99.98% of the atoms), or consists entirely of carbon, oxygen and hydrogen atoms.

13. The modified polyester of any of claims 1 through 12, wherein the mole percentage of the aliphatic polyol in the modified polyester is 5 – 50 %, preferably 10 – 50%, more preferably 15 – 50% and most preferably 25 – 50 %.

14. The modified polyester of any of claims 1 through 12, wherein the total mole percentage of the aliphatic carboxylic acid and the aliphatic anhydride in the modified polyester is 5 – 50 %, preferably 10 – 50%, more preferably 15 – 50% and most preferably 25 – 50 %.

15. The modified polyester of any of claims 1 through 14, wherein: the concentration of the aliphatic polyol in the modified polyester is less than 50 mole percent (e.g., 45 mole percent or less, 40 mole percent or less, or 35 mole percent or less); and / or the total concentration of the aliphatic carboxylic acid and the aliphatic anhydride in the modified polyester is less than 50 mole percent (e.g., 45 mole percent or less, 40 mole percent or less, or 35 mole percent or less).

16. The modified polyester of any of claims 1 through 15, wherein the total mole percentage of the modified aliphatic polyol (if any), the modified aliphatic carboxylic acid (if any) and the modified aliphatic anhydride (if any) in the polyester polymer is 5 – 50 %.

17. The modified polyester of any of claims 1 through 16, wherein the modified polyester is characterized by a tensile strength of 0.5 Pa or more, preferably about 1 Pa or more, more preferably about 2 Pa or more, more preferably about 4 Pa or more, and most preferably about 7 Pa or more.

18. The modified polyester of any of claims 1 through 17, wherein the modified polyester is characterized by a shear strength (adhesion) of about 0.5 Pa or more, about 1.0Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO Pa or more, about 1.5 Pa or more, about 5 Pa or more, about 10 Pa or more, or about 20 Pa or more.

19. The modified polyester of any of claims 1 through 18, wherein the modified polyester is characterized by a KIT value of about 6 or more, preferably about 8 or more, more preferably about 10 or more, and most preferably about 12 or more, as measured according to ASTM TAPPI Test Method T559.

20. The modified polyester of any of claims 1 through 19, wherein the COBB 180 value measured on untreated and uncoated 15-lb brown kraft paper (water absorption test) is about 20 g / m² or less, preferably about 8 g / m² or less, more preferably about 3 g / m² or less and most preferably about 2 g / m² or less.

21. The modified polyester of any of claims 1 through 20, wherein the modified polyester is characterized by a WVTR 8 g / m² / day or less.

22. The modified polyester of any of claims 1 through 21, wherein the modified polyester is characterized by an oxygen transmission rate (OTR) of 15 (cc / m2) / 24 hours or less.

23. The modified polyester of any of claims 1 through 22, wherein the modified polyester is characterized by a weight average or number average molecular weight of about 3,000 g / mole or more, about 5,000 g / mole or more, or about 7,000 g / mole or more, wherein the molecular weight is measured using gel permeation chromatography.

24. The modified polyester of any of claims 1 through 23, wherein a concentration of the pendant groups is about 0.01% or more, about 0.03% or more, about 0.1% or more, about 0.3% or more, about 1.0% or more, or about 3.0% or more, wherein the concentration is the ratio of the number of pendant groups attached to a backbone of the modified polyester to the number of carbon atoms; optionally wherein the concentration of the pendant groups is about 10% or less, about 8% or less, about 6% or less, about 4% or less, or about 3.2% or less.

25. The modified polyester of any of claims 1 through 24, wherein the modified polyester is free of long chain branching.Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO 26. The modified polyester of any of claims 1 through 25, wherein the aliphatic polyol is an aliphatic diol, the aliphatic carboxylic acid is an aliphatic dioic acid, the aliphatic anhydride has a functionality of 2, the modified aliphatic polyol is a modified aliphatic diol, the modified aliphatic carboxylic acid is an aliphatic dioic acid, the modified aliphatic anhydride has a functionality of 2, or any combination thereof.

27. The modified polyester of any of claims 1 to 26, wherein the aliphatic polyols includes two or more different aliphatic diols.

28. The modified polyester of any of claims 1 to 27, wherein the modified polyester includes two or more different aliphatic polyols having a functionality of two or more.

29. The modified polyester of any of claims 1 to 28, wherein the modified polyester includes one or more non-aliphatic diols.

30. The modified polyester of any of claims 1 to 29, wherein the modified polyester includes two or more different aliphatic carboxylic acids having two or more carboxyl groups and / or two or more different aliphatic anhydrides having a functionality of two or more.

31. The modified polyester of any of claims 1 to 30, wherein the modified polyester includes one or more of the aliphatic carboxylic acids having two or more carboxyl groups and one or more of the aliphatic anhydrides having a functionality of two or more.

32. The modified polyester of any of claims 1 to 31, wherein the modified polyester includes a monomeric ester.

33. The modified polyester of any of claims 1 to 32, wherein the modified polyester includes two or more different pendant groups.

34. The modified polyester of any of claims 1 to 33, wherein the molar ratio of hydroxyl groups to the total of the carboxyl groups and the twice the anhydride groups for the multifunctional monomers is about 0.95 or more, more preferably about 0.97 or more, even more preferably about 0.98 or more, and most preferably about 0.99 or more.Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO 35. The modified polyester of any of claims 1 to 34, wherein the molar ratio of hydroxyl groups to the total of the carboxyl groups and twice the anhydride groups for the multifunctional monomers is about 1.05 or less, more preferably about 1.03 or less, even more preferably about 1.02 or less, and most preferably about 1.01 or less.

36. The modified polyester of any of claims 1 to 35, wherein 60 weight percent or more of the modified polyester is aliphatic, preferably 70 weight percent or more of the modified polyester is aliphatic, and most preferably 80 weight percent or more of the modified polyester is aliphatic.

37. The modified polyester of any of claims 1 to 36, wherein 60 weight percent or more of the backbone of the modified polyester is aliphatic, preferably 70 weight percent or more of the backbone of the modified polyester is aliphatic, and most preferably 80 weight percent or more of the backbone of the modified polyester is aliphatic.

38. The modified polyester of any of claims 1 to 37, wherein 60 weight percent or more of the pendant group of the modified polyester is aliphatic, preferably 70 weight percent or more of the pendant group of the modified polyester is aliphatic, and most preferably 80 weight percent or more of the pendant group of the modified polyester is aliphatic.

39. The modified polyester of any of claims 1 to 38, wherein the concentration of ester groups, -C(O)O-, in the modified polyester is about 3 weight percent or more, about 5 weight percent or more, or about 7 weight percent or more and / or about 30 weight percent or less, about 25 weight precent or less, about 20 weight percent or less, or about 15 weight percent or less.

40. The modified polyester of any of claims 1 to 39, wherein the total concentration of the aliphatic polyol having functionality of two or more, the aliphatic anhydride, and the aliphatic carboxylic acid having two or more carboxyl groups is about 60 weight percent or more, preferably about 80 weight percent or more, more preferably aboutFiled via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO 85 weight percent or more, and most preferably about 90 weight percent or more, based on the total weight of the modified polyester.

41. The modified polyester of any of claims 1 to 40, wherein one or more ends of the modified polyester is capped, preferably by reacting with an aliphatic acid, such as aliphatic monoacid having 2 to 50 carbon atoms.

42. The modified polyester of any of claims 1 to 41, wherein the modified polyester includes a fumarate, a malonate, an aziridine, an epoxidized soyabean oil, or a polycaprolactone.

43. A composition including the modified polyester of any of claims 1 through 42.

44. The composition of Claim 43 wherein said the modified polyester is in an emulsion having a diluent or in a solution including a solvent, preferably wherein the diluent includes or consists of water.

45. The composition of claim 44, wherein the composition is a polymeric composition including one or more additives for improving: coating uniformity, adhesion, chemical resistance, mechanical resistance, barrier properties, or any combination thereof.

46. The composition of any of claims 43 to 45, wherein the coating is capable of being applied at a coating weight of 50 g / M2or less, preferably 35 g / M2or less, and more preferably 25 g / M2or less, and / or at a coating weight of 5 g / M2or more, preferably 8 g / M2or more, and more preferably 12 g / M2or more.

47. The composition of any of claims 43 to 46, wherein the composition includes a filler or further ingredient selected from one or any combination of a starch, a modified starch, and an aliphatic polyol.

48. The composition of any of claims 43 to 47, wherein the composition: is free of PFAS, is compostable, is biodegradable (preferably wherein the biodegradation product is free of microplastics), or any combination thereof.Filed via USPTO.gov on June 17, 2025 Attorney Docket No.: 2348.002WO 49. An article including a layer comprising the modified polyester of any of claims 1 through 42 in direct contact with a substrate.

50. An article comprising a layer including a substrate and the composition of any of claims 43 to 48 and / or formed by coating a substrate with the composition of any of claims 43 to 48.

51. The article of claim 49 or 50, wherein the substrate is a paper, a cardboard, or other cellulose-based material.

52. The article of any of claims 49 to 51, wherein the article is biodegradable, compostable, or both.

53. The article of any of claims 49 to 52, wherein the article is for one or more of the following applications, food, household products, personal care products, industrial, chemical and other applications where there is a need to reduce or eliminate permeability, preferably wherein the article is or includes a packaging.

Images