MELT PROCESSABLE CELLULOSE ESTER COMPOSITIONS CONTAINING ALKALINE FILLERS - Patent application

Abstract

The present application discloses a melt-processable cellulose ester composition comprising a cellulose ester, at least one alkaline additive, and at least one neutralizing agent. Optionally, a plasticizer can be used in the composition. The present application also discloses a method for preparing the composition, and an article that can be made from the composition. The composition shows improved decomposition properties.

Description

[Background technology]

[0001] There is a well-known global problem with waste disposal, especially with the disposal of large amounts of consumer products such as plastics or polymers that are not considered biodegradable within acceptable time limits. There is a societal desire to incorporate these types of waste into regenerative products by recycling, reusing, or otherwise reducing the amount of waste in circulation or landfills. This is especially true for disposable plastic articles / materials.

[0002] Consumer sentiment regarding the environmental fate of single-use plastics such as straws, takeaway cups, and plastic bags has become a global trend, with bans of plastic products being considered / enacted around the world in both developed and developing countries. Bans range from plastic shopping bags to straws, cutlery, and clamshell packaging, for example in the United States alone. Some countries have taken even stricter measures, for example across the EU, a list of 10 single-use items are banned, restricted in use, or required to have Extended Producer Responsibility. As a result, industry leaders, brand owners, and retailers are ambitious to implement recyclable, reusable, or compostable packaging in the coming years. While there are some applications where recyclable materials are desirable, there are others that are more suited to compostable and / or biodegradable materials, for example when items are contaminated with food or there are high levels of leakage into the environment due to poor waste management systems.

[0003] Disposable plastic articles are frequently used in food service, which are intended to be used once to store or serve food, after which the article is discarded. To prevent the persistence of these articles, it is desirable for the articles to disintegrate and biodegrade, even for thicker parts such as cup rims and utensils. Disintegration in composting is the end of life of these disposable plastic articles to divert them from landfills. Disposable plastic articles can range in thickness from less than 5 mils (e.g., straws) to more than 100 mils (e.g., utensils). For some materials, the rate of disintegration in composting is proportional to the thickness of the article, i.e., thicker articles take a longer time to disintegrate or may not disintegrate within the standard time frame of a composting cycle.

[0004] It is desirable to make articles from bio-based materials that are formulated to disintegrate in compost, even if the article has a thickness of 30 mils or more. Additionally, the appearance of the article should be suitable for the application (not dark and not opaque).

[0005] Thus, there is a need in the market for disposable consumer products that have appropriate performance characteristics for their intended use and that are compostable and / or biodegradable. It would be beneficial to provide a product that has such characteristics and that has a high content of renewable, recycled, and / or reused materials. Summary of the Invention [Means for solving the problem]

[0006] The present application relates to a melt-processable cellulose ester composition comprising: at least one cellulose ester, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of said alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt. % to about 35 wt. % based on the weight of the cellulose ester composition; or Disclosed is a cellulose ester composition comprising at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt % suspension of said alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and said alkaline filler is present in an amount of about 0.1 wt % to about 35 wt %, based on the weight of the cellulose acetate composition.

[0007] The present application discloses a method for producing a melt-processable cellulose ester composition. The method includes contacting at least one cellulose ester, optionally at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt% suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25°C is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt% to about 35 wt%, based on the weight of the cellulose ester composition.

[0008] The present application discloses a method for producing a melt-processable cellulose acetate composition. The method includes contacting at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt % suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt % to about 35 wt %, based on the weight of the cellulose acetate composition.

[0009] The present application discloses an article comprising a melt-processable cellulose ester composition, the cellulose ester composition comprising: at least one cellulose ester, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt. % to about 35 wt. % based on the weight of the cellulose ester composition; or A composition comprising at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt. % to about 35 wt. % based on the weight of the cellulose acetate composition.

[0010] The present application discloses that a cellulose acetate tow band is provided that includes a cellulose acetate composition; at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt % suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt % to about 35 wt %, based on the weight of the cellulose acetate composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present application relates to a melt-processable cellulose ester composition comprising: at least one cellulose ester, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt. % to about 35 wt. % based on the weight of the cellulose ester composition; or Disclosed is a cellulose ester composition comprising at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt % suspension of the alkaline additive has a pH of 8 or greater, the water solubility of the alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and the alkaline filler is present in an amount of about 0.1 wt % to about 35 wt %, based on the weight of the cellulose acetate composition.

[0012] Cellulose Ester The cellulose esters utilized in the present invention can be any known in the art. The cellulose esters that can be used in the present invention generally contain repeating units of the following structure:

[0013] [ka] In the formula, R 1 , R 2 , and R 3are independently selected from the group consisting of hydrogen, acetyl, propyl or butyl. The substitution level of cellulose esters is usually expressed in terms of the degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups that can be substituted on each AGU unit, and therefore the DS can have a value between zero and 3. Natural cellulose is a large polysaccharide with a degree of polymerization of 250-5,000 even after pulping and purification, so the assumption that the maximum DS is 3.0 is approximately correct. Since DS is a statistical average, a value of 1 does not guarantee that any AGU has a single substitution. In some cases, there may be unsubstituted anhydroglucose units, some with two and some with three substituents, and typically the value will be a non-integer. The total DS is defined as the average total number of substituents per anhydroglucose unit. The degree of substitution per AGU can also refer to a specific substituent, such as hydroxyl or acetyl. In an embodiment, n is an integer in the range of 25 to 250, or 25 to 200, or 25 to 150, or 25 to 100, or 25 to 75.

[0014] In an embodiment of the present invention, the cellulose ester has at least two anhydroglucose rings and may have at least 50 to a maximum of 5,000 anhydroglucose rings, or at least 50 to less than 150 anhydroglucose rings. The number of anhydroglucose units per molecule is defined as the degree of polymerization (DP) of the cellulose ester. In an embodiment, the cellulose ester may have an intrinsic viscosity (IV) of about 0.2 to about 3.0, or about 0.5 to about 1.8, or about 1 to about 1.5 deciliters per gram, measured at a temperature of 25°C for a 0.25 gram sample in a 100 ml 60 / 40 weight ratio phenol / tetrachloroethane solution. In an embodiment, the cellulose ester useful herein may have a DS / AGU of about 1 to about 2.5, or 1 to less than 2.2, or 1 to less than 1.5, and the substituted ester is acetyl.

[0015] Cellulose ester can be produced by any method known in the art.The example of the process for producing cellulose ester is taught in Kirk-Othmer, Encuclopedia of Chemical Technology, 5th edition, vol.5, Wiley-Interscience, New York (2004), pp.394-444.The starting material cellulose for producing cellulose ester can be obtained in different grades and from different sources, for example, from cotton linters, softwood pulp, hardwood pulp, corn fiber and other agricultural sources, and especially from bacterial cellulose.

[0016] One method of producing cellulose ester is esterification of cellulose by mixing cellulose with appropriate organic acid, acid anhydride, and catalyst.The cellulose is then converted to cellulose triester.The ester hydrolysis is then carried out by adding a water-acid mixture to the cellulose triester, which can then be filtered to remove any gel particles or fibers.Water is then added to the mixture to precipitate the cellulose ester.The cellulose ester can then be washed with water to remove reaction by-products, followed by dehydration and drying.

[0017] The cellulose triester that is hydrolyzed can have three acetyl substituents. These cellulose esters can be prepared by several methods known to those skilled in the art. For example, cellulose esters can be prepared by the heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a catalyst such as H2SO4. Cellulose triester can also be prepared by the homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0018] Those skilled in the art will understand that the commercial term cellulose triester also includes cellulose ester that is not fully substituted with acyl groups.For example, the cellulose triacetate commercially available from Eastman Chemical Company, Kingsport, TN, USA typically has a DS of about 2.85 to about 2.99.

[0019] After esterification of cellulose to triester, some of the acyl substituents can be removed by hydrolysis or alcoholysis to produce secondary cellulose esters. As mentioned before, depending on the specific method used, the distribution of acyl substituents can be random or non-random. Secondary cellulose esters can also be prepared directly without hydrolysis by using a limited amount of acylating reagent. This process is particularly useful when the reaction is carried out in a solvent that dissolves cellulose. All of these methods result in cellulose esters that are useful in the present invention.

[0020] In one embodiment, or in combination with any of the mentioned embodiments, or in combination with any of the mentioned embodiments, the cellulose acetate is a cellulose diacetate having a polystyrene-equivalent number average molecular weight (Mn) of about 10,000 to about 100,000 as measured by gel permeation chromatography (GPC) using NMP as the solvent and ... or less than 10,000 to 55,000; or less than 10,000 to 50,000; or less than 10,000 to 50,000; or less than 10,000 to 45,000; or less than 10,000 to 40,000; or less than 10,000 to 30,000; or less than 20,000 to 60,000; or less than 20,000 to 55,000; or 20,000 to 50,000; or less than 20,000 to 50,000; or less than 20,000 to 45,000; or 20,000 to 40,000; or 20,000 to 35,000; or 20,000 to 30,000; or less than 30,000 to 60,000; or less than 30,000 to 55,000; or 30,000 to 50,000; or less than 30,000 to 50,000; or less than 30,000 to 45,000; or 30,000 to 40,000; or 30,000 to 35,000.

[0021] The most common commercial secondary cellulose esters are prepared by first acid-catalyzed heterogeneous acylation of cellulose to form a cellulose triester. After obtaining a homogeneous solution of the cellulose triester in the corresponding carboxylic acid, the cellulose triester is then subjected to hydrolysis until the desired degree of substitution is obtained. After isolation, a random secondary cellulose ester is obtained; that is, the relative degree of substitution (RDS) at each hydroxyl is approximately equal.

[0022] The cellulose esters useful in the present invention can be prepared using techniques known in the art and can be selected from various types of cellulose esters, such as those available from Eastman Chemical Company, Kingsport, TN, USA, such as Eastman™ Cellulose Acetate CA 398-30 and Eastman™ Cellulose Acetate CA 398-10, Eastman™ CAP 485-20 (cellulose acetate / propionate), Eastman™ CAB 381-2 (cellulose acetate / butyrate), etc.

[0023] In an embodiment of the present invention, cellulose ester can be prepared by converting cellulose into cellulose ester with reactants obtained from recycled materials, such as recycled plastic content syngas sources.In an embodiment, such reactants can be cellulose reactants, including organic acids and / or acid anhydrides, for example, used in esterification or acylation reactions of cellulose, as discussed herein.

[0024] In one embodiment of the present invention, or in combination with any of the above-mentioned embodiments, or in combination with any of the above-mentioned embodiments, a cellulose ester composition is provided, comprising at least one recycled cellulose ester, wherein the cellulose ester has at least one substituent on the anhydroglucose unit (AU) that is derived from recycled content material, such as recycled plastic content syngas.

[0025] Plasticizer In one embodiment, or in combination with any other embodiment, the melt-processible biodegradable cellulose ester composition can include at least one plasticizer. The plasticizer reduces the melt temperature, Tg, and / or melt viscosity of the cellulose ester. Plasticizers for cellulose esters include glycerol triacetate (triacetin), glycerol diacetate, dibutyl terephthalate, dimethyl phthalate, diethyl phthalate, poly(ethylene glycol) MW 200-600, triethylene glycol dipropionate, 1,2-epoxypropyl phenylethylene glycol, 1,2-epoxypropyl (m-cresyl) ethylene glycol, 1,2-epoxypropyl (o-cresyl) ethylene glycol, β-oxyethyl cyclohexene carboxylate, bis(cyclohexanate) diethylene glycol, triethyl citrate, polyethylene glycol, Benzoflex, propylene glycol, polysorbate, sucrose octaacetate, acetylated triethyl citrate, acetyl tributyl citrate, Admex, tripropionin, Scandiflex, poloxamer copoly mers, polyethylene glycol succinates, diisobutyl adipate, polyvinylpyrrolidone and glycol tribenzoate, triethyl citrate, acetyl triethyl citrate, polyethylene glycol, benzoate-containing plasticizers such as the Benzoflex™ plasticizer series, poly(alkyl succinates) such as poly(butyl succinate), polyethersulfone, adipate-based plasticizers, soybean oil epoxides such as the Paraplex™ plasticizer series, sucrose-based plasticizers, dibutyl sebacate, tributyrin, tripropionin, sucrose acetate isobutyrate, the Resolflex™ series of plasticizers, triphenyl phosphate, glycolate, methoxypolyethylene glycol, 2,2,4-trimethylpentane-1,3-diylbis(2-methylpropanoate), and polycaprolactone.

[0026] In one embodiment or in combination with any other embodiment, the plasticizer is a food-compatible plasticizer. Food-compatible means that it complies with applicable food additive and / or food contact regulations, and the plasticizer is permitted for use or recognized as safe by at least one (national or local) food safety regulatory agency (or organization), e.g., listed in the 21 CFR food additive regulations or otherwise generally recognized as safe (GRAS) by the US FDA. In one embodiment or in combination with any other embodiment, the food-compatible plasticizer is triacetin or a polyethylene glycol (PEG) having a molecular weight of about 200 to about 600. In embodiments, examples of food compatible plasticizers that may be considered include triacetin, triethyl citrate, polyethylene glycol, Benzoflex, propylene glycol, polysorbate, sucrose octaacetate, acetylated triethyl citrate, acetyl tributyl citrate, Admex, tripropionin, Scandiflex, poloxamer copolymers, polyethylene glycol succinate, diisobutyl adipate, polyvinylpyrrolidone, and glycol tribenzoate.

[0027] In one embodiment, or in combination with any other embodiment, the plasticizer may be present in an amount sufficient to allow the cellulose ester composition to be melt processed (or thermoformed) into a useful article in conventional melt processing equipment, for example, into a disposable plastic article. In one embodiment, or in combination with any other embodiment, the plasticizer is present in an amount of 1-40 wt% for most thermoplastic processing; or 5-25 wt%, or 10-25 wt%, or 12-20 wt%, based on the weight of the cellulose ester composition. In an embodiment, profile extrusion, sheet extrusion, thermoforming, and injection molding may be accomplished with plasticizer levels in the range of 10-30 wt%, or 12-25 wt%, or 15-20 wt%, or 10-25 wt%, based on the weight of the cellulose ester composition.

[0028] In one embodiment or in combination with any other embodiment, the plasticizer is a biodegradable plasticizer.Some examples of biodegradable plasticizers include triacetin, triethyl citrate, acetyl triethyl citrate, polyethylene glycol, benzoate-containing plasticizers, such as Benzoflex™ plasticizer series, poly(alkyl succinates), such as poly(butyl succinate), polyethersulfone, adipate-based plasticizers, soybean oil epoxides, such as Paraplex™ plasticizer series, sucrose-based plasticizers, dibutyl sebacate, tributyrin, Resoflex™ series plasticizers, triphenyl phosphate, glycolate, polyethylene glycol, 2,2,4-trimethylpentane-1,3-diylbis(2-methylpropanoate), and polycaprolactone.

[0029] PEG / MPEG Specific Compositions In one embodiment, or in combination with any other embodiment, the cellulose ester composition may contain a plasticizer selected from the group consisting of PEG and MPEG (methoxy PEG), a polyethylene glycol or methoxy polyethylene glycol composition having an average molecular weight of 200 Daltons to 600 Daltons, and the composition is melt processable, biodegradable, and disintegrable.

[0030] In one embodiment, or in combination with any other embodiment, the composition comprises polyethylene glycol or methoxy PEG having an average molecular weight of 300 to 550 daltons.

[0031] In one embodiment, or in combination with any other embodiment, the composition comprises polyethylene glycol having an average molecular weight of 300 to 500 daltons. In one embodiment, or in combination with any other embodiment, the cellulose ester composition may comprise from 1 wt% to 40 wt%, or from 5 wt% to 40 wt%, or from 10 wt% to 40 wt%, or from 12 wt% to 40 wt%, or from 13 wt% to 40 wt%, or from 15 wt% to 40 wt%, or from greater than 15 wt% to 40 wt%, or from 17 wt% to 40 wt%, or from 20 wt% to 40 wt%, all based on the total weight of the cellulose ester composition. % to 40wt%, or 25wt% to 40wt%, or 5wt% to 35wt%, or 10wt% to 35wt%, or 13wt% to 35wt%, or 15wt% to 35wt%, or more than 15wt% to 35wt%, or 17wt% to 35wt%, or 20wt% to 35wt%, or 5wt% to 30wt%, or 10wt% to 30wt%, or 13wt% to 30wt%, or 15wt% to 30wt%, or is more than 15wt% to 30wt%, or 17wt% to 30wt%, or 5wt% to 25wt%, or 10wt% to 25wt%, or 13wt% to 25wt%, or 15wt% to 25wt%, or more than 15wt% to 25wt%, or 17wt% to 25wt%, or 5wt% to 20wt%, or 10wt% to 20wt%, or 13wt% to 20wt%, or 15wt% to 20wt%, or more than 15wt% to 2 at least one plasticizer (as described herein) in an amount of 0 wt%, or between 17 wt% and 20 wt%, or between 5 wt% and 17 wt%, or between 10 wt% and 17 wt%, or between 13 wt% and 17 wt%, or between 15 wt% and 17 wt%, or between greater than 15 wt% and 17 wt%, or between 5 wt% and less than 17 wt%, or between 10 wt% and less than 17 wt%, or between 13 wt% and less than 17 wt%, or between 15 wt% and less than 17 wt%.

[0032] In one embodiment or in combination with any other embodiment, the at least one plasticizer comprises or is a food compatible plasticizer. In one embodiment or in combination with any other embodiment, the food compatible plasticizer comprises or is triacetin or PEG MW300-500.

[0033] In one embodiment, or in combination with any other embodiment, the cellulose ester composition comprises a biodegradable cellulose ester (BCE) component comprising at least one BCE, and a biodegradable polymer component comprising at least one other biodegradable polymer (other than BCE).In one embodiment, or in combination with any other embodiment, the other biodegradable polymer can be selected from polyhydroxyalkanoates (PHA and PHB), polylactic acid (PLA), polycaprolactone polymers (PCL), polybutylene adipate terephthalate (PBAT), polyethylene succinate (PES), polyvinyl acetate (PVA), polybutylene succinate (PBS) and copolymers (e.g. polybutylene succinate-co-adipate (PBSA)), cellulose esters, cellulose ethers, starches, proteins, derivatives thereof, and combinations thereof.In one embodiment, or in combination with any other embodiment, the cellulose ester composition comprises two or more biodegradable polymers. In one embodiment, or in combination with any other embodiment, the cellulose ester composition contains a biodegradable polymer (other than BCE) in an amount of 0.1 wt% to less than 50 wt%, or 1 wt% to 40 wt%, or 1 wt% to 30 wt%, or 1 wt% to 25 wt%, or 1 wt% to 20 wt%, based on the cellulose ester composition. In one embodiment, or in combination with any other embodiment, the cellulose ester composition contains a biodegradable polymer (other than BCE) in an amount of 0.1 wt% to less than 50 wt%, or 1 wt% to 40 wt%, or 1 wt% to 30 wt%, or 1 wt% to 25 wt%, or 1 wt% to 20 wt%, based on the total amount of BCE and biodegradable polymer.In one embodiment, or in combination with any other embodiment, the at least one biodegradable polymer has a refractive index of 10,000 to 1,000,000, or 50,000 to 1,000,000, or 100,000 to 1,000,000, or 250,000 to 1,000,000, as measured using gel permeation chromatography (GPC) with a refractive index detector and polystyrene standards using a solvent of methylene chloride. In one embodiment, or in combination with any other embodiment, the PHA may include a PHA having a weight average molecular weight (Mw) of polyhydroxybutyrate-co-hydroxyhexanoate.

[0034] Alkaline filler The alkaline filler suitable for the present invention is at least one selected from the group consisting of metal oxide, metal hydroxide, metal carbonate and mixtures thereof.A blend of alkaline fillers may be used in the cellulose ester composition.In one embodiment, or in combination with any other embodiment, the alkaline filler is at least one selected from the group consisting of alkaline earth metal oxide, alkaline earth metal hydroxide and alkaline earth carbonate.

[0035] Alkaline fillers have certain physical properties. To be suitable for this application, the water solubility of the alkaline filler at 20-25°C is only useful within a certain range. If the water solubility is too high, moisture in the melt-processed article may prematurely initiate the chemical reactions of disintegration. If the water solubility is too low, the basic ions (OH -1 or CO3 -2) cannot be released from the filler. Furthermore, the pH of the 1 wt% solution or suspension of the alkaline filler should be pH 8 or higher, which is related to the water solubility. If the pH is not 8 or higher, the conditions are not suitable for promoting the chemical reaction of disintegration. In one embodiment, or in combination with any other embodiment, the pH of the 1 wt% solution or suspension of the alkaline filler is pH 8.5 or higher. In one embodiment, or in combination with any other embodiment, the pH of the 1 wt% solution or suspension of the alkaline filler may be in the range of about 8 to about 12, about 8 to about 11.5, about 8 to about 11, about 8 to about 10.5, about 8 to about 10, 8.5 to about 12, about 8.5 to about 11.5, about 8.5 to about 11, about 8.5 to about 10.5, about 8.5 to about 10, about 9 to about 12, about 9 to about 11.5, about 9 to about 11, and about 9 to about 10.5. Not all metal oxides, hydroxides and carbonates are suitable in the present invention: for example, aluminum oxide (Al2O3) and titanium dioxide (TiO2) are insoluble in water, do not react with water to form the corresponding hydroxides, and do not change the pH of the water.

[0036] "Alkaline efficiency" is defined as moles of base divided by kilograms of alkaline filler. The alkaline efficiency of an alkaline filler also governs its ability to promote disintegration through chemical action. Alkaline efficiency is the moles of basic ions associated with a particular mass of filler in the presence of water. For example, CaO and MgO react with water to produce 2 moles of hydroxide ions (OH -1 ) is formed. Alkaline fillers with higher alkaline efficiency can accelerate the chemical reactions underlying the disintegration at lower filler loadings based on wt% in the formulation. A stoichiometric amount of alkaline catalyst is required for the base catalyzed hydrolysis of esters because the eventual acid formed neutralizes the base catalyst, inactivating it.

[0037] To be suitable in the present application, the water solubility of the alkaline filler at 20 to 25° C. should be more than 1 ppm but less than 1,000 ppm. In other embodiments of the present invention, the water solubility of the alkaline filler at 20 to 25° C. is about 2 ppm to about 1,000 ppm, about 2 ppm to about 950 ppm, about 2 ppm to about 900 ppm, about 2 ppm to about 850 ppm, about 2 ppm to about 800 ppm, about 2 ppm to about 750 ppm, about 2 ppm to about 700 ppm, about 2 ppm to about 650 ppm, about 2 ppm to about 600 ppm, about 2 ppm to about 550 ppm, about 2 ppm to about 500 ppm, about 2 ppm to about 450 ppm, about 2 ppm to about 4 ...00 ppm, about 2 ppm to about 500 ppm, about 2 ppm to about 500 ppm, about 2 ppm to about 500 ppm, about 2 ppm to about 650 ppm, about 2 ppm to about 600 ppm, about 2 ppm to about 750 ppm, about 2 ppm to about 700 ppm, about 2 ppm to about 850 ppm, about 2 ppm to about 800 ppm, about 2 ppm to about 950 ppm, about 2 ppm to about 900 ppm, about 2 ppm to about 1000 ppm, about 2 ppm to about 1500 ppm, about 2 ppm to about 1000 ppm, about 2 ppm to about 1500 ppm, about 2 ppm to about 1500 ppm, about 2 ppm to about 1500 ppm, about 2 ppm m, about 2ppm to about 350ppm, about 2ppm to about 300ppm, 3ppm to about 1,000ppm, about 3ppm to about 950ppm, about 3ppm to about 900ppm, about 3ppm to about 850ppm, about 3ppm to about 800ppm, about 3ppm to about 750 ppm, about 3ppm to about 700ppm, about 3ppm to about 650ppm, about 3ppm to about 600ppm, about 3ppm to about 550ppm, about 3ppm to about 500ppm, about 3ppm to about 450ppm, about 3ppm to about 400ppm, about 3ppm to about 350 ppm, approximately 3ppm to approximately 300ppm, 4ppm to approximately 1,000ppm, approximately 4ppm to approximately 950ppm, approximately 4ppm to approximately 900ppm, approximately 4ppm to approximately 850ppm, approximately 4ppm to approximately 800ppm, approximately 4ppm to approximately 750ppm, approximately 4ppm to approximately 7 00ppm, about 4ppm to about 650ppm, about 4ppm to about 600ppm, about 4ppm to about 550ppm, about 4ppm to about 500ppm, about 4ppm to about 450ppm, about 4ppm to about 400ppm, about 4ppm to about 350ppm, about 4ppm to about 3 00 ppm, 5 ppm to about 1,000 ppm, about 5 ppm to about 950 ppm, about 5 ppm to about 900 ppm, about 5 ppm to about 850 ppm, about 5 ppm to about 800 ppm, about 5 ppm to about 750 ppm, about 5 ppm to about 700 ppm, about 5 ppm to about 650 ppm, about 5 ppm to about 600 ppm, about 5 ppm to about 550 ppm, about 5 ppm to about 500 ppm, about 5 ppm to about 450 ppm, about 5 ppm to about 400 ppm, about 5 ppm to about 350 ppm, and about 5 ppm to about 300 ppm.

[0038] In one embodiment, or in combination with any other embodiment, the pH of a 1 wt% suspension of the alkaline filler should be 8 or greater, and the alkaline efficiency should be at least 5. In one embodiment, or in combination with any other embodiment, the alkaline efficiency is at least 6, at least 7, at least 8, at least 9, or at least 10. The following table shows comparative properties of selected alkaline fillers, only some of which meet all of the criteria of the present invention. Examples of alkaline fillers that meet the criteria include calcium carbonate (CaCO3), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), magnesium carbonate (MgCO3), and barium carbonate (BaCO3). Effective and readily available alkaline fillers are calcium carbonate (CaCO3), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), and magnesium carbonate (MgCO3). Moreover, these alkaline fillers are particularly suitable for food contact applications.

[0039] In one embodiment, or in combination with any other embodiment, the alkaline filler is a mixture of calcium carbonate and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate, where the calcium carbonate is present at 5-25 wt % based on the total weight of the cellulose ester composition, and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate is present at 1-20 wt %. In one embodiment, or in combination with any other embodiment, the alkaline filler is a mixture of calcium carbonate and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate, where the calcium carbonate is present at 5-15 wt % based on the total weight of the cellulose ester composition, and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate is present at 1-20 wt %. In one embodiment, or in combination with any other embodiment, the alkaline filler is a mixture of calcium carbonate and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate, where the calcium carbonate is present at 5-10 wt % based on the total weight of the cellulose ester composition, and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate is present at 1-20 wt %.

[0040] The alkaline fillers may be hydrated. Blends of alkaline fillers are also an option to create alkaline conditions to promote disintegration. The alkaline fillers, hydrates or blends may be natural or synthetic blends, compounds or minerals. For example, magnesium carbonate may be mined as the mineral magnesite or may be prepared in the laboratory by reacting soluble magnesium salts with sodium bicarbonate. Examples of mineral hydrates and blends include basic magnesium carbonate (BMC, typically hydrated with 3-5 water molecules), artignite (4MgCO3·Mg(OH)2·3H2O), hydromagnesite (Mg5(CO3)4(OH)2·4H2O), daipingite (4MgCO3·Mg(OH)2·5H2O) and dolomite (CaCO3·MgCO3). When a soluble magnesium salt (e.g., magnesium chloride or sulfate) is treated with sodium carbonate or bicarbonate, depending on the reaction temperature and CO2 partial pressure, the resulting precipitate may contain hydrated complexes of magnesium carbonate and / or magnesium hydroxide, such as [MgCO3·3H2O] or [4MgCO3·Mg(OH)2·4H2O]. Blends may also be made by combining anhydrous or hydrated forms of MgO, Mg(OH)2 and / or MgCO3 with each other or with another mineral within the same water solubility range (e.g., CaCO3 or BaCO3).

[0041] [Table 1] Although not required, it is beneficial for the alkaline filler to have the ability to produce volume expansion. For example, hydration of MgO to magnesium hydroxide (Mg(OH)2) results in an increase in volume. During hydration, the weight of one mole of MgO increases from 40.3 g to 58.3 g (i.e., an increase of 44.7%), and the filler volume can increase by 2.2 times after full hydration. Localized volume expansion can create tensile stresses in melt-processed articles, leading to the formation of cracks and fissures that contribute to collapse. Similarly, MgCO3 can hydrate, which changes the filler density and greatly increases the molar volume. MgCO3 can also react with aqueous acid solutions to release CO2 and water, simultaneously producing volume expansion within the thermoformed article, which results in tensile stresses, physical deformation and / or fracture.

[0042] [Table 2] To be useful in the present invention, the amount of alkaline filler is limited to a certain range in the formulation. The amount should be high enough to promote the chemical reaction of disintegration without causing premature decomposition of the formulation. If the alkaline filler is present at more than 35wt%, the alkalinity or free alkali, combined with the heat of processing, may cause premature decomposition of the formulation. If the alkaline filler is present at too low a dosage, it may be ineffective in promoting the chemical reaction of disintegration. In one embodiment, or in combination with any other embodiment, the alkaline filler is present in the cellulose ester composition in an amount by weight of about 0.1 wt% to about 30 wt%, or about, about 0.1 wt% to about 25 wt%, or about 0.1 wt% to about 20 wt%, or about 0.1 wt% to about 15 wt%, or about 1 wt% to about 35 wt%, or about 1 wt% to about 30 wt%, or about 1 wt% to about 25 wt%, or about 1 wt% to about 20 wt%. wt%, or about 1 wt% to about 15 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%, or about 5 wt% to about 35 wt%, or about 5 wt% to about 30 wt%, or about 5 wt% to about 25 wt%, or about 5 wt% to about 20 wt%, or about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, or about 10 wt% to about 35 wt%, or about 10 wt% to about 30 wt%, or is about 10wt% to about 25wt%, or about 10wt% to about 20wt%, or about 10wt% to about 15wt%, or about 15wt% to about 35wt%, or about 15wt% to about 30wt%, or about 15wt% to about 25wt%, or about 15wt% to about 20wt%, or about 15wt% to about 20wt%, or about 20wt% to about 35wt%, or about 20wt% to about 30wt%, or about 20wt% to about 25wt%, or about 25 wt% to about 35 wt%, or about 25 wt% to about 30 wt%, or about 0.1 wt% to about 10 wt%, and are present in the cellulose ester composition at about 0.5 wt% to about 10 wt%, or about 1 wt% to about 10 wt%, or about 1 wt% to about 10 wt%, or about 1.5 wt% and about 10 wt%, or about 2 wt% and about 10 wt%, or about 2.5 wt% and about 10 wt%, or about 3 wt% and about 10 wt%, or about 3.5 wt% and about 10 wt%, or about 4 wt% to about 10 wt%, or about 4.5 wt% to about 10 wt%, or about 5 wt% to about 10 wt%, or 0.1 wt% and about 9.5 wt%, and are present in the cellulose ester composition at about 0.5 wt% to about 9.5 wt%, or about 1 wt% to about 9.5 wt%, or about 1.5 wt% and about 9.5 wt%, or about 2 wt% and about 9.5 wt%, or about 2.5 wt% and about 9.5 wt%, or about 3 wt% and about 9.5 wt%, or about 3.5 wt% and about 9. 5 wt%, or about 4 wt% and about 9.5 wt%, or about 4.5 wt% and about 9.5 wt%, or about 5 wt% and about 9.5 wt%, or 0.1 wt% and about 9 wt%, or about 0.5 wt% to about 9 wt%, or about 1 wt% to about 9 wt%, or about 1.5 wt% and about 9 wt%, or about 2 wt% and about 9 wt%, or about 2.5 wt% and about 9 wt%, or about 3 wt% and about 9 wt%, or about 3.5 wt% and about 9 wt%, or about 4 wt% % and about 9 wt%, or about 4.5 wt% and about 9 wt%, or about 5 wt% and about 9 wt%, or 0.1 wt% and about 8.5 wt%, or about 0.5 wt% to about 8.5 wt%, or about 1 wt% to about 8.5 wt%, or about 1.5 wt% and about 8.5 wt%, or about 2 wt% and about 8.5 wt%, or about 2.5 wt% and about 8.5 wt%, or about 3 wt% and about 8.5 wt%, or about 3.5 wt% and about 8.5 wt%, or about 4 wt% and about 8.5 wt%, or about 5 wt% and about 8.5 wt%, or about 6 wt% and about 8.5 wt%, or about 7 wt% and about 8.5 wt%, or about 9 wt% and about 9 wt%, or about 10 wt% and about 8.5 ... and about 8.5 wt%, or about 4.5 wt% and about 8.5 wt%, or about 5 wt% and about 8.5 wt%, or 0.1 wt% and about 8 wt%, and are present at about 0.5 wt% to about 8 wt%, or about 1 wt% to about 8 wt%, or about 1.5 wt% to about 8 wt%, or about 2 wt% to about 8 wt%, or about 2.5% to about 8%, or about 3% to about 8%, or about 3.5% to about 8 wt%, or about 4 wt% to about 8%, or about 4.5% to about 8%, or about 5% to about 8% by weight based on the cellulose ester composition.

[0043] Neutralizer The melt processable cellulose ester composition also contains at least one neutralizing agent. A neutralizing agent is also required in the formulation to manage alkalinity or free alkali as a source of color. The neutralizing agent is a carboxylic acid having a first pKa in the range of about 2 to about 7 or about 2 to about 6. Examples of neutralizing agents include, but are not limited to, citric acid, malic acid, succinic acid, adipic acid, fumaric acid, formic acid, lactic acid, maleic acid, tartaric acid, malonic acid, glutamic acid, glutaric acid, gluconic acid, isophthalic acid, terephthalic acid, glycolic acid, itaconic acid, ferulic acid, mandelic acid, aconitic acid, benzoic acid, aspartic acid, and vanillic acid.

[0044] In one embodiment, or in combination with any other embodiment, the neutralizing agent is selected from the group consisting of citric acid, malic acid, succinic acid, adipic acid, and fumaric acid, particularly for use of the cellulose ester composition in food contact applications. In one embodiment, or in combination with any other embodiment, the neutralizing agent is selected from the group consisting of citric acid, adipic acid, or fumaric acid.

[0045] The minimum amount of neutralizing agent is sufficient to neutralize the free alkali in the cellulose ester composition.However, an excess amount may be added.In one embodiment, or in combination with any other embodiment, about 0.5wt% to about 5wt% of neutralizing agent is added based on the weight of the cellulose ester composition. In one embodiment, or in combination with any other embodiment, the neutralizing agent is present in an amount of from about 0.5 wt % to about 5 wt %, or from about 0.5 wt % to about 4.5 wt %, or from about 0.5 wt % to about 4 wt %, or from about 0.5 wt % to about 3.5 wt %, or from about 0.5 wt % to about 3 wt %, or from about 0.5 wt % to about 2.5 wt %, or from about 0.5 wt % to about 2 wt %, or from about 0.5 wt % to about 1 wt %, or from about 1.5 wt % to about 5 wt %, or from about 1.5 wt % to about 4.5 wt %, or from 1 wt % to about 5 wt %, or from about 1 wt % to about 4.5 wt %, based on the weight of the cellulose ester composition. is present at about 1 wt% to about 4 wt%, or about 1 wt% to about 3.5 wt%, or about 1 wt% to about 3 wt%, or about 1 wt% to about 2.5 wt%, or about 1.5 wt% to about 5 wt%, or about 1.5 wt% to about 4.5 wt%, or about 1.5 wt% to about 4 wt%, or about 1.5 wt% to about 3.5 wt%, or about 1.5 wt% to about 3 wt%, or about 1.5 wt% to about 2.5 wt%, or about 2 wt% to about 5 wt%, or about 2 wt% to about 4.5 wt%, or about 2 wt% to about 4 wt%, or about 2 wt% to about 3.5 wt%, or about 2 wt% to about 3 wt%, and a neutralizing agent is added.

[0046] exterior The appearance of an article comprising a melt-processable cellulose ester composition is important to its acceptability in many applications. For example, bright color and clarity are desirable properties for many melt-processed articles, such as packaging, bags, films, bottles, food containers, straws, stir sticks, cups, plates, bowls, take-out trays and lids, and cutlery.

[0047] CIE L * a * b * In color space, L * The value is a measure of lightness, L* = 0 is black, L * = 100 is white. Therefore, the color of the object is * The value is in the upper half of the range, or L * In one embodiment, or in combination with any other embodiment, the L of the cellulose ester composition is 0.01 to 0.05. * can be in the range of 50-100, 50-95, 50-90, 50-85, 50-80, 50-75, 55-100, 55-95, 55-90, 55-85, 55-80, 55-75, 60-100, 60-95, 60-90, 60-85, 60-80, 60-75, 65-100, 65-95, 65-90, 65-85, 65-80, or 65-75.

[0048] Opacity is a measure of the light transmission through a film or article. Transparency refers to the optical clarity with which an object can be observed when viewed through a film or sheet. The perceived opacity and transparency depend on the thickness of the sample. In the above applications, the thickness of the article can range from about 1 mil for packaging films to 60 mils or more for injection molded cutlery. Clarity can be particularly important for viewing the contents of a container, for example, through the side of a bottle or through the lid of a container. The thickness of melt processed containers, cups and lids varies from about 10 mils to about 30 mils, while bottles are about 20 mils thick.

[0049] The boundary between transparent, translucent and opaque is often highly subjective. In this study, opacity was measured as the % transmission of 600 nm light through a 30 mil thick film. In one embodiment, or in combination with any other embodiment, the % transmission of the cellulose ester composition of the present invention can range from about 1% to about 100%, about 1% to about 90%, about 1% to about 80%, about 1% to about 70%, about 1% to about 60%, about 1% to about 50%, about 1% to about 40%, about 1% to about 30%, about 1% to about 20%, about 1% to about 10%, and about 1%.

[0050] Clarity was quantified as color difference, Delta E (CIE76). On a typical scale, Delta E values ​​range from 0 to 100. The ability of the human eye to distinguish between two colors is related to Delta E, such that colors with Delta E<1 cannot be perceived as different, whereas colors with Delta E>10 are perceived as different at a glance. We used a Delta E cutoff of 20 to designate the easily perceived difference between black and white when viewed through a 30 mil extruded film. The formula for Delta E (CIE76) is:

[0051]

number

[0052] Other elements of the composition In one embodiment, or in combination with any other embodiment, the melt-processable cellulose ester composition may further comprise at least one selected from the group consisting of non-alkaline fillers, additives, biopolymers, stabilizers, and / or odor control agents. Examples of additives include waxes, compatibilizers, biodegradation accelerators, dyes, pigments, colorants, fragrances, gloss control agents, lubricants, antioxidants, viscosity modifiers, antifungal agents, antifogging agents, flame retardants, heat stabilizers, impact modifiers, antibacterial agents, softeners, mold release agents, and combinations thereof. It should be noted that the same type of compound or material may be identified or contained in multiple categories of components in the cellulose ester composition. For example, polyethylene glycol (PEG) may function as a plasticizer or as an additive that does not function as a plasticizer, such as a hydrophilic polymer or a biodegradation accelerator, e.g., a lower molecular weight PEG has a plasticizing effect, and a higher molecular weight PEG functions as a hydrophilic polymer but does not have a plasticizing effect.

[0053] In one embodiment, or in combination with any other embodiment, the cellulose ester composition comprises at least one stabilizer.Desirably, the cellulose ester composition is configurable and / or biodegradable, but a certain amount of stabilizer may be added to provide a selected life span or stability, such as stability against light exposure, oxidation stability, or hydrolysis stability.In various embodiments, the stabilizer may comprise UV absorbers, antioxidants (such as ascorbic acid, BHT, BHA, etc.), other acids and radical scavengers, epoxidized oils, such as epoxidized soybean oil, or combinations thereof.

[0054] Antioxidants may be divided into several classes, including primary and secondary antioxidants. Primary antioxidants are generally known to function essentially as free radical terminators (scavengers). Secondary antioxidants are generally known to break down hydroperoxides (ROOH) into non-reactive products before they decompose into alkoxy and hydroxyl radicals. Secondary antioxidants are often used in combination with free radical scavengers (primary antioxidants) to achieve synergistic inhibition, and secondary AOs are used to extend the life of phenolic-type primary AOs.

[0055] A "primary antioxidant" is an antioxidant that acts by reacting with peroxide radicals via hydrogen transfer to quench the radical. Primary antioxidants generally contain reactive hydroxy or amino groups, such as hindered phenols and secondary aromatic amines. Examples of primary antioxidants are BHT, Irganox™ 1010, 1076, 1726, 245, 1098, 259, and 1425; Ethanox™ 310, 376, 314, and 330; Evernox™ 10, 76, 1335, 1330, 3114, MD1024, 1098, 1726, 120.2246, and 565; Anox™ 20, 29, 330, 70, IC-14, and 1315; Includes Lowinox™ 520, 1790, 22IB46, 22M46, 44B25, AH25, GP45, CA22, CPL, HD98, TBM-6 and WSP; Naugard™ 431, PS48, SP and 445; Songnox™ 1010, 1024, 1035, 1076CP, 1135LQ, 1290PW, 1330FF, 1330PW, 2590PW and 3114FF; and ADK Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 and AO-330.

[0056] "Secondary antioxidants" are often called hydroperoxide decomposers. Secondary antioxidants act by reacting with hydroperoxides to break them down into non-radical, non-reactive and thermally stable products. Secondary antioxidants are often used in conjunction with primary antioxidants. Examples of secondary antioxidants include the organophosphorus (e.g., phosphites, phosphonites) and organosulfur classes of compounds. The phosphorus and sulfur atoms of these compounds react with peroxides, converting them to alcohols. Examples of secondary antioxidants are Ultranox 626, Ethanox™ 368, 326 and 327; Doverphos™ LPG11, LPG12, DP S-680, 4, 10, S480, S-9228, S-9228T; Evernox™ 168 and 626; Irgafos™ 126 and 168; Weston™ DPDP, DPP, EHDP, PDDP, TDP, TLP and TPP; Mark™ CH302, CH55, TNPP, CH66, CH 300, CH301, CH302, CH304 and CH305; ADK Stab 2112, HP-10, PEP-8, PEP-36, 1178, 135A, 1500, 3010, C and TPP; Weston 439, DHOP, DPDP, DPP, DPTDP, EHDP, PDDP, PNPG, PTP, PTP, TDP, TLP, TPP, 398, 399, 430, 705, 705T, TLTTP and TNPP; Alkanox 240, 626, 626A, 627AV, 618F and 619F; and Songnox™ 1680FF, 1680PW and 6280FF.

[0057] In one embodiment, or in combination with any other embodiment, the cellulose ester composition comprises at least one stabilizer, and the stabilizer comprises one or more secondary antioxidants.In one embodiment, or in combination with any other embodiment, the stabilizer comprises a first stabilizer component selected from one or more secondary antioxidants, and a second stabilizer component selected from one or more primary antioxidants, or a combination thereof.

[0058] In one embodiment, or in combination with any other embodiment, the stabilizer is present in an amount, by weight percent of the total amount of secondary antioxidants, based on the total weight of the composition, from 0.01 to 0.8, or from 0.01 to 0.7, or from 0.01 to 0.5, or from 0.01 to 0.4, or from 0.01 to 0.3, or from 0.01 to 0.25, or from 0.01 to 0.2, or from 0.05 to 0.8, or from 0.05 to 0.7. or 0.05-0.5, or 0.05-0.4, or 0.05-0.3, or 0.05-0.25, or 0.05-0.2, or 0.08-0.8, or 0.08-0.7, or 0.08-0.5, or 0.08-0.4, or 0.08-0.3, or 0.08-0.25, or 0.08-0.2. In one class of this embodiment, the stabilizer comprises a secondary antioxidant that is a phosphite compound. In one class of this embodiment, the stabilizer comprises a secondary antioxidant that is a phosphite compound, and another secondary antioxidant that is DLTDP.

[0059] In one subclass of this class, the stabilizer further comprises a second stabilizer component comprising one or more primary antioxidants in an amount in the range of 0.05 to 0.7, or 0.05 to 0.6, or 0.05 to 0.5, or 0.05 to 0.4, or 0.05 to 0.3, or 0.1 to 0.6, or 0.1 to 0.5, or 0.1 to 0.4, or 0.1 to 0.3, based on the total weight of the composition. In another subclass of this class, the stabilizer further comprises a second stabilizer component comprising citric acid in an amount in the range of 0.05 to 0.2, or 0.05 to 0.15, or 0.05 to 0.1, based on the total weight of the composition, as a percentage by weight of the total amount of citric acid. In another subclass of this class, the stabilizer further comprises a second stabilizer component comprising one or more primary antioxidants and citric acid in the amounts discussed herein. In a subclass of this class, the stabilizer contains less than 0.1 wt.% of a primary antioxidant, based on the total weight of the composition, or no primary antioxidant.In a subclass of this class, the stabilizer contains less than 0.05 wt.% of a primary antioxidant, based on the total weight of the composition, or no primary antioxidant.

[0060] In one embodiment, or in combination with any other embodiment, the cellulose ester composition comprises at least one non-alkaline filler.In one embodiment, or in combination with any other embodiment, the other filler is at least one selected from the group consisting of carbohydrates (sugar and salt), cellulose and organic fillers (ground nut shells, cork powder, cereal by-products [e.g., rice husk, oat bran], wood flour, wood fiber, hemp, carbon, coal particles, graphite and starch), mineral and inorganic fillers (talc, silica, silicates, titanium dioxide, glass fiber, glass spheres, boron nitride, aluminum trihydrate, alumina and clay), food waste or by-products (egg shells, distillers grains, and coffee powder), desiccant (e.g., calcium sulfate, magnesium sulfate), alkaline fillers other than those defined in the claims (e.g., CaO, Na2CO3), or combinations (e.g., mixtures) of these fillers.In one embodiment, or in combination with any other embodiment, the cellulose ester composition may comprise at least one filler that also functions as a color additive. In one embodiment, or in combination with any other embodiment, the color additive filler may be selected from carbon, graphite, titanium dioxide, opacifiers, dyes, pigments, toners, and combinations thereof. In one embodiment, or in combination with any other embodiment, the cellulose ester composition may include at least one filler that also functions as a stabilizer or flame retardant.

[0061] In one embodiment, or in combination with any other embodiment, the cellulose ester composition may comprise from 1 to 60 wt%, or from 5 to 55 wt%, or from 5 to 50 wt%, or from 5 to 45 wt%, or from 5 to 40 wt%, or from 5 to 35 wt%, or from 5 to 30 wt%, or from 5 to 25 wt%, or from 10 to 55 wt%, or from 10 to 50 wt%, or from 10 to 45 wt%, or from 10 to 40 wt%, or from 10 to 35 wt%, or or 10-30 wt%, or 10-25 wt%, or 15-55 wt%, or 15-50 wt%, or 15-45 wt%, or 15-40 wt%, or 15-35 wt%, or 15-30 wt%, or 15-25 wt%, or 20-55 wt%, or 20-50 wt%, or 20-45 wt%, or 20-40 wt%, or 20-35 wt%, or 20-30 wt%.

[0062] In one embodiment, or in combination with any other embodiment, depending on the application, for example in disposable food contact applications, the cellulose ester composition may include at least one odor control additive. In one embodiment, or in combination with any other embodiment, depending on the application and the ingredients used in the cellulose ester composition, suitable odor control additives may be selected from vanillin, Pennyroyal M-1178, almond, cinnamyl, spices, spice extracts, volatile organic compounds or small molecules, and Plastidor. In one embodiment, or in combination with any other embodiment, the odor control additive may be vanillin. In one embodiment, or in combination with any other embodiment, the cellulose ester composition may include an amount of odor control additive of 0.01 to 1 wt%, or 0.1 to 0.5 wt%, or 0.1 to 0.25 wt%, or 0.1 to 0.2 wt%, based on the total weight of the composition. The mechanism of the odor control additive may include masking, scavenging, trapping, or a combination thereof.

[0063] As discussed above, the cellulose ester composition may include other additives. In one embodiment, or in combination with any other embodiment, the cellulose ester composition may include at least one compatibilizer. In one embodiment, or in combination with any other embodiment, the compatibilizer may be either a non-reactive compatibilizer or a reactive compatibilizer. The compatibilizer may improve the ability of the cellulose ester or another component to reach a desired small particle size to improve the dispersion of the selected component in the composition. In such an embodiment, depending on the desired formulation, the biodegradable cellulose ester may be in either the continuous or discontinuous phase of the dispersion. In one embodiment, or in combination with any other embodiment, the compatibilizer used may improve the mechanical and / or physical properties of the composition by adjusting the interfacial interaction / bonding between the biodegradable cellulose ester and another component, such as another biodegradable polymer.

[0064] In one embodiment, or in combination with any other embodiment, the cellulose ester composition comprises a compatibilizer in an amount of about 1 to about 40 wt%, or about 1 to about 30 wt%, or about 1 to about 20 wt%, or about 1 to about 10 wt%, or about 5 to about 20 wt%, or about 5 to about 10 wt%, or about 10 to about 30 wt%, or about 10 to about 20 wt%, based on the weight of the cellulose ester composition.

[0065] In one embodiment, or in combination with any other embodiment, if desired, the cellulose ester composition may include a biodegradation and / or decomposition agent, for example, a hydrolysis aid or any intentional degradation-promoting additive added during or after the production of a biodegradable cellulose ester (BCE) and melted or solvent blended with the BCE to form the cellulose ester composition may be added to or contained in the cellulose ester composition. In one embodiment, or in combination with any other embodiment, the additive may promote hydrolysis by releasing acidic or basic residues, and / or may accelerate photo (UV) or oxidative degradation, and / or may promote the growth of selective microbial colonies in compost and soil media to aid in disintegration and biodegradation. In addition to promoting degradation, these additives may have additional functions, such as improving the processability of the article, or improving desired mechanical properties.

[0066] A set of examples of possible decomposition agents include inorganic carbonates, synthetic carbonates, nepheline syenite, talc, aluminum hydroxide, diatomaceous earth, natural or synthetic silica, calcined clay, etc. In embodiments, it may be desirable for these additives to be sufficiently dispersed in the cellulose ester composition matrix.Additives may be used alone or in combination of two or more.

[0067] Another example of a class of possible decomposition agents are aromatic ketones used as oxidative decomposition agents, including benzophenone, anthraquinone, anthrone, acetylbenzophenone, 4-octylbenzophenone, etc. These aromatic ketones may be used alone or in combination of two or more.

[0068] Other examples include transition metal compounds used as oxidative decomposition agents, such as salts of cobalt or magnesium, such as aliphatic carboxylic acids (C12-C20) salts of cobalt or magnesium, or cobalt stearate, cobalt oleate, magnesium stearate and magnesium oleate; alternatively, anatase titanium dioxide, or titanium dioxide may be used. Mixed phase titanium dioxide particles may be used, in which both rutile and anatase crystal structures are present within the same particle. The particles of the photoactivator may have a relatively high surface area, for example, from about 10 to about 300 sq.m / g, or from 20 to 200 sq.m / g, as measured by the BET surface area method. The photoactivator may be added to a plasticizer if desired. These transition metal compounds may be used alone or in combination of two or more.

[0069] Examples of rare earth compounds that can be used as oxidative decomposition agents include rare earths belonging to Group 3A of the periodic table and their oxides. Specific examples thereof include cerium (Ce), yttrium (Y), neodymium (Nd), rare earth oxides, hydroxides, rare earth sulfates, rare earth nitrates, rare earth acetates, rare earth chlorides, rare earth carboxylates, etc. More specific examples thereof include cerium oxide, cerium sulfate, ammonium cerium sulfate, ammonium cerium nitrate, cerium acetate, lanthanum nitrate, cerium chloride, cerium nitrate, cerium hydroxide, cerium octylate, lanthanum oxide, yttrium oxide, scandium oxide, etc. These rare earth compounds may be used alone or in combination of two or more kinds.

[0070] In one embodiment, or in combination with any other embodiment, the melt-processible cellulose ester composition includes additives with degradation-promoting functionality to enhance biodegradability, including enzymes, bacterial cultures, sugars, glycerol, or other energy sources. The additives may also include hydroxylamine esters and thio compounds.

[0071] In certain embodiments, other possible biodegradation and / or degradation agents may include swelling agents and disintegration agents. Swelling agents may be hydrophilic materials that increase in volume after absorbing water and exert pressure on the surrounding matrix. Disintegration agents may be additives that promote the breakage of the matrix into smaller pieces in an aqueous environment. Examples include minerals and polymers, including crosslinked or modified polymers and swellable hydrogels. In embodiments, the BCE composition may include water-swellable minerals or clays and their salts, such as laponite and bentonite; hydrophilic polymers, such as poly(acrylic acid) and salts, poly(acrylamide), poly(ethylene glycol) and poly(vinyl alcohol); polysaccharides and gums, such as starch, alginate, pectin, chitosan, psyllium, xanthan gum; guar gum, locust bean gum; and modified polymers, such as crosslinked PVP, sodium starch glycolate, carboxymethylcellulose, gelatinized starch, croscarmellose sodium; or combinations of these additives.

[0072] Examples of other hydrophilic polymers or biodegradation-promoting agents may include glycols, polyglycols, polyethers and polyhydric alcohols, or other biodegradable polymers, such as poly(glycolic acid), poly(lactic acid), polyethylene glycols, polypropylene glycols, polydioxanes, polyoxalates, poly(α-esters), polycarbonates, polyanhydrides, polyacetals, polycaprolactones, poly(orthoesters), polyamino acids, poly(hydroxyalkanoates), aliphatic polyesters, such as poly(butylene) succinate, poly(ethylene) succinate, starch, regenerated cellulose, or aliphatic-aromatic polyesters, such as PBAT, as well as co-polyesters of any of these.

[0073] In one embodiment, or in combination with any other embodiment, examples of colorants are carbon black, iron oxides, such as red or blue iron oxide, titanium dioxide, silicon dioxide, cadmium red, calcium carbonate, kaolin clay, aluminum hydroxide, barium sulfate, zinc oxide, aluminum oxide; and organic pigments, such as azo and diazo and triazo pigments, condensed azo, azo lakes, naphthol pigments, anthrapyrimidines, benzimidazolones, carbazoles, diketopyrrolopyrroles, flavanthrones, indigoid pigments, isoindolinones, isoindolines, isoviolanthrones, metals. Complex pigments, oxazines, perylenes, perinones, pyranthrones, pyrazoloquinazolones, quinophthalones, triarylcarbonium pigments, triphendioxazines, xanthenes, thioindigo, indanthrones, isoindanthrones, anthanthrones, anthraquinones, isodibenzanthrones, triphendioxazines, quinacridones and phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, as well as lakes of acid, base and mordant dyes, as well as isoindolinone pigments, as well as vegetable and vegetable dyes, as well as any other available colorants or dyes.

[0074] In one embodiment, or in combination with any other embodiment, gloss control agents and fillers for adjusting gloss level may include silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate, and the like.

[0075] Suitable flame retardants may include silica, metal oxides, phosphates, catechol phosphates, resorcinol phosphates, borates, inorganic hydrates, and aromatic polyhalides.

[0076] Antifungal and / or antibacterial agents include polyene antifungals (e.g., natamycin, rimocidin, filipin, nystatin, amphotericin B, candicin, and hamycin), imidazole antifungals such as miconazole (available as MICATIN® from WellSpring Pharmaceutical Corporation), ketoconazole (commercially available as NIZORAL® from McNeil consumer Healthcare), clotrimazole (available as LOTRAMIN® and LOTRAMIN® from Merck), and the like. AF® and available from Bayer as CANESTEN®), econazole, omoconazole, bifonazole, butoconazole, fenticonazole, isoconazole, oxiconazole, sertaconazole (commercially available as ERTACZO® from OrthoDematologics), sulconazole, and ticonazole; triazole antifungals such as fluconazole, itraconazole, isavuconazole, ravuconazole, posaconazole, voriconazole, terconazole, and albaconazole; thiazole antifungals such as abafungin, allylamine antifungals such as terbinafine (commercially available as LAMISIL® from Novartis Consumer Health, Inc.), naftifine (commercially available as NAFTIN® from Merz Pharmaceuticals), and butenafine (LOTRAMIN® from Merck). ULTRA®), echinocandin antifungals (e.g., anidulafungin, caspofungin, and micafungin), poligodial, benzoic acid, ciclopirox, tolnaftate (e.g., available as TINACTIN® from MDS Consumer Care, Inc.), undecylenic acid, flucytosine, 5-fluorocytosine, griseofulvin, haloprogin, caprylic acid, and any combination thereof.

[0077] Viscosity modifiers that may be used for the purpose of adjusting the melt flow index or viscosity of the biodegradable cellulose ester composition include polyethylene and polypropylene glycols, and glycerin.

[0078] In one embodiment, or in combination with any other embodiment, other components that may be included in the melt processable cellulose ester composition may function as mold release agents or lubricants (e.g., fatty acids, ethylene glycol distearate), antiblocking or slip agents (e.g., fatty acid esters, metal stearates (e.g., zinc stearate) and waxes), antifogging agents (e.g., surfactants), heat stabilizers (e.g., epoxy stabilizers, epoxidized soybean oil (ESBO), linseed oil and sunflower oil derivatives), antistatic agents, foaming agents, biocides, impact modifiers, or reinforcing fibers. There may be more than one component in the BCE composition. It is noted that an additional component may perform more than one function in the melt processable cellulose ester composition. The different (or specific) functionality of any particular additive (or component) to the melt processable cellulose ester composition may depend on its physical properties (e.g., molecular weight, solubility, melting temperature, Tg, etc.) and / or the amount of such additive / component in the overall composition. For example, polyethylene glycol can function as a plasticizer at one molecular weight, or as a hydrophilic agent (with little or no plasticizing effect) at another molecular weight.

[0079] In embodiments, fragrances may be added as desired. Examples of fragrances include spices, spice extracts, herb extracts, essential oils, scent enhancers, volatile organic compounds, volatile small molecules, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, ethyl butyrate, isoamyl acetate, pentyl butyrate, pentyl valerate, octyl acetate, myrcene, geraniol, nerol, citral, citronellal, citronellol, linalool, nerolidol, limonene, camphor, terpineol, alpha-ionone, thujone, benzaldehyde, eugenol, isoeugenol, cinnamaldehyde, ethyl maltol, Vanilla, vanillin, cinnamyl alcohol, anisole, anethole, estragole, thymol, furaneol, methanol, rosemary, lavender, citrus, freesia, apricot flower, green vegetables, peach, jasmine, rosewood, pine, thyme, oakmoss, musk, vetiver, myrrh, blackcurrant, bergamot, grapefruit, acacia, passionflower, sandalwood, tonka bean, mandarin, neroli, violet leaf, gardenia, red fruits, ylang ylang, goldenrod, mimosa, tonka bean, wood, ambergris, trumpet Daffodil, hyacinth, narcissus, blackcurrant bud, iris, raspberry, lily of the valley, sandalwood, vetiver, cedarwood, neroli, strawberry, carnation, oregano, honey, musk, heliotrope, caramel, coumarin, patchouli, dewberry, helonial, coriander, pimento berry, labdanum, goldenrod, aldehydes, orchid, amber, orris, moonflower, palmarosa, cinnamon, nutmeg, moss, snowbell, pineapple, foxglove, tulip, wisteria, clematis, annatto Bergris, gum, resin, musk, plum, beaver, musk, myrrh, geranium, rose violet, daffodil, spicy carnation, galbanum, petitgrain, iris, honeysuckle, pepper, raspberry, benzoin, mango, coconut, hesperides, beaver, sweet osmanthus, oakmoss, nectarine, mint, anise, cinnamon, orris, apricot, plumeria, marigold, rose oil, daffodil, tolu balsam, frankincense, amber, orange blossom, bourbon vetiver, opopanax,White musk, papaya, sugar candy, jackfruit, nectar, lotus flower, lily of the valley, mulberry, wormwood, ginger, juniper berry, benzoin, peony, violet, lemon, lime, hibiscus, white rum, basil, lavender, balsamics, fo-ti-tieng, sweet osmanthus, karo karunde, white orchid, calla lily, white rose, emperor lily, tagetes, ambergris, ivy, grass, rubber tree, spearmint, clary sage, cottonwood, grape, brimbelle, lotus, cyclamen, orchid, glycine, tiare flower, flowering plant, green osmanthus, passionflower, blue rose, bay laurel, goldenrod, African tagetes, Anatolian rose rose, Auvergne narcissus, British broom, British broom chocolate, Bulgarian rose, Chinese patchouli, Chinese gardenia, Calabrian mandarin, Comoros Island tuberose, Ceylonese cardamom, Caribbean passion fruit, rosa damascena, Georgia peach, lady's lily, Egyptian jasmine, Egyptian marigold, Ethiopian musk, Farnesian cassie, Florentine iris, French jasmine, French daffodil, French hyacinth, Guinea oranges, Guyana wacapua, Grasse petitgrain petitgrain), Grasse rose, Grasse tuberose, Haitian vetiver, Hawaiian pineapple, Israeli basil, Indian sandalwood, Indian Ocean vanilla, Italian bergamot, Italian iris, Jamaican pepper, May rose, Madagascar ylang ylang, Madagascar vanilla,Molokan jasmine, Molokan rose, Molokan oak moss, Molokan orange blossom, Mysore sandalwood, Oriental rose, Russian leather, Russian coriander, Sicilian mandarin, South African marigold, South American tonka bean, Singapore patchouli, Spanish orange blossom, Sicilian lime, Reunion vetiver, Turkish rose, Thai benzoin, Tunisian orange blossom, Yugoslavian oak moss, Virginian cedarwood, Utah yarrow, West Indian rosewood, and the like, and any combination thereof.

[0080] In one embodiment, or in combination with any other embodiment, the cellulose ester composition and any article made from or containing such a composition comprises a biodegradable cellulose ester (BCE) containing some recycled content. In an embodiment, the recycled content is provided by a reactant derived from a recycled material that is the source of one or more acetyl groups on the BCE. In an embodiment, the reactant is derived from recycled plastic. In an embodiment, the reactant is derived from recycled plastic content syngas. By "recycled plastic content syngas" is meant a syngas obtained from a syngas operation utilizing a feedstock containing at least some content of recycled plastic, as more fully described herein below in various embodiments. In an embodiment, the recycled plastic content syngas can be made according to any of the processes for producing syngas described herein; can include or consist of any of the syngas compositions or syngas composition streams described herein; or can be made from any of the feedstock compositions described herein.

[0081] In one embodiment, or in combination with any other embodiment, the feedstock (for the syngas operation) may be in the form of a combination of one or more particulate fossil fuel sources and particulate recycled plastics. In one embodiment, or in any of the mentioned embodiments, the solid fossil fuel source may include coal. In one embodiment, or in combination with any other embodiment, the feedstock is fed to a gasifier along with an oxidant gas, and the feedstock is converted to syngas.

[0082] In one embodiment, or in combination with any other embodiment, recycled plastic content syngas is utilized to make at least one chemical intermediate in the reaction scheme for making recycled cellulose ester.In one embodiment, or in combination with any other embodiment, recycled plastic content syngas can be a component of the feedstock (used to make at least one CA intermediate), including other syngas sources, hydrogen, carbon monoxide, or combinations thereof.In one embodiment, or in any of the mentioned embodiments, the only syngas source used to make CA intermediate is recycled plastic content syngas.

[0083] In one embodiment, or in combination with any other embodiment, the CA intermediates produced using recycled content syngas, such as recycled plastic content syngas, can be selected from methanol, acetic acid, methyl acetate, acetic anhydride, and combinations thereof. In one embodiment, or in combination with any other embodiment, the CA intermediates can be at least one reactant or at least one product in one or more of the following reactions: (1) syngas conversion to methanol; (2) syngas conversion to acetic acid; (3) methanol conversion to acetic acid, such as the carbonylation of methanol to produce acetic acid; (4) the production of methyl acetate from methanol and acetic acid; and (5) conversion of methyl acetate to acetic anhydride, such as the carbonylation of methyl acetate and methanol to acetic acid and acetic anhydride.

[0084] In one embodiment, or in combination with any other embodiment, the recycled plastic content syngas is used to produce at least one cellulose reactant. In an embodiment, the recycled plastic content syngas is used to produce at least one recycled cellulose ester.

[0085] In one embodiment, or in combination with any other embodiment, recycled plastic content syngas is utilized to make acetic anhydride. In one embodiment, or in combination with any other embodiment, syngas containing recycled plastic content syngas is first converted to methanol, which is then used in a reaction scheme to make acetic anhydride. "RPS acetic anhydride" refers to acetic anhydride derived from recycled plastic content syngas. Derived from means that at least a portion of the raw feedstock (used in any reaction scheme to make CA intermediate) has some content of recycled plastic content syngas.

[0086] In one embodiment, or in combination with any other embodiment, RPS acetic anhydride is utilized as a CA intermediate reactant for the esterification of cellulose to prepare recycled BCE, as discussed more fully above. In one embodiment, or in combination with any other embodiment, RPS acetate is utilized as a reactant to prepare cellulose esters or cellulose diacetate.

[0087] In one embodiment, or in combination with any other embodiment, recycled CA is prepared from a cellulose reactant that includes acetic anhydride derived from recycled plastic content syngas.

[0088] In one embodiment, or in combination with any other embodiment, the recycled plastic content syngas comprises a gasification product from a gasification feedstock. In one embodiment, or in combination with any other embodiment, the gasification product is produced by a gasification process using a gasification feedstock comprising recycled plastic. In an embodiment, the gasification feedstock comprises coal.

[0089] In an embodiment, the gasification feedstock comprises a liquid slurry comprising coal and recycled plastics. In an embodiment, the gasification process comprises gasifying the gasification feedstock in the presence of oxygen.

[0090] In one embodiment, or in combination with any other embodiment, a recycled cellulose ester composition is provided that includes at least one biodegradable cellulose ester having at least one substituent on the anhydroglucose unit (AGU) derived from one or more chemical intermediates, at least one of the chemical intermediates being derived, at least in part, from recycled plastic content syngas.

[0091] In one embodiment, or in combination with any other embodiment, the recycled cellulose ester is biodegradable and contains a content derived from renewable sources, such as cellulose from wood or cotton linters, and a content derived from recycled material sources, such as recycled plastics.Thus, in an embodiment, a melt-processable material is provided that is biodegradable and contains both renewable and recycled content, i.e., is made from renewable and recycled sources.

[0092] In one embodiment, or in combination with any other embodiment, a cellulose ester composition is provided, comprising a recycled cellulose ester prepared by an integrated process comprising the following processing steps: (1) preparing a recycled plastic content syngas in a syngas operation utilizing a feedstock containing a solid fossil fuel source and at least some recycled plastic content; (2) preparing at least one chemical intermediate from the syngas; (3) reacting the chemical intermediate in a reaction scheme to prepare at least one cellulose reactant for preparing a recycled cellulose ester, and / or selecting a chemical intermediate to be the at least one cellulose reactant for preparing a recycled cellulose ester; and (4) reacting at least one cellulose reactant to prepare a recycled cellulose ester, wherein the recycled cellulose ester comprises at least one substituent on an anhydroglucose unit (AGU) derived from the recycled plastic content syngas.

[0093] In one embodiment, or in combination with any other embodiment, the process steps (1)-(4) are carried out in a system with fluid and / or gas communication (i.e., including the possibility of a combination of fluid and gas communication). It should be understood that in one or more of the reaction schemes for producing recycled cellulose esters starting from recycled plastic content syngas, chemical intermediates may be temporarily stored in a storage vessel and then reintroduced into the integrated process system.

[0094] In one embodiment, or in combination with any other embodiment, at least one chemical intermediate is selected from methanol, methyl acetate, acetic anhydride, acetic acid, or a combination thereof.In an embodiment, one chemical intermediate is methanol, and methanol is used in the reaction scheme to make a second chemical intermediate that is acetic anhydride.In an embodiment, the cellulose reactant is acetic anhydride.

[0095] The biodegradable cellulose ester useful in the embodiments of the present invention may have a degree of substitution in the range of 1.0 to 2.5. In some cases, the cellulose ester described herein may have an average degree of substitution of at least about 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45 or 1.5, and / or no more than about 2.5, 2.45, 2.4, 2.35, 2.3, 2.25, 2.2, 2.15, 2.1, 2.05, 2.0, 1.95, 1.9, 1.85, 1.8 or 1.75.

[0096] In one embodiment, or in combination with any other embodiment, the biodegradable cellulose ester can have a number average molecular weight (Mn) of 100,000 or less, or 90,000 or less, measured using gel permeation chromatography in terms of polystyrene and using N-methyl-2-pyrrolidone (NMP) as a solvent. In some cases, the biodegradable cellulose ester can have an Mn of at least about 10,000, at least about 20,000, 25,000, 30,000, 35,000, 40,000 or 45,000, and / or about 100,000, 95,000, 90,000, 85,000, 80,000, 75,000, 70,000, 65,000, 60,000 or 50,000 or less.

[0097] Biodegradation and disintegration In embodiments, cellulose ester-containing articles can be biodegradable and can have a certain degree of disintegration.Biodegradation refers to the mineralization of a substance by the action of microbial metabolism, or the conversion into biomass, CO2 and water.On the other hand, disintegration refers to the visible destruction of a material, often by the combined action of physical, chemical and biological mechanisms.

[0098] In one embodiment, or in combination with any other embodiment, the melt-processable cellulose ester composition shows improved disintegration compared to formulations that do not contain alkaline fillers. The improvement can be measured as thicker section disintegration in the same time, or it can be referred to as faster rate of disintegration. The degree of disintegration can be characterized by the weight loss of the sample over a given period of exposure to a certain environmental condition. In some cases, the melt-processable cellulose ester composition can show at least about 5, 10, 15 or 20 percent weight loss after 60 days of burial in soil, and / or at least about 15, 20, 25, 30 or 35 percent weight loss after 15 days of exposure to a typical municipal solid waste composting device. However, the rate of degradation can vary depending on the specific end use of the article, and the composition of the article, as well as the specific test. Exemplary test conditions are described in U.S. Pat. No. 5,970,988 and U.S. Pat. No. 6,571,802.

[0099] In some embodiments, melt-processable cellulose ester compositions can be in the form of biodegradable disposable (molded / formed) articles.The melt-processable cellulose ester compositions described herein can exhibit improved levels of environmental non-persistence, characterized by greater than expected decomposition under various environmental conditions.The cellulose ester-containing articles described herein can meet or exceed the acceptance criteria set by international testing methods and authorities for industrial compostability, home compostability, and / or soil biodegradability.

[0100] Disintegration refers to the physical destruction of materials. Disintegration of materials can be influenced by biological, chemical and / or physical processes. Methods for monitoring disintegration during composting can be performed under standardized laboratory conditions, in synthetic compost, or as field tests in reliable industrial or home composting systems. Standardized methods for monitoring disintegration in industrial composts are defined in ISO-20200 and ISO-16929. Qualitative screening tests can also be based on these standardized tests.

[0101] Home composting can be simulated under laboratory conditions, for example by running ISO-16929 or ISO-20200 at lower temperatures or by monitoring the breakdown of test materials in a home composting vessel. Home composting can also be carried out under conditions similar to those described in the standardized methods, but on a larger scale in outdoor home composting bins.

[0102] To be considered "compostable", a material must meet four criteria: (1) the material should pass the biodegradation requirements when tested under controlled composting conditions at elevated temperature (58°C) according to ISO14855-1 (2012), which corresponds to 90% absolute biodegradation, or 90% relative biodegradation to a control polymer; (2) the material must reach 90% disintegration when tested under aerobic composting conditions according to ISO16929 (2013) or ISO20200; (3) the test material must meet all of the requirements for volatile solids, heavy metals and fluorine as specified in ASTM D6400 (2012), EN13432 (2000) and ISO17088 (2012); and (4) the material should not cause adverse effects on plant growth. As used herein, the term "biodegradable" generally refers to the biological transformation and consumption of organic molecules. Biodegradability is an inherent property of the material itself, and materials may exhibit different degrees of biodegradability depending on the particular conditions to which they are exposed. The term "disintegrable" refers to the tendency of a material to physically break down into smaller pieces when exposed to certain conditions. Disintegration depends on both the material itself and the physical size and composition of the article being tested. Ecotoxicity is a measure of the impact of a material on vegetation, and the heavy metal content of a material is determined according to procedures set out in standard test methods.

[0103] The cellulose ester composition (or an article containing it) may exhibit at least 70 percent biodegradation in a period of 50 days or less when tested under aerobic composting conditions at ambient temperature (28° C.±2° C.) according to ISO 14855-1 (2012). In some cases, the cellulose ester composition (or an article containing it) may exhibit at least 70 percent biodegradation in a period of 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, or 37 days or less when tested under these conditions, also referred to as "home composting conditions." These conditions do not have to be aqueous or anaerobic. In some cases, the cellulose ester composition (or article containing it) may exhibit at least about 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, or 88 percent total biodegradation when tested according to ISO 14855-1 (2012) for a period of 50 days under home composting conditions, which may represent a relative biodegradation of at least about 95, 97, 99, 100, 101, 102, or 103 percent compared to cellulose subjected to the same test conditions.

[0104] To be considered "biodegradable" under home composting conditions according to French standard NF T51-800 and Australian standard AS5810, a material must show at least 90% total biodegradation (e.g., compared to the initial sample), or at least 90% of the maximum degradation of a suitable reference material after both the reference and test material reach a plateau. The maximum test period for biodegradation under home composting conditions is 1 year. The cellulose ester composition described herein may show at least 90% biodegradation within 1 year under home composting conditions, as measured according to 14855-1 (2012). In some cases, the cellulose ester composition (or an article containing it) may exhibit at least about 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 percent biodegradation under home composting conditions within one year, as measured according to 14855-1(2012), or the cellulose ester composition (or an article containing it) may exhibit 100 percent biodegradation within one year.

[0105] Additionally or alternatively, the cellulose ester compositions described herein (or articles comprising same) may exhibit at least 90 percent biodegradation within about 350, 325, 300, 275, 250, 225, 220, 210, 200, 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, or 50 days under home composting conditions, as measured according to ISO 14855-1 (2012). In some cases, the cellulose ester compositions (or articles comprising same) may be at least about 97, 98, 99, or 99.5 percent biodegradable within about 70, 65, 60, or 50 days under home composting conditions, as measured according to ISO 14855-1 (2012). As a result, cellulose ester compositions (or articles containing them) can be considered biodegradable when tested under home composting conditions, for example according to French standard NF T51-800 and Australian standard AS5810.

[0106] The cellulose ester composition (or article containing it) may exhibit at least 60 percent biodegradation in a period of 45 days or less when tested under aerobic composting conditions at a temperature of 58° C. (±2° C.) in accordance with ISO 14855-1 (2012). In some cases, the cellulose ester composition (or article containing it) may exhibit at least 60 percent biodegradation in a period of 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, or 27 days or less when tested under these conditions, also referred to as "industrial composting conditions." These do not have to be aqueous or anaerobic conditions. In some cases, the cellulose ester composition (or article containing it) can exhibit at least about 65, 70, 75, 80, 85, 87, 88, 89, 90, 91, 92, 93, 94, or 95 percent total biodegradation when tested according to ISO 14855-1 (2012) for a period of 45 days under industrial composting conditions. This can represent a relative biodegradation of at least about 95, 97, 99, 100, 102, 105, 107, 110, 112, 115, 117, or 119 percent compared to the same cellulose ester composition (or article containing it) subjected to the same test conditions.

[0107] To be considered "biodegradable" under industrial composting conditions according to ASTM D6400 and ISO17088, at least 90 percent of the organic carbon in the whole article (or for each component present in an amount greater than 1% by dry mass) must be converted to carbon dioxide by the end of the test period, either in comparison with a control or in absolute terms. According to European Standard ED13432 (2000), the material must show at least 90 percent biodegradation overall, or at least 90 percent of the maximum degradation of a suitable reference material after both the reference and test article reach a plateau. The maximum test period for biodegradability under industrial composting conditions is 180 days. The cellulose ester composition (or article containing it) described herein may show at least 90 percent biodegradation within 180 days under industrial composting conditions, measured according to ISO14855-1 (2012). In some cases, the cellulose ester composition (or an article comprising the same) may exhibit at least about 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 percent biodegradation within 180 days, as measured according to ISO 14855-1 (2012) under industrial composting conditions, or the cellulose ester composition (or an article comprising the same) may exhibit 100 percent biodegradation within 180 days.

[0108] Additionally or alternatively, the cellulose ester compositions described herein (or articles comprising same) may exhibit at least 90 percent biodegradation within about 175, 170, 165, 160, 155, 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, or 45 days under industrial composting conditions as measured according to ISO14855-1 (2012). In some cases, the cellulose ester compositions (or articles comprising same) may be at least about 97, 98, 99, or 99.5 percent biodegradable within about 65, 60, 55, 50, or 45 days under industrial composting conditions as measured according to ISO14855-1 (2012). As a result, the cellulose ester compositions described herein (or articles containing same) can be considered biodegradable according to ASTM D6400 and ISO 17088 when tested under industrial composting conditions.

[0109] The cellulose ester composition (or article containing it) may exhibit at least 60 percent biodegradation in soil within 130 days, measured according to ISO 17556 (2012) under aerobic conditions at ambient temperature. In some cases, the cellulose ester composition (or article containing it) may exhibit at least 60 percent biodegradation within a period of 130, 120, 110, 100, 90, 80, or 75 days, when tested under these conditions, also referred to as "soil composting conditions". These may not be aqueous or anaerobic conditions. In some cases, the cellulose ester composition (or article containing it) may exhibit at least about 65, 70, 72, 75, 77, 80, 82, or 85 percent total biodegradation, when tested according to ISO 17556 (2012) under soil composting conditions for a period of 195 days. This can represent a relative biodegradation of at least about 70, 75, 80, 85, 90, or 95 percent as compared to the same cellulose ester composition (or article containing it) subjected to the same test conditions.

[0110] To be considered "biodegradable" under soil composting conditions according to Vincotte's OK Biodegradable SOIL Certificate of Conformity and DIN CERTCO's DIN Gepruft Soil Biodegradability Certification Scheme, a material must demonstrate at least 90 percent overall biodegradation (e.g. compared to the initial sample) or at least 90 percent of the maximum degradation of a suitable reference material after a plateau has been reached for both the reference and test articles. The maximum test period for biodegradation under soil composting conditions is 2 years.

[0111] The cellulose ester compositions described herein (or articles containing them) may exhibit at least 90 percent biodegradation within 2 years, 1.75 years, 1 year, 9 months, or 6 months under soil composting conditions, as measured according to ISO17556 (2012). In some cases, the cellulose ester compositions (or articles containing them) may exhibit at least about 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 percent biodegradation within 2 years, or the cellulose ester compositions (or articles containing them) may exhibit 100 percent biodegradation within 2 years, as measured according to ISO17556 (2012) under soil composting conditions.

[0112] Additionally or alternatively, the cellulose ester compositions described herein (or articles comprising same) may exhibit at least 90 percent biodegradation within about 700, 650, 600, 550, 500, 450, 400, 350, 300, 275, 250, 240, 230, 220, 210, 200, or 195 days under soil composting conditions, as measured according to ISO 17556 (2012). In some cases, the cellulose ester compositions (or articles comprising same) may be at least about 97, 98, 99, or 99.5 percent biodegradable within about 225, 220, 215, 210, 205, 200, or 195 days under soil composting conditions, as measured according to ISO 17556 (2012). As a result, the cellulose ester compositions described herein (or articles containing same) may meet the requirements to receive Vincotte's OK Biodegradable SOIL Certification and to meet the standards of DIN CERTCO's DIN Gepruft soil biodegradability certification scheme.

[0113] In some embodiments, the cellulose ester composition of the present invention (or the article comprising it) may contain less than 1, 0.75, 0.50, or 0.25 weight percent of unknown biodegradable components.In some cases, the cellulose ester composition described herein (or the article comprising it) may not contain unknown biodegradable components.

[0114] To monitor the biodegradation of polymeric materials, the Aquatic Biodegradation Test - O2 Consumption (OECD 301F) can be used. OECD 301F is an aquatic aerobic biodegradation test that determines the biodegradability of a material by measuring the oxygen consumption. OECD 301F is most frequently used for insoluble and volatile materials. The purity or proportion of the main components of the test material is important in calculating the theoretical oxygen demand (ThOD). As with other 301 test methods, the standard test period for OECD 301F is a minimum of 28 days. A solution or suspension in mineral medium of the test substance is seeded and incubated under aerobic conditions in the dark or under diffuse light. Cellulose is tested in parallel as a positive control to check the operation of the procedure.

[0115] Aqueous biodegradation is another measure of the biodegradability of the material blend materials. Biological oxygen demand [BOD] was measured over time using an OxiTop® Control OC110 respirometer system. This is accomplished by measuring the negative pressure that is created when oxygen is consumed in a closed bottle system. NaOH tablets are added to the system to collect the CO2 that is generated when O2 is consumed. The CO2 and NaOH react to form Na2CO3, which pulls CO2 from the gas phase, resulting in a measurable negative pressure. The OxiTop measuring head records this negative pressure value and wirelessly relays the information to a controller, which converts the generated CO2 to BOD in a 1:1 ratio. The measured biological oxygen demand can be compared to the theoretical oxygen demand of each test material to determine the percentage of biodegradation. In one embodiment of the present invention, if an alkaline filler is included in the blend, the aqueous biodegradation rate can be the same or different.

[0116] In addition to being biodegradable under industrial and / or home composting conditions, the cellulose ester composition described herein (or the article containing it) may also be compostable under home and / or industrial conditions.As mentioned above, a material is considered compostable if it meets or exceeds the requirements set forth in EN13432 for biodegradability, disintegrability, heavy metal content, and ecotoxicity.The cellulose ester composition described herein (or the article containing it) may exhibit sufficient compostability under home and / or industrial composting conditions to meet the requirements for receiving the OK Compost and OK Compost HOME certification from Vincotte.

[0117] In some cases, the cellulose ester composition (or the article containing it) described herein can have a volatile solids concentration, heavy metals and fluorine content that meets all of the requirements set forth in EN13432 (2000).In addition, the cellulose ester composition (or the article containing it) can have no adverse effect on compost quality (including chemical parameters and ecotoxicity tests).

[0118] In some cases, the cellulose ester composition (or an article comprising it) may exhibit at least 90 percent disintegration under industrial composting conditions within 26 weeks as measured according to ISO 16929 (2013) or ISO 20200. In some cases, the cellulose ester composition (or an article comprising it) may exhibit at least about 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 percent disintegration under industrial composting conditions within 26 weeks, or the cellulose ester composition (or an article comprising it) may exhibit 100 percent disintegration under industrial composting conditions within 26 weeks. Alternatively, or in addition, the cellulose ester composition (or article comprising same) may exhibit at least 90 percent disintegration within about 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 weeks under industrial composting conditions, as measured according to ISO 16929 (2013) or ISO 20200. In some cases, the cellulose ester composition (or article comprising same) described herein may exhibit at least 97, 98, 99, or 99.5 percent disintegration within about 12, 11, 10, 9, or 8 weeks under industrial composting conditions, as measured according to ISO 16929 (2013) or ISO 20200.

[0119] In some cases, the cellulose ester composition (or an article comprising it) may exhibit at least 90 percent disintegration under home composting conditions within 26 weeks as measured according to ISO 16929 (2013) or ISO 20200. In some cases, the cellulose ester composition (or an article comprising it) may exhibit at least about 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.5 percent disintegration under home composting conditions within 26 weeks, or the cellulose ester composition (or an article comprising it) may exhibit 100 percent disintegration under home composting conditions within 26 weeks. Alternatively, or in addition, the cellulose ester composition (or article comprising same) may exhibit at least 90 percent disintegration within about 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, or 15 weeks under home composting conditions, as measured according to ISO 16929 (2013) or ISO 20200. In some cases, the cellulose ester composition (or article comprising same) described herein may exhibit at least 97, 98, 99, or 99.5 percent disintegration within 20, 19, 18, 17, 16, 15, 14, 13, or 12 weeks under home composting conditions, as measured according to ISO 16929 (2013) or ISO 20200.

[0120] In one embodiment, or in combination with any other embodiment, when the cellulose ester composition is formed into a film having a maximum thickness of 0.02, or 0.05, or 0.07, or 0.10, or 0.13, or 0.25, or 0.38, or 0.51, or 0.64, or 0.76, or 0.89, or 1.02, or 1.14, or 1.27, or 1.40, or 1.52, or 1.78, or 2.0, or 2.3, or 2.5, or 3.0, or 3.3, or 3.8 mm, or injection molded into an article having such a maximum thickness, the film or article exhibits greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO16929(2013) or ISO20200. In certain embodiments, when the cellulose ester composition is formed into a film having a maximum thickness of 0.02, or 0.05, or 0.07, or 0.10, or 0.13, or 0.25, or 0.38, or 0.51, or 0.64, or 0.76, or 0.89, or 1.02, or 1.14, or 1.27, or 1.40, or 1.52, or 1.78, or 2.0, or 2.3, or 2.5, or 3.0, or 3.3, or 3.8 mm, or injection molded into an article having such a maximum thickness, the film or article exhibits greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO (2013) or ISO 20200. In certain embodiments, when the cellulose ester composition is formed into a film having a thickness of 0.13, or 0.25, or 0.38, or 0.51, or 0.64, or 0.76, or 0.89, or 1.02, or 1.14, or 1.27, or 1.40, or 1.52 mm, the film exhibits greater than 90, or 95, or 96, or 97, or 98, or 99% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200.In one particular embodiment, the cellulose ester composition has a carboxyl group content of 0.02, or 0.05, or 0.07, or 0.10, or 0.13, or 0.25, or 0.38, or 0.51, or 0.64, or 0.76, or 0.89, or 1.02, or 1.14, or 1.27, or 1.40, or 1.52, or 1.78, or 2.0, or 2.3, or 2.5, or 3.0, or 3.3, When formed into a film having a maximum thickness of 3.8 mm or injection molded into an article having such a maximum thickness, the film or article exhibits greater than 90, or 95, or 96, or 97, or 98, or 99% disintegration after 8, or 9, or 10, or 11, or 12, or 13, or 14, or 15, or 16 weeks according to the disintegration testing protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200.

[0121] In some embodiments, the cellulose ester composition (or article containing it) described herein may be substantially free of photodecomposition agents. For example, the cellulose ester composition (or article containing it) may contain about 1, 0.75, 0.50, 0.25, 0.10, 0.05, 0.025, 0.01, 0.005, 0.0025, or 0.001 weight percent or less of photodecomposition agents based on the total weight of the cellulose ester composition (or article containing it), or the cellulose ester composition (or article containing it) may be free of photodecomposition agents. Examples of such photodecomposition agents include, but are not limited to, pigments that act as photooxidation catalysts and may be optionally enhanced by the presence of one or more metal salts, oxidative poromotors, and combinations thereof. The pigments may include coated or uncoated anatase or rutile titanium dioxide, which may be present alone or in combination with one or more of the reinforcing components, such as various types of metals. Other examples of photodegradants include benzoin, benzoin alkyl ethers, benzophenone and its derivatives, acetophenone and its derivatives, quinones, thioxanthones, phthalocyanines and other photosensitizers, ethylene-carbon monoxide copolymers, aromatic ketone-metal salt sensitizers, and combinations thereof.

[0122] End use In one embodiment, or in combination with any other embodiment, a biodegradable, disintegrable and / or compostable article is provided that comprises the cellulose ester composition described herein.In an embodiment, the cellulose ester composition may be extrudable, moldable, castable, thermoformable, or 3D printable.

[0123] In one embodiment, or in combination with any other embodiment, the cellulose ester composition can be melt-processed and formed into a useful molded article, such as a disposable food contact article, that is biodegradable and / or compostable.In one embodiment, or in combination with any other embodiment, the article is non-persistent.By "non-persistent" environmentally, it is meant that when the biodegradable cellulose ester reaches an advanced level of degradation, it is suitable for complete consumption by natural microbial populations.The decomposition of biodegradable cellulose ester ultimately results in its conversion into carbon dioxide, water and biomass. In one embodiment, or in combination with any other embodiment, there is provided an article comprising a cellulose ester composition (as discussed herein) having a maximum thickness of 150 mil, or 140 mil, or 130 mil, or 120 mil, or 110 mil, or 100 mil, or 90 mil, or 80 mil, or 70 mil, or 60 mil, or 50 mil, or 40 mil, or 30 mil, or 25 mil, or 20 mil, or 15 mil, or 10 mil, or 5 mil, or 2 mil, or up to 1 mil, and which is biodegradable and compostable (i.e., passes industrial or home compostability tests / standards as discussed herein). In one embodiment, or in combination with any other embodiment, there is provided an article comprising a cellulose ester composition having a maximum thickness of 150 mils, or 140 mils, or 130 mils, or 120 mils, or 110 mils, up to 100 mils, or 90 mils, or 80 mils, or 70 mils, or 60 mils, or 50 mils, or 40 mils, or 30 mils, or 25 mils, or 20 mils, or 15 mils, or 10 mils, or 5 mils, or 2 mils, or up to 1 mil, which is environmentally non-sustainable (as discussed herein).

[0124] In one embodiment, or in combination with any other embodiment, an article comprising the cellulose ester composition is provided, and the article is used in food service and food products, horticulture, agriculture, recreation, coating, textile, nonwoven, and home / office applications. Examples of food service and food products include, but are not limited to, straws, cup lids, composite lids, portion cups, beverage cups, trays, bowls, plates, food containers, container lids, clamshell containers, cutlery, cookware, stir sticks, jars, jar lids, bottles, bottle caps, bags, flexible packaging, wraps, produce baskets, produce stickers, and twine. Examples of horticulture and / or agriculture applications include, but are not limited to, flower pots, germination trays, transplant pots, plant tags, buckets, soil and mulch bags, trimmer strings, agricultural films, mulch films, greenhouse films, silage films, compostable bags, film posts, and hay baling twine. Examples of recreational articles include, but are not limited to, toys, sports equipment, fishing equipment, golf equipment, and camping equipment. Toys may include, but are not limited to, beach toys, blocks, wheels, propellers, sippy cups, doll accessories, and pet toys. Sporting goods may include, but are not limited to, whistles, wiffle balls, paddles, nets, foam balls and darts, and artificial turf. Fishing equipment may include, but are not limited to, floats, lures, nets, and traps. Golf equipment includes, but is not limited to, tees, practice balls, ball markers, divot tools. Camping equipment includes, but is not limited to, tent stakes, utensils, and cords / ropes). Examples of home and office items include, but are not limited to, gift cards, credit cards, signs, labels, report covers, envelopes, tape, tool handles, toothbrush handles, writing implements, combs, film containers, wire insulation, screw caps, and bottles.

[0125] In one embodiment, or in combination with any other embodiment, an article is made from a moldable thermoplastic material comprising the cellulose ester composition described herein. In one embodiment, or in combination with any other embodiment, the article is a disposable food contact article. Examples of such articles that can be made using the cellulose ester composition include cups, trays, trays with multiple compartments, clamshell packaging, candy bars, films, sheets, trays and lids (e.g., thermoformed), straws, plates, bowls, portion cups, food packaging, liquid carriers, solid or gel carriers, and cutlery. In one embodiment, or in combination with any other embodiment, the cellulose ester can be a coating or layer of the article. The article can include fibers. In one embodiment, or in combination with any other embodiment, the article can be a horticultural article. Examples of such articles that can be made using the cellulose ester composition include flower pots, plant tags, mulch films, and agricultural ground covers.

[0126] In one embodiment, or in combination with any other embodiment, the cellulose ester has a number average molecular weight ("M") in the range of 10,000 to 90,000 Daltons as measured by GPC. n In one embodiment, or in combination with any other embodiment, the cellulose ester has a number average molecular weight ("M") in the range of 30,000 to 90,000 daltons as measured by GPC. n In one embodiment, or in combination with any other embodiment, the cellulose ester has a number average molecular weight ("M") in the range of 40,000 to 90,000 daltons as measured by GPC. n ").

[0127] In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.38 mm, the film exhibits greater than 5% disintegration after 6 weeks and greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.38 mm, the film exhibits greater than 10% disintegration after 6 weeks and greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.38 mm, the film exhibits greater than 20% disintegration after 6 weeks and greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.38 mm, the film exhibits greater than 30% disintegration after 6 weeks and greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.38 mm, the film exhibits greater than 50% disintegration after 6 weeks and greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013). In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.38 mm, the film exhibits greater than 70% disintegration after 6 weeks and greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200.

[0128] In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.76 mm, the film exhibits greater than 30% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.76 mm, the film exhibits greater than 50% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.76 mm, the film exhibits greater than 70% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.76 mm, the film exhibits greater than 90% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200. In one embodiment, or in combination with any other embodiment, when the composition is formed into a film having a thickness of 0.76 mm, the film exhibits greater than 95% disintegration after 12 weeks according to the disintegration test protocol described herein, or alternatively according to ISO 16929 (2013) or ISO 20200.

[0129] In one embodiment, or in combination with any other embodiment, when the composition is molded into an article having a thickness of 3.7 millimeters or less, at least 90% of the article disintegrates in 90 days at 58°C according to standard ISO 20200, or when the composition is molded into an article having a thickness of 1.89 millimeters or less, at least 90% of the article disintegrates in 90 days at a temperature of 20-30°C according to standard ISO 20200.

[0130] In another embodiment, a cellulose acetate tow band is provided comprising a cellulose acetate composition comprising at least one cellulose ester, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein the cellulose acetate composition is biodegradable according to ASTM D6400 when tested under industrial composting conditions.

[0131] A typical cigarette filter is made from a continuous filament tow band of cellulose acetate-based fibers, called cellulose acetate tow or simply acetate tow. The use of acetate tow to make filters is described in various patents, and the tow may be plasticized. See, for example, U.S. Patent No. 2,794,239.

[0132] Instead of continuous fibers, staple fibers may be used which are shorter and may aid in the eventual disintegration of the filter. See, for example, U.S. Patent No. 3,658,626, which discloses the manufacture of staple fiber cigarette filter elements and the like directly from continuous filament tow. These staple fibers may also be plasticized.

[0133] Acetate tow for cigarette fibers is typically made of small filament denier fibers in a Y-shape that are intentionally highly crimped and entangled, as described in U.S. Pat. No. 2,953,838. The Y-shape allows for optimal cigarette filters with the lowest weight for a given pressure drop compared to other fiber shapes. See U.S. Pat. No. 2,829,027. Small filament denier fibers, typically in the range of 1.6 to 8 denier per filament (dpf), are used to make efficient filters. In constructing filters, crimping of the fibers allows for improved filter stiffness and reduced tow weight for a given pressure drop.

[0134] The conversion of acetate tow into cigarette filters can be accomplished using a tow conditioning system and plug maker, for example, as described in U.S. Pat. No. 3,017,309. The tow conditioning system draws the tow from the bale, spreads and de-registers the fibers ("blooms"), and delivers the tow to the plug maker. The plug maker compresses the tow, wraps it with plug wrap paper, and cuts it into rods of suitable length. To further increase the stiffness of the filter, non-volatile solvents can be added to solvent bond the fibers together. These solvent binders are commercially called plasticizers, and historically have included triacetin (glycerol triacetate), diethylene glycol diacetate, triethylene glycol diacetate, tripropionin, acetyl triethyl citrate, and triethyl citrate. Waxes have also been used to increase the stiffness of the filter. See, for example, U.S. Pat. No. 2,904,050.

[0135] Conventional plasticizer interfiber binders are useful for binding and selective filtration. However, plasticizers are typically not water soluble, and fibers remain bound together for long periods of time. In fact, conventional cigarette filters can take years to decompose and disintegrate when discarded due to the highly entangled nature of filter fibers, the solvent bonding between fibers, and the inherent slow degradability of cellulose acetate polymer. Therefore, attempts have been made to develop cigarette filters with improved degradability.

[0136] Specific embodiments Embodiment 1. A melt-processable cellulose ester composition comprising: at least one cellulose ester, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of said alkaline filler has a pH of 8 or greater, the water solubility of said alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and said alkaline filler is present in an amount of about 0.1 wt. % to about 35 wt. %, based on the weight of the cellulose ester composition; or 1. A melt processable cellulose ester composition comprising at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt % suspension of said alkaline additive has a pH of 8 or greater, wherein the water solubility of said alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and wherein said alkaline filler is present in an amount of from about 0.1 wt % to about 35 wt %, based on the weight of the cellulose ester composition.

[0137] Embodiment 2. The melt-processible cellulose ester composition of embodiment 1, wherein the alkaline filler is present in an amount of about 0.1% to about 10% by weight, based on the weight of the cellulose ester composition.

[0138] Embodiment 3. The melt-processible cellulose ester composition of embodiment 1 or 2, wherein the cellulose ester is cellulose acetate.

[0021] Embodiment 4. The melt-processible cellulose ester composition of any one of embodiments 1 to 3, wherein the cellulose ester is prepared by converting cellulose to a cellulose ester with reactants obtained from recycled materials.

[0139] Embodiment 5. The plasticizer is selected from the group consisting of glycerol triacetate (triacetin), glycerol diacetate, dibutyl terephthalate, dimethyl phthalate, diethyl phthalate, poly(ethylene glycol) MW 200-600, triethylene glycol dipropionate, 1,2-epoxypropyl phenylethylene glycol, 1,2-epoxypropyl (m-cresyl) ethylene glycol, 1,2-epoxypropyl (o-cresyl) ethylene glycol, β-oxyethyl cyclohexene carboxylate, bis(cyclohexanate) diethylene glycol, triethyl citrate, polyethylene glycol, Benzoflex, propylene glycol, polysorbate, sucrose octaacetate, acetylated triethyl citrate, acetyl tributyl citrate, Admex, tripropionin, Scandiflex, poloxamer copolymer, polyethylene glycol succinate, diisobutyl adipate, poly 5. The melt-processable cellulose ester composition of any one of the preceding claims, wherein the at least one selected from the group consisting of rivinylpyrrolidone and glycol tribenzoate, triethyl citrate, acetyl triethyl citrate, polyethylene glycol, benzoate-containing plasticizers such as the Benzoflex™ plasticizer series, poly(alkyl succinates) such as poly(butyl succinate), polyethersulfone, adipate-based plasticizers, soybean oil epoxides such as the Paraplex™ plasticizer series, sucrose-based plasticizers, dibutyl sebacate, tributyrin, tripropionin, sucrose acetate isobutyrate, the Resolflex™ series of plasticizers, triphenyl phosphate, glycolate, methoxypolyethylene glycol, 2,2,4-trimethylpentane-1,3-diylbis(2-methylpropanoate), and polycaprolactone.

[0140]

[0023] Embodiment 6. The melt-processible cellulose ester composition of any one of embodiments 1 to 5, wherein the plasticizer is present in an amount of 1 to 40 wt %. Embodiment 7. The melt-processible cellulose ester composition of any one of embodiments 1 to 6, comprising a biodegradable cellulose ester (BCE) component and at least one other biodegradable polymer other than BCE.

[0141]

[0023] Embodiment 8. The melt-processible cellulose ester composition of any one of embodiments 1 to 7, wherein the pH of a 1 wt % solution or suspension of the alkaline filler ranges from about 8 to about 12.

[0142] Embodiment 9. The melt-processable cellulose ester composition of any one of embodiments 1 to 8, wherein the alkaline filler has a water solubility at 20 to 25° C. of from about 2 ppm to about 400 ppm.

[0143]

[0023] Embodiment 10. The melt-processible cellulose ester composition of any one of embodiments 1 to 9, wherein the pH of a 1 wt. % suspension of the alkaline filler is 8 or greater and the alkaline efficiency is at least 5.

[0144]

[0023] Embodiment 11. The melt-processible cellulose ester composition of any one of embodiments 1 to 10, wherein the composition has an Alkaline Efficiency of at least 6. Embodiment 12. The melt-processible cellulose ester composition of any one of embodiments 1 to 11, wherein the alkaline filler is at least one selected from the group consisting of calcium carbonate (CaCO3), magnesium oxide (MgO), magnesium hydroxide (Mg(OH)2), magnesium carbonate (MgCO3), barium carbonate (BaCO3), and hydrated forms of these compounds.

[0145] Embodiment 13. The melt-processable cellulose ester composition of any one of embodiments 1 to 12, wherein the alkaline filler is a mixture of calcium carbonate and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate, wherein the calcium carbonate is present at 5 to 25 wt % and the at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate is present at 1 to 20 wt %, based on the total weight of the cellulose ester composition.

[0146]

[0023] Embodiment 14. The melt-processible cellulose ester composition of any one of embodiments 1 to 13, wherein the alkaline filler produces a volume expansion.

[0031] Embodiment 15. The melt-processible cellulose ester composition of any one of embodiments 1 to 14, wherein the alkaline filler is present in the cellulose ester composition at about 10% to about 20% by weight.

[0147] Embodiment 16. The melt-processible cellulose ester composition of any one of embodiments 1 to 15, wherein the neutralizing agent is at least one selected from the group consisting of citric acid, malic acid, succinic acid, adipic acid, fumaric acid, formic acid, lactic acid, maleic acid, tartaric acid, malonic acid, glutamic acid, glutaric acid, gluconic acid, isophthalic acid, terephthalic acid, glycolic acid, itaconic acid, ferulic acid, mandelic acid, aconitic acid, benzoic acid, aspartic acid, and vanillic acid.

[0148] Embodiment 17. The melt-processible cellulose ester composition of any one of embodiments 1 to 16, wherein the neutralizing agent has a pKa of 4.5 or less and a boiling point or decomposition temperature of 170° C. or more.

[0149] Embodiment 18. The melt-processible cellulose ester composition of any one of embodiments 1 to 17, wherein the neutralizing agent is citric acid, adipic acid, or fumaric acid. Embodiment 19. The melt-processible cellulose ester composition of any one of embodiments 1 to 18, wherein about 0.5% to about 5% by weight of a neutralizing agent is present in the cellulose ester composition, based on the weight of the cellulose ester composition.

[0150] Embodiment 20. The melt-processable cellulose ester composition of any one of embodiments 1 to 19, wherein when the composition is molded into an article having a thickness of 3.7 millimeters or less, at least 90% of the article disintegrates in 90 days at 58° C. according to standard ISO 20200, or when the composition is molded into an article having a thickness of 1.89 millimeters or less, at least 90% of the article disintegrates in 90 days at a temperature of 20-30° C. according to standard ISO 20200. EXAMPLES

[0151] Abbreviation CA is cellulose acetate, mm is millimeters, TA is triacetin, wt is weight, wt% is weight percent, g is grams, °C is degrees Celsius, °F is degrees Fahrenheit, mL is milliliters, L is liters, ppm is parts per million, CAP is cellulose acetate / propionate, h is hours, TGA is thermogravimetric analysis, TDS is total distillation residue, and EC is electrical conductivity.

[0152] Example 1 Free alkali content of inorganic fillers The free alkalinity of the inorganic fillers was determined by titration: 2.0 g of test material was boiled in 100 mL of water in a covered beaker for 5 minutes and filtered while hot. 50 mL of the cooled filtrate was titrated with 0.10 N sulfuric acid.

[0153] [Table 3] Example 2 The CA formulation was melt processed.

[0154] Compounded Pellets: An 18 mm (Leistritz) twin screw extruder with a single hole die was used to extrude pellets that were then later used for film extrusion. These pellets were made from a raw material consisting of powdered cellulose acetate CA-398-30 obtained from Eastman Chemical Company, liquid plasticizer (polyethylene glycol (PEG400) or TA) and additives. Any dry ingredients were added to the base powder and dry blended to produce a free flowing powder and added to a (Coperion) twin screw weight loss type feeder. Plasticizer was fed to zone 2 by a liquid injection unit equipped with a (Witte) gear pump, Hardy 4060 controller, and an injector with a 0.020" orifice. The compounded strand was passed through a water bath and pelletized (using a ConAir pelletizer).

[0155] Film Extrusion: A (1.5 inch Killion) single screw extruder equipped with a (Maddock) mixer screw was used to produce the films. Compounded cellulose acetate pellets were loaded into a hopper and the material was passed through the barrel, which transported the material towards the die. The barrel housing the screw was heated in three zones so that the pellets melted as they passed over the screw along a very narrow gap, allowing high shear and a high degree of dispersive mixing. A homogeneous polymer mixture was observed to form as it approached the die, and the mixture was forced through the die by the screw, resulting in extrusion. The extrusion produced a flat molten film as it exited the die, and the film solidified on a temperature controlled polished chrome roll (roll stack). Film samples were removed intermittently after extrusion to determine film thickness. If the extruder was producing the proper film thickness, the film was attached to a receiving roller and carefully wound up until the final roll was completed.

[0156] Example 3 (counterexample) A 5 wt% MgO in formulation with plasticizer and CA could not be formulated in the absence of a neutralizer.

[0157] Formulations with only CA, plasticizer and 5 wt% alkaline filler were not successfully melt processed. Cellulose acetate (CA-398-30) plasticized with 20 wt% triacetin (TA) or 20 wt% PEG400 and 5 wt% MgO were formulated according to Example 3. The formulated pellets of formulations 4 and 6 were porous, brittle, had a strong odor and dark color, and an intact film could not be extruded from the pellets.

[0158] [Table 4] Example 4 Appearance of melt-processed compounds of plasticized CA The melt processed CA formulations were characterized for their appearance. After pellets were compounded, 30 mil thick films were extruded as in Example 2 and 60 mil thick plaques were injection molded. Some of the formulations contained alkaline fillers and neutralizers and the appearance of the melt processed articles was evaluated.

[0159] Using a Konika Minolta Chroma Meter, CR-400, and SpectraMagic NX software, the color of the 60 mil plaques was measured against a white background in CIE L * a * b * Measured in color space. * The value is a measure of lightness, L * = 0 is black, L * =100 is white. * If the value was >50, the plaque color was characterized as "light."

[0160] Opacity was measured as the percent transmission of light (%T, 600 nm) through a 30 mil extruded film using a Beckman DU530 spectrophotometer. Clarity was evaluated as the color difference (Delta E) between white and black surfaces when measured through the 30 mil extruded film. The appearance of the test articles is summarized in Table 5.

[0161] [Table 5]

[0162] [Table 6] Example 5 Melt processed articles with less than 5 wt% MgO content and citric acid or malic acid as a neutralizing agent The melt processed CA-398-30 formulations were characterized for their appearance according to Example 4. The appearance of the test formulations was characterized as summarized in Table 7.

[0163] [Table 7] Example 6 Melt processed articles containing 2-5 wt% MgO Appearance of Melt Processed Articles with 2-5 wt% MgO Including Addition of Antioxidant (BHT), Chelant (EDA) and / or Brightener (TiO2) Melt processed CA398-30 formulations were characterized for their appearance according to Example 4. Table 8 below summarizes the appearance of the test articles. (BHT = butylated hydroxytoluene, EDA = etidronic acid)

[0164] [Table 8] Example 7 Melt-processed articles having Mg(OH)2 as an alkaline additive When a neutralizing agent is added to melt processed articles with Mg(OH)2, the color and clarity are improved. Mg(OH)2 can be included up to 5% in melt processed formulations with a neutralizing agent.

[0165] The melt processed CA-398-30 formulations were characterized for their appearance according to Example 4. In Table 9 below, the test formulations were evaluated for appearance.

[0166] [Table 9] Example 8 Aqueous biodegradation of CA resin with 2wt% MgO The screening test for biodegradation in freshwater aquatic organisms was based on the OECD 301F Manometric Respirometry Test. Biological oxygen demand [BOD] was measured over time using an OxiTop® Control OC110 respirometer system. Eastman sludge was used as the wastewater inoculum and vacuum filtered to remove solid particles. The test was run for 56 days. With a longer period, the test can be used to screen for materials that can be classified as readily or inherently biodegradable.

[0167] CA resin (Eastman CA398-30) was formulated as a blend with a plasticizer (15 wt% PEG400) and an optional alkaline additive MgO at 2 wt%. The formulation components were accurately weighed and thoroughly mixed. Good mixing of the components was verified by close agreement of three independent replicates. The formulations were not melt processed or dissolved prior to the aqueous biodegradation test. The initial pH of the mineral medium was 7.48. 2 wt% MgO did not affect the rate of biodegradation of CA-398-30 with PEG400 in the blend.

[0168] [Table 10] Example 9 Disintegration in industrial compost (OWS SAW-27) The qualitative screening test was based on ISO 16929 and assessed the disintegration of test articles during 12 weeks of composting to simulate industrial composting conditions for monitoring purposes. The 30 mil extruded film test materials of Examples 4-7 were added as 10 cm x 10 cm pieces, mixed with biowaste, and composted in a 200 liter composting bin. The mixture in the bin was manually stirred periodically while the test articles were visually monitored for disintegration.

[0169] After 12 weeks of composting, very few small specimen pieces were observed for specimens with material numbers 9, 10, 16, 17, 28, and 29 (test codes NZ-46, NZ-47, NZ-49, NZ-50, NZ-52, NZ-53). In contrast, larger specimen pieces with material numbers 18 and 30 (test codes NZ-51, NZ-54) could be retrieved from the test bin. A summary of the most notable visual observations and changes during the disintegration of the specimens is shown in Table 12.

[0170] [Table 11]

[0171] [Table 12]

[0172] [Table 13] Example 10 Disintegration of 60 mil injection molded plaques in home compost bins. CA398-30 was formulated with triacetin (TA) or PEG400, and optionally CaCO3 or MgO according to Table 15. Plaques (4 inch square and 0.060 inch thick) were injection molded from the formulated pellets. The plaques were cut into 1 inch by 4 inch strips, labeled with colored duct tape, and weighed. Twelve pieces of each test article were then placed in a home outdoor compost bin.

[0173] The compost bin was a black plastic tumbler for outdoor use with a total capacity of 140 liters, sold for home use. The bin was placed outdoors and filled to the center axis (approximately 70 liters) with industrially matured compost from a local supplier. Additional ingredients were added: approximately 24 liters of pine shavings and approximately 6 liters of alfalfa pellets (commercially available adult rabbit food). Water was added to approximately 60% using a squeeze test. The bin was rotated approximately once a week. After rotation, the bin was opened to ensure all samples were submerged in the compost. Every 6 weeks, the compost was fed with 0.5 L of alfalfa pellets. The pH of the compost varied between 6 and 7.5, while the C:N ratio was between 7 and 17.

[0174] Triplicate samples of each test material were retrieved from the outdoor tumbler after 8, 14, 20 and 26 weeks. Samples were cleaned of surface debris, dried and reweighed. The presence of 5 wt% MgO or 15 wt% CaCO3 increased decomposition, measured as weight loss, in a home compost bin.

[0175] [Table 14] Example 11 Disintegration of 125 mil injection molded tensile bars in home compost bins. CA398-30 was formulated with PEG400 and optionally CaCO3 or MgO according to Table 16. Tensile bars (also known as dogbones, 8.5 inches long, 1 / 5 to 3 / 4 inches wide, and 0.125 inches thick) were injection molded from the formulated pellets. The tensile bars were cut in half, labeled with colored duct tape, and weighed. Twelve pieces of each test article were then placed in a home outdoor compost bin.

[0176] The compost bin was a black plastic tumbler for outdoor use with a total capacity of 140 liters, sold for home use. The bin was placed outdoors and filled to the center axis (approximately 70 liters) with industrially matured compost from a local supplier. Additional ingredients were added: approximately 24 liters of pine shavings and approximately 6 liters of alfalfa pellets (commercially available adult rabbit food). Water was added to approximately 60% using a squeeze test. The bin was rotated approximately once a week. After rotation, the bin was opened to ensure all samples were submerged in the compost. Every 6 weeks, the compost was fed with 0.5 L of alfalfa pellets. The pH of the compost varied between 6 and 7.5, while the C:N ratio was between 10 and 13.

[0177] Triplicate samples of each test material were retrieved from the outdoor tumbler after 8, 14, 20 and 26 weeks. Samples were cleaned of surface debris, dried and reweighed. The presence of CaCO3 (15 wt%) or MgO (5 wt%) increased decomposition, measured as weight loss, in a home compost bin.

[0178] [Table 15] Example 12 Disintegration of 50-130 mil injection molded cutlery in home compost bins. CA-398-30 was compounded with PEG400 and optionally CaCO3 or MgO according to Table 16. Cutlery was injection molded from the compounded pellets. The knives were labeled with colored duct tape and weighed. Twelve pieces of each test article were then placed in a home outdoor compost bin.

[0179] The compost bin was a black plastic tumbler for outdoor use with a total capacity of 140 liters, sold for home use. The bin was placed outdoors and filled to the center axis (approximately 70 liters) with industrially matured compost from a local supplier. Additional ingredients were added: approximately 24 liters of pine shavings and approximately 6 liters of alfalfa pellets (commercially available adult rabbit food). Water was added to approximately 60% using a squeeze test. The bin was turned approximately once a week. After turning, the bin was opened to ensure all samples were submerged in the compost. Every 6 weeks, the compost was fed with 0.5 L of alfalfa pellets. The pH of the compost varied between 6 and 7.5, while the C:N ratio was between 10 and 13.

[0180] Samples of each test material were retrieved from the outdoor tumbler after 26 weeks. Samples were cleaned of surface debris, dried, and reweighed. The presence of 2-5 wt% MgO or 2-5 wt% Mg(OH)2 increased decomposition, measured as weight loss, in a home compost bin.

[0181] [Table 16] Example 13 Disintegration in industrial compost field trials. Industrial composting field trials were conducted at a facility using a turned windrow system. Test articles were photographed, tagged, and placed in nylon mesh bags. The mesh bags were filled with compost and placed in the windrow at the beginning of the active phase of composting. In the trials, the starting material C:N ratio averaged about 24. The average temperature in the windrow over the 90 day active phase was about 160°F (71°C) and the moisture content varied between 50-60%. The piles were subjected to an additional 90 day maturation phase. After recovery of the test articles from the mesh bags, the % disintegration was estimated from images of the partially disintegrated test articles.

[0182] [Table 17] Example 14 Hydrated MgCO3, hydromagnesite and basic magnesium carbonate as alkaline additives Hydromagnesite (hydrated MgCO3) was precipitated from a solution of soluble salts. Precipitation was carried out at 90°C. Starting materials were USP grade MgSO4·7H2O and food grade sodium bicarbonate. For the precipitation reaction, the 0.5M Mg salt solution was heated to at least 70°C before sodium bicarbonate solid was added slowly with stirring, and the reaction was then held at 90°C overnight. The resulting solid precipitate was washed with DI water until the TDS of the filtrate was measured below 120 ppm by a portable EC meter. The precipitate was dried to constant weight and passed through a sieve to break up any agglomerates. The reaction product was confirmed to be hydromagnesite by TGA and from the plate-like crystal morphology using SEM. The molecular formula of hydromagnesite is 4MgCO3·Mg(OH)2·4H2O.

[0183] Basic magnesium carbonate (BMC320-FCC, Brenntag Specialty Ingredients) was estimated by TGA to have approximately three bound water molecules, suggesting an artignite-like molecular formula of 4MgCO3·Mg(OH)2·3H2O.

[0184] Colorimetric pH paper was used to estimate the pH of 1% suspensions of different Mg-based alkaline minerals, and a portable electrical conductivity (EC) meter measured the total dissolved solids (TDS) of 1 wt% suspensions at 21 °C and reported in ppm.

[0185] [Table 18] Dry blends of CA-398-30 with 5 wt% MgCO3 (hydrate) and 15 wt% PEG400 were made by sieving the dry ingredients together three times to disperse the mineral additives in the CA powder. The PEG400 was then added and the mixtures blended together with an electric grinder to disperse the plasticizer. Each dry blend was weighed into an aluminum pan and dried at 80°C for 24 hours. Films (10 mil and 20 mil) were compressed for a total of 4 minutes in a heated press with top and bottom platens preheated to 425°F. The pre-dried CA / PEG400 / MgO / acid dry blends were applied to the center of a 4 inch square, 10 mil thick frame between top and bottom layers of aluminum foil, all between two steel plates. The assembly was placed in a press and heated at 0 pressure for 1 minute to dry and premelt the puck, then compressed at 12,000 PHI for 1 minute, increased to higher pressure for approximately 30 seconds, and finally held at 20,000 PHI for 1.5 minutes (ram force in pounds).

[0186] The compression molded formulations were characterized for their appearance according to Example 4 and are summarized in Table 19 below.

[0187] [Table 19] Example 15 Appearance of melt-processed compounds of plasticized CA Formulations with PEG400 as a plasticizer and 1 wt% to 5 wt% hydromagnesite as an alkaline additive were prepared and 30 mil films were extruded according to Example 2. The appearance of the 30 mil extruded films was characterized according to Example 4 and is summarized in Table 20.

[0188] [Table 20] Example 16 Melt-processed articles of CAP with alkaline additives Compression Molded CAP Films: For the control film sample without MgO, the CE powder was used as is. For the sample with MgO, 95g of Eastman CAP-485-20 powder was mixed with 5g of MgO using a planetary mixer (Thinky mixer). The powder was then sieved to ensure the mixture was clump-free. The powder was compression molded into a 30 mil film using a compression molding machine. The CAP formulations with and without MgO were compression molded at 232°C (450F) for up to 4 minutes.

[0189] Example 17 CAB melt processed articles with alkaline additives Compression Molded CAB Films: For the control film sample without MgO, the CE powder was used as is. For the sample with MgO, 95g of Eastman CAB-381-2 powder was mixed with 5g of MgO using a planetary mixer (Thinky mixer). The powder was then sieved to ensure the mixture was free of agglomerates. The powder was compression molded into a 30 mil film using a compression molding machine. CAB formulations with and without MgO were compression molded at 232°C (420°F) for up to 4 minutes.

[0190] Example 18 Investigation of metal oxides, hydroxides and carbonates as alkaline additives Selected metal oxides, hydroxides and carbonates were screened as alkaline additives to accelerate the degradation of CA films (Table 21). Films were cast from acetone dopes of CA-394-60S containing 12 wt% PEG400 and a combination of minerals listed in Table 23. Weight loss from the films after 12 weeks in deionized water at 50°C was used to estimate the environmental degradation of the films. Only ZnO, Mg(OH)2 and BMC were effective in increasing weight loss from the films when included as the only additives. Only Mg(OH)2 and BMC were effective in increasing weight loss from the films when combined with 15 wt% CaCO3. The highest %wt loss in water at 50°C was measured when the film contained 15 wt% CaCO3 and 5 wt% MgO plus 5 wt% Mg(OH)2.

[0191] [Table 21]

[0192] [Table 22]

[0193] [Table 23] Example 19 CaCO3 in combination with MgO and / or Mg(OH)2 Films were cast from acetone dopes of CA-394-60S containing 12 wt% PEG400 and the mineral combinations listed in Table 25. Weight loss from the films, predictive of environmental degradation, is maximized by the combination of calcium carbonate (CaCO3) from multiple sources with 5 wt% MgO or a combination of 5 wt% MgO and 5 wt% Mg(OH)2. In contrast, film degradation, measured as weight loss, was not improved by the inclusion of the neutral filler kaolin.

[0194] [Table 24-1]

[0195] [Table 24-2]

[0196] [Table 25] Example 20 Changes in the ratio of MgO to Mg(OH)2 in mixtures with CaCO3 Films were cast from acetone dopes of CA-394-60S containing 12 wt% PEG400 and the mineral combinations listed in Table 26. Weight loss from the films after 12 weeks in deionized water at 50° C., predictive of environmental degradation, is increased by combining the alkaline additives MgO and / or Mg(OH)2 with CaCO3.

[0197] [Table 26] Example 21 Changes in the ratio of MgO to Mg(OH)2 in mixtures with CaCO3 Films were cast from acetone dopes of CA-394-60S containing 12 wt% PEG400 and the mineral combinations listed in Table 27. Weight loss from the films after 12 weeks in deionized water at 50°C, predictive of environmental degradation, varies only slightly with different ratios of alkaline additives MgO and Mg(OH)2 with CaCO3.

[0198] [Table 27] Example 22 The preferred neutralizing agents are heat stable carboxylic acids.

[0199] Dry blends were made for compression molding. First, CA398-30 and MgO (Marinco FCC) were pre-sieved separately to remove agglomerates, then combined in the required ratio (158g CA+10g MgO) and sieved together three times to thoroughly disperse. To avoid variations in MgO content, this CA:MgO master blend was used for all subsequent blends. To incorporate the acids, approximately 1 gram of solids was ground to a fine powder in a mortar and pestle. Each ground acid was pre-sieved separately, then 0.3 grams of acid was combined with the CA:MgO pre-blend and sieved together three times to disperse the acid. Finally, PEG400 was added to the powders and the final blend was mixed with a coffee grinder to disperse the PEG400. Each complete dry blend was pre-weighed (5.5g) into an aluminum pan and dried at 70°C for 16 hours. Each dry blend contained 79 wt% CA-398-30, 15 wt% PEG400, 5 wt% MgO and 1 wt% acid (or none).

[0200] The film was compressed in a heated press with top and bottom platens preheated to 425°F (218°C) for a total of 4 minutes. The pre-dried CA / PEG400 / MgO / acid dry blend was applied to the center of a 4 inch square, 10 mil thick frame between top and bottom layers of aluminum foil, all between two steel plates. The assembly was placed in the press and heated for 1 minute at 0 pressure to dry and premelt the puck, then compressed for 1 minute at 12,000 PHI, increased to higher pressure for approximately 30 seconds, and finally held at 20,000 PHI for 1.5 minutes (ram force in pounds).

[0201] Observations regarding the appearance of the compression molded films are included in Table 28. Thin films composed of CA, 15 wt% PEG400 and 5 wt% MgO cast at 425°F / 218°C produced a characteristic dark brown color and burnt odor in the absence of a neutralizing acid. When 1 wt% citric acid was included, the color was much lighter, but bubble-like defects appeared, believed to be caused by water vapor formed during the thermal dehydration of the citric acid. The citric acid used in the formulation was anhydrous. Other acids produced mixed results. Benzoic and aspartic acids were poor neutralizing additives when combined with MgO in the compression molded films. The films formed a dark color and produced a strong odor during casting. In contrast, films cast with 1 wt% adipic or fumaric acid had a lighter color and showed no obvious signs of thermal degradation.

[0202] [Table 28] Disintegration in compost Example 23 Disintegration in a home compost bin Injection molded knives made from different formulations were added to residential compost bins to monitor disintegration during home composting. The dimensions of the molded cutlery that served as the control and test formulations of the present invention are detailed in Table 29.

[0203] [Table 29] The compost bin was a black plastic household tumbler with a capacity of 140 L, initially filled with approximately 100 L of material (70 L mature compost, 24 L pine shavings, 4-5 L alfalfa pellets, 60% moisture). Adjust initial C:N ratio to >2 with alfalfa pellets and / or KNO3. Side vent was fully opened. Material was added to the empty bin. Starting material volume was approximately 100 L.

[0204] [Table 30] Test articles were labeled with colored tape and added to the bin. The bin was rotated weekly and the squeeze test was used to maintain moisture levels. At 8, 14, 20, and 26 weeks, the compost was fed approximately 1 L of alfalfa. Pine shavings were added to keep the compost volume above the central axis. The breakdown of the articles in the home compost bin was monitored as weight loss from the dry articles collected from the bin. After 26 weeks in the home compost bin, the final % weight loss was determined. Only articles with a combination of the alkaline minerals CaCO3 and MgO reached the goal of >90% weight loss after 26 weeks.

[0205] [Table 31] Example 24 Collapse according to ISO 20200 at high temperatures The US standard ASTM D6400, Standard Specification for Labeling of Plastics Designed to be Aerobically Composted in Municipal or Industrial Facilities (2021), specifies that a minimum of 90% disintegration is required for certification.

[0206] The test articles were forks molded from a formulation containing 66 wt% CA-394-60S, 12 wt% PEG400, 5 wt% MgO, 15 wt% CaCO3, and 1 wt% citric acid. The thickness of the test articles varied from 1.5 mm at the tip of the handle to 3.7 mm at the thickest part of the handle. Disintegration of the test articles in the laboratory compost was carried out according to ISO20200. The synthetic compost contained rabbit feed, corn starch, sugar, corn oil, urea, sawdust, and wood chips. The raw material was inoculated using mature compost from a local industrial composting facility. The initial C:N ratio of 30:1 was adjusted with urea, and the moisture content was adjusted to 55% by adding water. The test article (14.6 grams) was added to each reactor along with 1 kg of the synthetic compost mix. The reactors were run in triplicate. The mixture was composted for 12 weeks and temperature was controlled at 58°C + / - 2. The average % decay across the three tanks was 99.4%.

[0207] Example 25 Decay according to ISO 20200 at ambient temperature The French standard specification NF T51-800, Plastics - Specifications for plastics suitable for home composting (2015), the Australian standard specification AS5810, Biodegradable plastics - Biodegradable plastics suitable for home composting (2010), and the OK COMPOST HOME certification scheme of TUV AUSTRIA Belgium state that in a quantitative test according to ISO 20200 (2015) at ambient temperature (20-30°C), a material has demonstrated sufficient disintegration for home composting if after 26 weeks of composting at least 90% of the test material has been reduced to a size of less than 2 mm.

[0208] Test formulations containing CA-394-60S (66 wt%), PEG400 (12 wt%), MgO (5 wt%), CaCO3 (15 wt%) and citric acid (1 wt%) were used to mold forks with dimensions ranging from 0.84 mm at the thinnest part (middle of the handle) to 1.89 mm at the thickest part (neck). The items were tested for disintegration in home compost according to ISO 20200 "Plastics - Determination of the degree of disintegration of plastic materials under simulated composting conditions in a laboratory-scale test" (2015). The test was modified by incubating the test samples and compost at 28°C ± 2°C to simulate home composting conditions. The composite compost mixture contained 2 kg of mature compost fraction less than 10 mm per reactor plus freshly milled vegetable, garden and fruit waste. Decomposition of the commodity was 90.1% after 26 weeks.

Claims

1. 1. A melt-processable cellulose ester composition comprising: at least one cellulose ester, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of said alkaline filler has a pH of 8 or greater, the water solubility of said alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and said alkaline filler is present in an amount of about 0.1 wt. % to about 35 wt. % based on the weight of the cellulose ester composition; or 1. A melt-processible cellulose ester composition comprising at least one cellulose acetate, at least one plasticizer, at least one alkaline additive, and at least one neutralizing agent, wherein a 1 wt. % suspension of said alkaline additive has a pH of 8 or greater, and wherein the water solubility of said alkaline filler at 20-25° C. is greater than 1 ppm but less than 1,000 ppm, and wherein said alkaline filler is present in an amount of from about 0.1 wt. % to about 35 wt. % based on the weight of the cellulose ester composition.

2. 10. The melt-processible cellulose ester composition of claim 1, wherein the alkaline filler is present in an amount of from about 0.1% to about 10% by weight, based on the weight of the cellulose ester composition.

3. 3. The melt-processible cellulose ester composition of claim 1, wherein the cellulose ester is cellulose acetate.

4. 3. The melt-processible cellulose ester composition of claim 1, wherein the cellulose ester is prepared by converting cellulose to a cellulose ester with reactants obtained from recycled materials.

5. The plasticizer may be selected from the group consisting of glycerol triacetate (triacetin), glycerol diacetate, dibutyl terephthalate, dimethyl phthalate, diethyl phthalate, poly(ethylene glycol) MW 200-600, triethylene glycol dipropionate, 1,2-epoxypropyl phenylethylene glycol, 1,2-epoxypropyl (m-cresyl)ethylene glycol, 1,2-epoxypropyl (o-cresyl)ethylene glycol, β-oxyethyl cyclohexene carboxylate, bis(cyclohexanate)diethylene glycol, triethyl citrate, polyethylene glycol, Benzoflex, propylene glycol, polysorbate, sucrose octaacetate, acetylated triethyl citrate, acetyl tributyl citrate, Admex, tripropionin, Scandiflex, poloxamer copolymer, polyethylene glycol succinate, diisobutyl adipate, 3. The melt-processible cellulose ester composition of claim 1, wherein the at least one plasticizer selected from the group consisting of ethylene glycol, polyvinylpyrrolidone and glycol tribenzoate, triethyl citrate, acetyl triethyl citrate, polyethylene glycol, benzoate-containing plasticizers such as the Benzoflex™ plasticizer series, poly(alkyl succinates) such as poly(butyl succinate), polyethersulfone, adipate-based plasticizers, soybean oil epoxides such as the Paraplex™ plasticizer series, sucrose-based plasticizers, dibutyl sebacate, tributyrin, tripropionin, sucrose acetate isobutyrate, the Resolflex™ series of plasticizers, triphenyl phosphate, glycolate, methoxypolyethylene glycol, 2,2,4-trimethylpentane-1,3-diylbis(2-methylpropanoate), and polycaprolactone.

6. 3. The melt-processible cellulose ester composition of claim 1, wherein the plasticizer is present in an amount of 1 to 40 wt %.

7. 3. The melt-processible cellulose ester composition of claim 1, wherein the cellulose ester composition comprises a biodegradable cellulose ester (BCE) component and at least one other biodegradable polymer other than the BCE.

8. 3. The melt-processible cellulose ester composition of claim 1, wherein the pH of a 1 wt. % solution or suspension of the alkaline filler ranges from about 8 to about 12.

9. 3. The melt-processible cellulose ester composition of claim 1, wherein the alkaline filler has a water solubility of from about 2 ppm to about 400 ppm at 20 to 25°C.

10. 3. The melt-processible cellulose ester composition of claim 1, wherein the pH of a 1 wt. % suspension of the alkaline filler is 8 or greater and the alkaline efficiency is at least 5.

11. 3. The melt-processible cellulose ester composition of claim 1 or 2, having an alkaline efficiency of at least 6.

12. The alkaline filler is calcium carbonate (CaCO ３ ), magnesium oxide (MgO), magnesium hydroxide (Mg(OH) ２ ), magnesium carbonate (MgCO ３ ), barium carbonate (BaCO ３ 3. The melt-processible cellulose ester composition of claim 1, wherein the cellulose ester is at least one selected from the group consisting of: hydroxybenzoates, ...

13. 3. The melt-processible cellulose ester composition of claim 1, wherein the alkaline filler is a mixture of calcium carbonate and at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate, wherein the calcium carbonate is present at 5 to 25 wt % and the at least one of magnesium oxide, magnesium hydroxide, or magnesium carbonate is present at 1 to 20 wt %, based on the total weight of the cellulose ester composition.

14. 3. The melt-processible cellulose ester composition of claim 1, wherein the alkaline filler produces a volume expansion.

15. 3. The melt-processible cellulose ester composition of claim 1, wherein the alkaline filler is present in the cellulose ester composition at about 10% to about 20% by weight.

16. 3. The melt-processible cellulose ester composition of claim 1, wherein the neutralizing agent is at least one selected from the group consisting of citric acid, malic acid, succinic acid, adipic acid, fumaric acid, formic acid, lactic acid, maleic acid, tartaric acid, malonic acid, glutamic acid, glutaric acid, gluconic acid, isophthalic acid, terephthalic acid, glycolic acid, itaconic acid, ferulic acid, mandelic acid, aconitic acid, benzoic acid, aspartic acid, and vanillic acid.

17. 3. The melt-processible cellulose ester composition of claim 1 or 2, wherein the neutralizing agent has a pKa of 4.5 or less and a boiling point or decomposition temperature of 170°C or more.

18. 3. The melt-processible cellulose ester composition of claim 1 or 2, wherein the neutralizing agent is citric acid, adipic acid, or fumaric acid.

19. 3. The melt-processible cellulose ester composition of claim 1, wherein from about 0.5% to about 5% by weight of the neutralizing agent is present in the cellulose ester composition, based on the weight of the cellulose ester composition.

20. 3. The melt-processible cellulose ester composition of claim 1 or 2, wherein when the composition is molded into an article having a thickness of 3.7 millimeters or less, at least 90% of the article disintegrates in 90 days at 58°C according to standard ISO 20200, or when the composition is molded into an article having a thickness of 1.89 millimeters or less, at least 90% of the article disintegrates in 90 days at a temperature of 20-30°C according to standard ISO 20200.