Oil-absorbing microbeads obtained from mixed cellulose esters.

Abstract

Provided are biodegradable beads formed from mixed cellulose esters, such as cellulose acetate butyrate and cellulose acetate propionate, which exhibit excellent oil absorption properties. Both the biodegradable beads and the mixed cellulose esters are freshwater biodegradable and can be used in a variety of downstream applications where biodegradable components are desired and required.

Description

[Background technology]

[0001] In the natural environment, conventional non-biodegradable plastics are mechanically broken down and remain in the environment as tiny plastic fragments called microplastics. Other sources of microplastics are single-use plastics such as microbeads used in health and beauty products, and ultra-fine fibers from laundry lint. Due to their size, these microplastics end up in natural water bodies. To reduce the generation of microplastics, it is preferable to use plastics that can biodegrade in freshwater. Summary of the Invention

[0002] The present application discloses biodegradable beads comprising mixed cellulose esters. Generally, the biodegradable beads exhibit an oil absorption of at least 30 mL per 100 g as measured according to ASTM D281. Additionally, the mixed cellulose esters have (a) no acetyl substituents and an average degree of substitution (DS) of the acetyl substituents of less than 2.3. Ac ), (b) an average degree of substitution (DS Pr ) or the average degree of substitution of the butyryl substituent (DS Bu ), and (c) the average degree of substitution (DS OH ) contains at least 0.6 hydroxyl substituents.

[0003] The present application also discloses biodegradable beads comprising mixed cellulose esters. Typically, the biodegradable beads exhibit an oil absorption of at least 30 mL per 100 g as measured according to ASTM D281. Additionally, the mixed cellulose esters have (a) an average degree of substitution (DS) of acetyl substituents in the range of 0.9 to 2.3. Ac ), (b) the average degree of substitution of butyryl substituents (DS Bu ), and (c) the average degree of substitution of hydroxyl groups (DS) ranging from 0.7 to 1.4. OH ).

[0004] The present application also discloses a method of forming biodegradable beads. In general, the method includes the steps of: (a) forming a dope comprising mixed cellulose esters; (b) contacting at least a portion of the dope with an aqueous mixture under stirring, thereby forming a reaction mixture comprising a plurality of biodegradable beads; and (c) recovering at least a portion of the biodegradable beads from the reaction mixture. The biodegradable beads exhibit an oil absorption of at least 30 mL per 100 g as measured according to ASTM D281. Additionally, the mixed cellulose esters have (a) acetyl substituents and an average degree of substitution (DS) of the acetyl substituents of less than 2.3. Ac ), (b) an average degree of substitution (DS Pr ) or the average degree of substitution of the butyryl substituent (DS Bu ), and (c) the average degree of substitution (DS OH ) contains at least 0.6 hydroxyl substituents.

[0005] The present application also discloses a mixed cellulose ester (MCE), which comprises: (1) multiple acetyl substituents; (2) multiple propionyl substituents; and (3) containing multiple hydroxyl substituents; The degree of substitution (DS Ac ) is between 0.6 and 1.9, The degree of substitution (DS Pr ) is between 0.5 and 0.95, and The degree of substitution (DS OH ) is between 0.7 and 1.4.

[0006] The present application also discloses a mixed cellulose ester (MCE), which comprises: (1) multiple acetyl substituents; (2) multiple propionyl substituents; and (3) containing multiple hydroxyl substituents; The average degree of substitution (DS Ac) is between 0.6 and 1.2, The average degree of substitution (DS Pr ) is between 1.05 and 1.4, and The average degree of substitution (DS OH ) is between 0.7 and 1.4.

[0007] The present application also discloses a mixed cellulose ester (MCE), which comprises: (1) multiple acetyl substituents; (2) multiple butyryl substituents; and (3) containing multiple hydroxyl substituents; The average degree of substitution (DS Ac ) is between 0.9 and 2.4, The average degree of substitution (DS Bu ) is between 0.1 and 1.1, and The average degree of substitution of the hydroxyl substituents of the MCE is from 0.6 to 1.5.

[0008] The present application also discloses compositions, articles, beads, bead compositions and films made from the mixed ester compositions disclosed herein.

[0009] The present application also discloses cellulose ester particles formed from the cellulose ester composition. (I) mixed cellulose esters (MCE); and (II) cellulose acetate (CA), The mixed cellulose ester (MCE) (1) multiple acetyl substituents; (2) Multiple (C 2-3 ) alkyl-CO-substituents; and (3) containing multiple hydroxyl substituents; The average degree of substitution (DS Ac ) is between 0.6 and 2.4, The MCE (C 2-3) Alkyl-CO-substituent (DS AkCO ) has an average degree of substitution of 0.1 to 1.1; The hydroxyl substituent (DS OH ) has an average degree of substitution of 0.55 to 1.5; The cellulose acetate (CA) is (1) multiple acetyl substituents; and (2) Multiple hydroxyl substituents having The average degree of substitution of the acetyl substituent of the CA (DS Ac ) is between 1.5 and 2.6, The hydroxyl substituent of the CA (DS OH ) has an average degree of substitution of 0.4 to 1.5.

[0010] The present application also discloses a dope composition. (A) a cellulose ester composition, and (B) containing a solvent; The cellulose ester composition is (I) mixed cellulose esters (MCEs) and (II) cellulose acetate (CA), The mixed cellulose ester (MCE) is (1) multiple acetyl substituents, (2) Multiple (C 2-3 ) alkyl-CO- substituents, and (3) containing multiple hydroxyl substituents; The average degree of substitution (DS Ac ) is between 0.6 and 2.4, The MCE (C 2-3 ) Alkyl-CO-substituent (DS AkCO The average degree of substitution of ) is 0.1 to 1.1. The hydroxyl substituent (DS OH ) has an average degree of substitution of 0.55 to 1.5; The cellulose acetate (CA) is (1) multiple acetyl substituents; and (2) containing multiple hydroxyl substituents; The average degree of substitution of the acetyl substituent of the CA (DS Ac ) is between 1.5 and 2.6, The hydroxyl substituent of the CA (DS OH ) has an average degree of substitution of 0.4 to 1.5; The solvent is (1)Water (2) Acetic acid (C 1-2 ) alkyl, and (3)(C 1-5 ) alkanols, The dope composition exhibits a viscosity in the range of 3000 to 9000 cP.

[0011] The present disclosure is directed to cellulose acetate butyrate and cellulose acetate propionate polymers designed with the appropriate mixture of acetyl / propionyl butyrate and appropriate hydroxyl content to biodegrade in freshwater environments. The mixed cellulose esters disclosed herein are useful for preparing films, microbeads, and other molded articles.

[0012] The present invention can be better understood by referring to the following detailed description of the invention and the examples described therein. Of course, the present invention is not limited to the specific methods, compositions and conditions described. Furthermore, the terms used herein are intended to describe specific aspects of the present invention and are not intended to be limiting.

[0013] Values ​​can be expressed as "about" or "approximately" a given numerical value. Similarly, ranges may be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, it will be understood that the particular value forms the other aspect by use of the antecedent "about."

[0014] As used herein, the terms "a," "an," and "the" mean one or more.

[0015] As used herein, the term "and / or," when used in a list of more than one item, means that any one of the listed items may be taken alone, or any combination of two or more of the listed items may be taken. For example, if a composition is described as containing components A, B, and / or C, the composition may contain A alone; B alone; C alone; a combination of A and B; a combination of A and C, a combination of B and C; or a combination of A, B, and C.

[0016] As used herein, the terms "comprise," "including," and "comprising" are open-ended transitional terms used to transition from the subject matter described before the term to one or more elements described after the term, and the element or elements described after the transitional term are not necessarily the only elements that make up the subject matter.

[0017] As used herein, the terms "have", "has", and "having" have the same non-limiting meaning as "include", "including", and "including" set forth above.

[0018] As used herein, the terms "comprise" and "including" have the same non-limiting meaning as "include", "including", and "including" provided above.

[0019] As used herein, "mixed cellulose ester" is intended to refer to cellulose esters having at least two different ester substituents on a single cellulose ester polymer chain.

[0020] "Degree of substitution" is used to represent the average degree of substitution of the substituents per anhydroglucose unit (AGU). Generally, conventional cellulose has three replaceable hydroxyl groups on each AGU. Thus, DS can have a value between 0 and 3. However, low molecular weight cellulose mixed esters may have a total degree of substitution slightly greater than 3 due to the contribution of end groups. Low molecular weight cellulose mixed esters are described in more detail later in this disclosure. Because DS is a statistical average, a value of 1 does not guarantee that all AGUs have a single substituent. In some cases, there may be unsubstituted anhydroglucose units, some with two substituents, some with three substituents, and more often the value is not an integer. Total DS is defined as the average number of all substituents per anhydroglucose unit. The degree of substitution per AGU may refer to a specific substituent, such as, for example, hydroxyl, acetyl, butyryl, propionyl, etc. Additionally, the degree of substitution may specify a given hydroxyl based on the carbon units of the anhydroglucose unit.

[0021] Degree of substitution is hydroxyl, i.e. DS OH When referring to DS, it refers to the average hydroxyl groups per unsubstituted anhydroglucose. OH is not used in calculating the total degree of substitution.

[0022] Number range In this specification, numerical ranges are used to quantify certain parameters related to the present invention. Of course, when numerical ranges are provided, such ranges are interpreted as providing literal support for the claim limitations that recite only the lower limit of the range, and for the claim limitations that recite only the upper limit of the range. For example, a disclosed numerical range of 10 to 100 provides literal support for the claim recited as "greater than 10" (without upper limit) and the claim recited as "less than 100" (without lower limit).

[0023] Although specific numerical values ​​are used in this specification to quantify certain parameters related to the present invention, these specific numerical values ​​are not intended to be expressly intended to be part of a numerical range. Of course, each specific numerical value provided herein is intended to literally support a broad range, intermediate range, and narrow range. The broad range associated with each specific numerical value is plus or minus 60 percent of the numerical value, rounded to two significant digits. The intermediate range associated with each specific numerical value is plus or minus 30% of the numerical value, rounded to two significant digits. The narrow range associated with each numerical value is plus or minus 15% of the numerical value, rounded to two significant digits. For example, if a specific temperature of 62°F is stated in the specification, such statement literally supports a broad numerical range of 25°F to 99°F (62°F±37°F), an intermediate numerical range of 43°F to 81°F (62°F±19°F), and a narrow numerical range of 53°F to 71°F (62°F±9°F). These broad, intermediate, and narrow numerical ranges should not only apply to specific values, but also to the differences between those specific values. Thus, if a specification describes a first pressure of 110 psia and a second pressure of 48 psia (a difference of 62 psi), the broad, intermediate, and narrow numerical ranges for the pressure difference between those two streams are 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi, respectively.

[0024] Throughout this application, where patents or publications are referenced, the disclosures of these documents in their entireties are intended to be incorporated by reference into this application, to the extent not inconsistent with the present invention, in order to more fully describe the state of the art to which this invention pertains.

[0025] Mixed Cellulose Esters Generally, cellulose ester can be produced by any method known in the art.The method of producing cellulose ester is, for example, taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol.5, Wiley-Interscience, New York (2004), pp.394-444, the disclosure of which is incorporated by reference in its entirety.The cellulose that is the starting material for producing cellulose ester can be obtained from different grades, such as cotton linters, softwood pulp, hardwood pulp, corn fiber and other agricultural sources, as well as bacterial cellulose.

[0026] One method of producing cellulose esters is by esterification. In such a method, cellulose is mixed with a suitable organic acid, anhydride and catalyst, and then converted to a cellulose triester. Ester hydrolysis is carried out by adding a mixture of water and acid to the cellulose triester, which can then be filtered to remove any gel particles or fibers. Water is added to the mixture to precipitate the cellulose ester. The cellulose ester is then washed with water to remove reaction by-products, dehydrated and dried.

[0027] The acylating reagent suitable for use herein may include, but is not limited to, alkyl or aryl carboxylic anhydrides, carboxylic acid halides, and / or carboxylic acid esters, including the alkyl or aryl groups described above, suitable for use in the acyl substituent of the substituted cellulose ester described herein. Examples of suitable carboxylic acid anhydrides include, but are not limited to, acetic anhydride, propionic anhydride, butyric anhydride, pivaloyl anhydride, benzoic anhydride, and naphthoyl anhydride. Examples of carboxylic acid halides include, but are not limited to, acetyl, propionyl, butyryl, pivaloyl, benzoyl, and naphthoyl chlorides or bromides. Examples of carboxylic acid esters include, but are not limited to, acetyl, propionyl, butyryl, pivaloyl, benzoyl, and naphthoyl methyl esters. In one or more embodiments, the acylating reagent may be one or more carboxylic acid anhydrides selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, pivaloyl anhydride, benzoyl anhydride, and naphthoyl anhydride.

[0028] In various embodiments, the cellulose triester to be hydrolyzed can have three substituents independently selected from alkanoyl having 2 to 12 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, cellulose tributyrate, or mixed triesters of cellulose such as cellulose acetate propionate and cellulose acetate butyrate. These cellulose triesters can be prepared by many methods known to those skilled in the art. For example, cellulose triesters can be prepared by heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a catalyst such as H2SO4. Cellulose triesters can also be prepared by homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl / DMAc or LiCl / NMP.

[0029] After esterification of cellulose to triester, some of the acyl substituents can be removed by hydrolysis or alcoholysis to obtain secondary cellulose ester.Secondary cellulose ester can also be prepared directly without hydrolysis by using a limited amount of acylating reagent.This method is particularly useful when the reaction is carried out in a solvent that dissolves cellulose.

[0030] The cellulose esters thus prepared generally contain the following structure:

[0031] [ka]

[0032] In the formula, R 2 , R 3 and R 6 is hydrogen (but R 2 , R 3 and R 6 but not simultaneously hydrogen), alkyl-acyl groups, and / or aryl-acyl groups (such as those mentioned above) which are attached to the cellulose by ester bonds.

[0033] The degree of polymerization (DP) of the cellulose esters prepared by these methods can be at least 10. In other embodiments, the DP of the cellulose esters can be at least 50, at least 100, or at least 250. In other embodiments, the DP of the cellulose esters can be in the range of about 5 to about 100, or in the range of about 10 to about 50. As used herein, the term "degree of polymerization" when referring to cellulose esters is intended to indicate the average number of anhydroglucose monomer units per cellulose polymer chain.

[0034] In one embodiment, or in combination with other embodiments, the cellulose esters can have a DP of at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, and / or up to 350, up to 325, or up to 300.

[0035] The present application discloses, in a first aspect, a mixed cellulose ester (MCE), the mixed cellulose ester comprising: (1) a plurality of acetyl substituents; (2) a plurality of propionyl substituents; and (3) a plurality of hydroxyl substituents, the average degree of substitution (DS) of the acetyl substituents of the MCE. Ac ) is 0.6 to 2.3, and the average degree of substitution (DS Pr ) is 0.1 to 0.95, and the average degree of substitution (DS OH ) is between 0.5 and 1.5.

[0036] In one embodiment, or in combination with other embodiments, classes or subclasses of this first aspect, DS Acis from 0.6 to 2.2, or from 0.6 to 2.1, or from 0.6 to 2.0, or from 0.6 to 1.9, or from 0.6 to 1.8, or from 0.7 to 2.3, or from 0.7 to 2.2, or from 0.7 to 2.1, or from 0.7 to 2.0, or from 0.7 to 1.9, or from 0.8 to 2.3, or from 0.8 to 2.2, or from 0.8 to 2.1, or from 0.8 to 2.0, or from 0.8 to 1.9, or from 0.9 to 2.3, or from 0.9 to 2.2, or from 0.9 to 2.1, or from 0.9 to 2.0, or from 0.9 to 1.9, or from 1.0 to 2.3, or from 1.0 to 2.2, or 1.0 to 2.1, or 1.0 to 2.0, or 1.0 to 1.9, or 1.1 to 2.3, or 1.1 to 2.2, or 1.1 to 2.1, or 1.1 to 2.0, or 1.1 to 1.9, or 1.2 to 2.3, or 1.2 to 2.2, or 1.2 to 2.1, or 1.2 to 2.0, or 1.2 to 1.9, or 0.6 to 1.5, or 0.6 to 1.3, or 0.6 to 1.1, or 0.6 to 0.9, or 0.7 to 1.5, or 0.7 to 1.3, or 0.7 to 1.1, or 0.7 to 0.9.

[0037] In one embodiment, or in combination with other embodiments, classes or subclasses of this first aspect, DS Pris 0.1 to 0.9, or 0.1 to 0.85, or 0.1 to 0.8, or 0.1 to 0.75, or 0.1 to 0.7, or 0.1 to 0.6, or 0.1 to 0.5, or 0.1 to 0.4, or 0.15 to 0.95, or 0.15 to 0.9, or 0.15 to 0.85, or 0.15 to 0.8, or 0.15 to 0.75, or 0.15 to 0.7, or 0.15 to 0.65, or 0.2 to 0.95, or 0.2 to 0.9 , or 0.2 to 0.85, or 0.2 to 0.8, or 0.2 to 0.75, or 0.2 to 0.7, or 0.2 to 0.65, 0.25 to 0.95, or 0.25 to 0.9, or 0.25 to 0.85, or 0.25 to 0.8, or 0.25 to 0.75, or 0.25 to 0.7, or 0.25 to 0.65, or 0.3 to 0.95, or 0.3 to 0.9, or 0.3 to 0.85, or 0.3 to 0.8, or 0.3 to 0.7 5, or 0.3 to 0.7, or 0.3 to 0.65, or 0.35 to 0.95, or 0.35 to 0.9, or 0.35 to 0.85, or 0.35 to 0.8, or 0.35 to 0.75, or 0.35 to 0.7, or 0.35 to 0.65, or 0.4 to 0.95, or 0.4 to 0.9, or 0.4 to 0.85, or 0.4 to 0.8, or 0.4 to 0.75, or 0.4 to 0.7, or 0.4 to 0.65, or 0.4 5 to 0.95, or 0.45 to 0.9, or 0.45 to 0.85, or 0.45 to 0.8, or 0.45 to 0.75, or 0.45 to 0.7, or 0.45 to 0.65, or 0.5 to 0.95, or 0.5 to 0.9, or 0.5 to 0.85, or 0.5 to 0.8, or 0.5 to 0.75, or 0.5 to 0.7, or 0.5 to 0.65, or 0.1 to 0.9, or 0.1 to 0.85, or 0.1 to 0.8.

[0038] In one embodiment, or in combination with other embodiments, classes or subclasses of this first aspect, DS OHis 0.5 to 1.5, or 0.5 to 1.45, or 0.5 to 1.40, or 0.5 to 1.35, or 0.5 to 1.30, or 0.5 to 1.25, or 0.5 to 1.2, or 0.5 to 1.15, or 0.5 to 1.1, or 0.5 to 1.05, or 0.5 to 1.0, or 0.5 to 0.95, or 0.5 to 0.9, or 0.55 to 1.5, or 0.55 to 1.45, or 0.55 to 1.40, or 0.55 to 1.35, or 0.55 to 1.30, or 0.55 to 1.25, or 0.55 to 1.2, or 0.55 to 1.15, or 0.55 to 1.1, or 0.55 to 1.05, or 0.55 to 1.0, or 0.55 to 0.95, or 0.55 to 0.9, or 0.6 to 1.5, or 0.6 to 1.45, or 0.6 to 1.40, or 0.6 to 1.35, or 0.6 to 1.30, or 0.6 to 1.25, or 0.6 to to 1.2, or 0.6 to 1.15, or 0.6 to 1.1, or 0.6 to 1.05, or 0.6 to 1.0, or 0.6 to 0.95, or 0.6 to 0.9, or 0.65 to 1.5, or 0.65 to 1.45, or 0.65 to 1.40, or 0.65 to 1.35, or 0.65 to 1.30, or 0.65 to 1.25, or 0.65 to 1.2, or 0.65 to 1.15, or 0.65 to 1.1, or 0.65 to 1.05, or 0.65 to 1.0, or 0.65 to 0.95, or 0.65 to 0.9, or 0.7 to 1.5, or 0.7 to 1.45, or 0.7 to 1.40, or 0.7 to 1.35, or 0.7 to 1.30, or 0.7 to 1.25, or 0.7 to 1.2, or 0.7 to 1.15, or 0.7 to 1.1, or 0.7 to 1.05, or 0.7 to 1.0, or 0.7 to 0.95, or 0.7 to 0.9.

[0039] In one embodiment, or in combination with other embodiments, classes or subclasses of this first aspect, DS Pr and D.S. AcThe sum of is 1.9 to 2.44, or 1.9 to 2.0, or 1.9 to 2.1, or 1.9 to 2.2, or 1.9 to 2.3, or 2.0 to 2.44, or 2.0 to 2.1, or 2.0 to 2.2, or 2.0 to 2.3, or 2.1 to 2.44, or 2.1 to 2.2, or 2.1 to 2.3, or 2.2 to 2.44, or 2.2 to 2.3.

[0040] In one embodiment, or in combination with other embodiments, classes or subclasses of this first aspect, the MCE exhibits at least 40% biodegradability after 56 days, or at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, or at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability according to OECD 301F test method.

[0041] In one embodiment, or in combination with other embodiments, classes or subclasses of this first aspect, the MCE has a weight average molecular weight in the range of 5,000 to 100,000 Da, or 5,000 to 50,000 Da, or 5,000 to 25,000 Da, or 15,000 to 100,000 Da, or 15,000 to 50,000 Da, or 15,000 to 25,000 Da, or 50,000 to 100,000 Da, or 75,000 to 100,000 Da, or 15,000 to 250,000 Da.

[0042] In a second aspect, the present application discloses a mixed cellulose ester (MCE) comprising: (1) a plurality of acetyl substituents; (2) a plurality of propionyl substituents; and (3) a plurality of hydroxyl substituents, the MCE having an average degree of substitution (DS) of the acetyl substituents. Ac ) was 0.6 to 1.2, and the average degree of substitution (DS Pr) was 1.05 to 1.4, and the average degree of substitution (DS OH ) is between 0.7 and 1.4.

[0043] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, DS Ac is 0.6 to 0.7, or 0.6 to 0.8, or 0.6 to 0.9, or 0.6 to 1.0, or 0.6 to 1.1, or 0.7 to 0.9, or 0.7 to 1.0, or 0.7 to 1.1, or 0.7 to 1.2, or 0.8 to 0.9, or 0.8 to 1.0, or 0.8 to 1.1, or 0.8 to 1.2, or 0.9 to 1.0, or 0.9 to 1.1, or 0.9 to 1.2, or 1.0 to 1.1, or 1.0 to 1.2, or 1.1 to 1.2.

[0044] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, DS Pr is between 1.05 and 1.35, or between 1.05 and 1.3, or between 1.05 and 1.25, or between 1.05 and 1.2, or between 1.05 and 1.15, or between 1.05 and 1.1, or between 1.1 and 1.4, or between 1.1 and 1.35, or between 1.1 and 1.3, or between 1.1 and 1.25, or between 1.1 and 1.2, or between 1.1 and 1.15, or between 1.15 and 1.4, or is 1.15 to 1.35, or 1.15 to 1.3, or 1.15 to 1.25, or 1.15 to 1.2, or 1.2 to 1.4, or 1.2 to 1.35, or 1.2 to 1.3, or 1.2 to 1.25, or 1.25 to 1.4, or 1.25 to 1.35, or 1.25 to 1.3, or 1.3 to 1.4, or 1.3 to 1.35.

[0045] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, DS OHis 0.7 to 1.35, or 0.7 to 1.3, or 0.7 to 1.25, or 0.7 to 1.2, or 0.7 to 1.15, or 0.7 to 1.1, or 0.7 to 1.05, or 0.7 to 1.0, or 0.7 to 0.95, or 0.7 to 0.9, or 0.7 to 0.85, or 0.7 to 0.8, or 0.7 to 0.75, or 0.75 to 1.4, or 0.75 to 1.35, or 0.75 to 1.3, or 0.75 to 1.25, or 0.75 to 1.2, or 0.75 to 1.15, or 0.75 to 1.1, or 0.75 to 1.05, or 0.75 to 1.0, or 0.75 to 0.95, or 0.8 to 1.4, or 0.8 to 1.35, or 0.8 to 1.3, or 0.8 to 1.25, or 0.8 to 1.2, or 0.8 to 1.15, or 0.8 to 1.1, or 0.8 to 1.05, or 0.85 to 1.4, or 0.85 to 1.35, or 0.85 to 1.3, or 0.85 to 1.25, or 0.85 to 1.2, or 0.85 to 1.15, or 0.85 to 1.1, or 0.85 to 1.05, or 0.9 to 1.4, or 0.9 to 1.35, or 0.9 to 1.3, or 0.9 to 1.25, or 0.9 to 1.2, or 0.9 to 1.15, or 0.9 to 1.1, or 0.9 to 1.05.

[0046] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, DS Pr and D.S. AcThe sum of is 1.65 to 2.3, or 1.65 to 2.2, or 1.65 to 2.1, or 1.65 to 2.0, or 1.65 to 1.9, or 1.65 to 1.8, or 1.7 to 2.3, or 1.7 to 2.2, or 1.7 to 2.1, or 1.7 to 2.0, or 1.7 to 1.9, or 1.7 to 1.8, or 1.75 to 2.3, or 1.75 to 2.2, or 1 .75 to 2.1, or 1.75 to 2.0, or 1.75 to 1.9, or 1.8 to 2.3, or 1.8 to 2.2, or 1.8 to 2.1, or 1.8 to 2.0, or 1.8 to 1.9, or 1.9 to 2.3, or 1.9 to 2.2, or 1.9 to 2.1, or 1.9 to 2.0, or 2.0 to 2.3, or 2.0 to 2.2, or 2.0 to 2.1.

[0047] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, DS OHis 0.6 to 0.7, or 0.7 to 1.35, or 0.7 to 1.3, or 0.7 to 1.25, or 0.7 to 1.2, or 0.7 to 1.15, or 0.7 to 1.1, or 0.7 to 1.05, or 0.7 to 1.0, or 0.7 to 0.95, or 0.7 to 0.9, or 0.7 to 0.85, or 0.7 to 0.8, or 0.7 to 0.75, or 0.75 to 1.4, or 0.75 to 1.35, or 0.75 to 1.3, or 0.75 to 1.25, or 0.75 to 1.2, or 0.75 to 1.15, or 0.75 to 1.1, or 0.75 to 1.05, or 0.75 to 1.0, or 0.75 to 0.95, or or 0.8 to 1.4, or 0.8 to 1.35, or 0.8 to 1.3, or 0.8 to 1.25, or 0.8 to 1.2, or 0.8 to 1.15, or 0.8 to 1.1, or 0.8 to 1.05, or 0.85 to 1.4, or 0.85 to 1.35, or 0.85 to 1.3, or 0.85 to 1.25, or 0.85 to 1.2, or 0.85 to 1.15, or 0.85 to 1.1, or 0.85 to 1.05, or 0.9 to 1.4, or 0.9 to 1.35, or 0.9 to 1.3, or 0.9 to 1.25, or 0.9 to 1.2, or 0.9 to 1.15, or 0.9 to 1.1, or 0.9 to 1.05.

[0048] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, the MCE exhibits at least 40% biodegradability, or at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, or at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability after 56 days according to OECD 301F test method.

[0049] In one embodiment, or in combination with other embodiments, classes or subclasses of this second aspect, the MCE has a weight average molecular weight in the range of 5,000 to 100,000 Da, or 5,000 to 50,000 Da, or 5,000 to 25,000 Da, or 15,000 to 100,000 Da, or 15,000 to 50,000 Da, or 15,000 to 25,000 Da, or 50,000 to 100,000 Da, or 75,000 to 100,000 Da, or 15,000 to 250,000 Da.

[0050] The present application also discloses, in a third aspect, a mixed cellulose ester (MCE), the ester comprising: (1) a plurality of acetyl substituents; (2) a plurality of butyryl substituents; and (3) a plurality of hydroxyl substituents, the average degree of substitution (DS) of the acetyl substituents of the MCE. Ac ) is 0.9 to 2.4, and the butyryl substituent (DS Bu The average degree of substitution of the hydroxyl substituents (DS OH ) has an average degree of substitution of 0.6 to 1.5.

[0051] In one embodiment, or in combination with other embodiments, classes or subclasses of this third aspect, DS Acis from 0.9 to 2.4, or from 0.9 to 2.3, or from 0.9 to 2.2, or from 0.9 to 2.1, or from 0.9 to 2.0, or from 0.9 to 1.9, or from 0.9 to 1.8, or from 0.9 to 1.7, or from 0.9 to 1.6, or from 0.9 to 1.4, or from 0.9 to 1.3, or from 0.9 to 1.2, or from 0.9 to 1.1, or from 0.9 to 1.0, or from 0.92 to 2.4, or from 0.92 to 2.3, or from 0.92 to 2.2, or from 0.92 to 2.1, or from 0.92 to 2.0, or from 0.92 to 1.9, or from 0 .92 to 1.8, or 0.92 to 1.7, or 0.92 to 1.6, or 0.92 to 1.4, or 0.92 to 1.3, or 0.92 to 1.2, or 0.92 to 1.1, or 0.92 to 1.0, or 0.94 to 2.4, or 0.94 to 2.3, or 0.94 to 2.2, or 0.94 to 2.1, or 0.94 to 2.0, or 0.94 to 1.9, or 0.94 to 1.8, or 0.94 to 1.7, or 0.94 to 1.6, or 0.94 to 1.4, or 0.94 to 1.3, or 0.9 4 to 1.2, or 0.94 to 1.1, or 0.94 to 1.0, or 0.96 to 2.4, or 0.96 to 2.3, or 0.96 to 2.2, or 0.96 to 2.1, or 0.96 to 2.0, or 0.96 to 1.9, or 0.96 to 1.8, or 0.96 to 1.7, or 0.96 to 1.6, or 0.96 to 1.4, or 0.96 to 1.3, or 0.96 to 1.2, or 0.96 to 1.1, 0.96 to 1.0, or 0.98 to 2.4, or 0.98 to 2.3, or 0.98 to 2.2 , or 0.98 to 2.1, or 0.98 to 2.0, or 0.98 to 1.9, or 0.98 to 1.8, or 0.98 to 1.7, or 0.98 to 1.6, or 0.98 to 1.4, or 0.98 to 1.3, or 0.98 to 1.2, or 0.98 to 1.1, or 0.98 to 1.0, or 1.0 to 2.4, or 1.0 to 2.3, or 1.0 to 2.2, or 1.0 to 2.1, or 1.0 to 2.0, or 1.0 to 1.8, or 1.0 to 1.7, or 1.0 to 1.6, or 1.0 to 1.4, or 1.0 to 1.3, or 1.0 to 1.2, or 1.0 to 1.1, or 1.1 to 2.4, or 1.1 to 2.3, or 1.1 to 2.2, or 1.1 to 2.1, or 1.1 to 2.0, or 1.1 to 1.9, or 1.1 to 1.8, or 1.1 to 1.7, or 1.1 to 1.6, or 1.1 to 1.4, or 1.1 to 1.3, 1.1 to 1.2, or 1.2 to 2.4, or 1.2 to 2.3, or 1.2 to 2.2, or 1.2 to 2.1, or 1.2 to 2.1, or 1.2 to 2.0 , or 1.2 to 1.9, or 1.2 to 1.8, or 1.2 to 1.7, or 1.2 to 1.6, or 1.2 to 1.4, or 1.2 to 1.3, or 1.3 to 2.4, or 1.3 to 2.3, or 1.3 to 2.2, or 1.3 to 2.1, or 1.3 to 2.0, or 1.3 to 1.9, or 1.3 to 1.8, or 1.3 to 1.7, or 1.3 to 1.6, or 1.3 to 1.4, or 1.4 to 2.4, or 1.4 to 2.3, or 1.4 to 2.2, or 1.4 to 2.1, or 1.4 to 2 .0, or 1.4 to 1.9, or 1.4 to 1.8, or 1.4 to 1.7, or 1.4 to 1.6, or 1.5 to 2.4, or 1.5 to 2.3, or 1.5 to 2.2, or 1.5 to 2.1, or 1.5 to 2.0, or 1.5 to 1.9, or 1.5 to 1.8, or 1.5 to 1.7, or 1.5 to 1.6, or 1.6 to 2.4, or 1.6 to 2.3, or 1.6 to 2.2, or 1.6 to 2.1, or 1.6 to 2.0, or 1.6 to 1.9, or 1.6 to 1.8, or 1.6 et 1.7, or 1.7 to 2.4, or 1.7 to 2.3, or 1.7 to 2.2, or 1.7 to 2.1, or 1.7 to 2.0, or 1.7 to 1.9, or 1.7 to 1.8, or 1.8 to 2.3, or 1.8 to 2.1, or 1.8 to 2.0, or 1.8 to 1.9, or 1.9 to 2.3, or 1.9 to 2.2, or 1.9 to 2.1, or 1.9 to 2.0, or 2.0 to 2.4, or 2.0 to 2.3, or 2.0 to 2.2, or 2.0 to 2.1, or 2.1 to 2.4, or 2.1 to 2.3, or 2.1 to 2.2, or 2.2 to 2.3.

[0052] In one embodiment, or in combination with other embodiments, classes or subclasses of this third aspect, DS Buis 0.1 to 1.35, or 0.1 to 1.3, or 0.1 to 1.25, or 0.1 to 1.2, or 0.1 to 1.15, or 0.1 to 1.1, or 0.1 to 1.0, or 0.1 to 0.8, or 0.1 to 0.6, or 0.2 to 1.35, or 0.2 to 1.3, or 0.2 to 1.25, or 0.2 to 1.2, or 0.2 to 1.15, or 0.2 to 1.1, or 0.2 to 1.0, or 0.2 to 0.8, or 0.2 to 0.6, or 0.2 to 0.4, or 0.3 to 1.35, or 0.3 to 1.3, or 0.3 to 1.25, or 0.3 to 1.2, or 0.3 to 1.15, or 0.3 to 1.1, or 0.3 to 1.0, or 0.3 to 0.8, or 0.3 to 0.6, or 0.3 to 0.5, or 0.4 to 1.35, or 0.4 to 1.3, or 0.4 to 1.25, or 0.4 to 1.2, or 0.4 to 1.15, or 0.4 to 1.1, or 0.4 to 1.0, or 0.4 to 0.8, or 0.4 to 0.6, or 0.5 to 1.35, or 0.5 to 1.3, or 0.5 to 1.25, or 0.5 to 1.2, or 0.5 to 1.15, or 0.5 to 1.1, or 0.5 to 1.0, or 0.5 to 0.8, or 0.5 to 0.7, or 0.6 to 1.35, or 0.6 to 1.3, or 0.6 to 1.25, or 0.6 to 1.2, or 0.6 to 1.15, or 0.6 to 1.1, or 0.6 to 1.0, or 0.6 to 0.8, or 0.7 to 1.35, or 0.7 to 1.3, or 0.7 to 1.25, or 0.7 to 1.2, or 0.7 to 1.15, or 0.7 to 1 .1, or 0.7 to 1.0, or 0.8 to 1.35, or 0.8 to 1.3, or 0.8 to 1.25, or 0.8 to 1.2, or 0.8 to 1.15, or 0.8 to 1.1, or 0.8 to 1.0, or 0.9 to 1.35, or 0.9 to 1.3, or 0.9 to 1.25, or 0.9 to 1.2, or 0.9 to 1.15, or 0.9 to 1.1, or 1.0 to 1.35, or 1.0 to 1.3, or 1.0 to 1.25, or 1.0 to 1.2, or 1.0 to 1.15, or 1.0 to 1.1, or 1.05 to 1.35, or 1.05 to 1.3, or 1.05 to 1.25, or 1.05 to 1.2, or 1.05 to 1.15, or 1.05 to 1.1, or 1.1 to 1.4, or 1.1 to 1.35, or 1.1 to 1.3, or 1.1 to 1.25, or 1.1 to 1.2, or 1.1 to 1.15, or 1.15 to 1.4, or 1.15 to 1.35, or 1.15 to 1.3, or 1.15 to 1.25, or 1.15 to 1.2, or 1.2 to 1.4, or 1.2 to 1.35, or 1.2 to 1.3, or 1.2 to 1.25, or 1.25 to 1.4, or 1.25 to 1.35, or 1.25 to 1.3, or 1.3 to 1.4, or 1.3 to 1.35.

[0053] In one embodiment, or in combination with other embodiments, classes or subclasses of this third aspect, DS OH is 0.5 to 1.0, or 0.5 to 0.95, or 0.5 to 0.9, or 0.5 to 0.85, or 0.5 to 0.8, or 0.5 to 0.75, or 0.5 to 0.7, or 0.5 to 0.65, or 0.5 to 0.6, or 0.5 to 0.55, or 0.55 to 1.0, or 0.55 to 0.95, or 0.55 to 0.9, or 0.55 to 0.85, or 0.55 to 0.8, or 0.55 to 0.75, or 0.55 to 0.7, or 0.55 to 0.65, or 0.55 to 0.6, or 0.6 to 0.65, or 0.6 to 0.7, or 0.6 to 0.75, or 0.6 to 0.8, or 0.6 to 0.85, or 0.6 to 0.9, or 0.6 to 0.95, or 0.6 to 1.0, or 0.65 to 0.7, or 0.65 to 0.75, or 0.65 to 0.8, or 0.65 to 0.85, or 0.65 to 0.9, or 0.65 to 0.95, or 0.65 to 1.0.

[0054] In one embodiment, or in combination with other embodiments, classes or subclasses of this third aspect, DS Bu and D.S.Ac The sum of 1.65 to 2.3, or 1.65 to 2.2, or 1.65 to 2.1, or 1.65 to 2.0, or 1.65 to 1.9, or 1.65 to 1.8, or 1.7 to 2.3, or 1.7 to 2.2, or 1.7 to 2.1, or 1.7 to 2.0, or 1.7 to 1.9, or 1.7 to 1.8, or 1.75 to 2.3, or 1.75 to 2.2, or 1.75 to to 2.1, or 1.75 to 2.0, or 1.75 to 1.9, or 1.8 to 2.3, or 1.8 to 2.2, or 1.8 to 2.1, or 1.8 to 2.0, or 1.8 to 1.9, or 1.9 to 2.3, or 1.9 to 2.2, or 1.9 to 2.1, 1.9 to 2.0 or 2.0 to 2.4, or 2.0 to 2.3, or 2.0 to 2.2, or 2.0 to 2.1.

[0055] In one embodiment, or in combination with other embodiments, classes or subclasses of this third aspect, the MCE exhibits at least 40% biodegradability, or at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, or at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability after 56 days according to OECD 301F test method.

[0056] In one embodiment, or in combination with other embodiments, classes or subclasses of this third aspect, the MCE has a weight average molecular weight in the range of 5,000 to 100,000 Da, or 5,000 to 50,000 Da, or 5,000 to 25,000 Da, or 15,000 to 100,000 Da, or 15,000 to 50,000 Da, or 15,000 to 25,000 Da, or 50,000 to 100,000 Da, or 75,000 to 100,000 Da, or 15,000 to 250,000 Da.

[0057] Mixed Cellulose Ester Composition The present application further discloses, in a fourth aspect, a composition comprising any of the mixed cellulose esters disclosed above.

[0058] In one embodiment, or in combination with other embodiments, classes or subclasses of this fourth aspect, the composition may comprise at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95, or at least 99% by weight of one or more of the biodegradable mixed cellulose esters described herein, based on the total weight of the cellulose ester composition. Additionally or alternatively, the composition may comprise less than 99%, less than 95%, less than 90%, less than 85%, less than 80%, less than 75%, or less than 70% by weight of one or more of the biodegradable mixed cellulose esters described herein, based on the total weight of the cellulose ester composition.

[0059] In one embodiment, or in combination with any other embodiment, class or subclass of this fourth aspect, the composition further comprises a plasticizer. The plasticizer has a melting temperature T g , and / or reduce the melt viscosity.

[0060] In a class of this embodiment, or in combination with other embodiments, classes or subclasses of this fourth aspect, the plasticizer is triacetin, 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, polyvinylpyrrolidone, and glycol tribenzoate.

[0061] In a class of this embodiment, or in combination with other embodiments, classes or subclasses of this fourth aspect, the plasticizer is present in an amount of from 1 to 40 wt%, or 1 to 30 wt%, or 1 to 20 wt%, or 1 to 10 wt%, or 1 to 5 wt%, or 5 to 40 wt%, or 5 to 30 wt%, or 5 to 20 wt%, or 5 to 10 wt%, or 5 to 5 wt%, or 10 to 40 wt%, or 10 to 30 wt%, or 10 to 20 wt%, or 10 to 10 wt%, or 10 to 5 wt%, or 15 to 40 wt%, or 15 to 30 wt%, or 15 to 20 wt%, or 15 to 10 wt%, or 15 to 5 wt%, based on the weight of the cellulose ester composition.

[0062] In one class of this embodiment, the plasticizer is a biodegradable plasticizer. Examples of biodegradable plasticizers include triacetin, triethyl citrate, acetyl triethyl citrate, polyethylene glycol, benzoate-containing plasticizers such as the Benzoflex® plasticizer series, polyalkyl succinates such as polybutylene succinate, polyethersulfone, adipate plasticizers, epoxidized soybean oil such as the Paraplex® plasticizer series, sucrose-based plasticizers, dibutyl sebacate, tributyrin, sucrose acetate isobutyrate, the Resolflex® plasticizer series, triphenyl phosphate, glycolate, polyethylene glycol, 2,2,4-trimethylpentane-1,3-diylbis(2-methylpropanoate), and polycaprolactone.

[0063] In one embodiment, or in combination with other embodiments, classes or subclasses of this fourth aspect, the composition further comprises at least one biodegradable polymer different from the MCE.

[0064] In one class of this embodiment, or in combination with any other embodiment of this fourth aspect, class or subclass, the biodegradable polymer is selected from polyhydroxyalkanoates (PHAs and PHBs), polylactic acids (PLAs), polycaprolactones (PCLs), poly(butylene adipate-co-butylene terephthalate) (PBATs), polyethylene succinates (PESs), polyvinyl acetates (PVAs), copolymers such as polybutylene succinates (PBSs) and poly(butylene succinates-co-adipates) (PBSAs), other cellulose esters, cellulose ethers, starches, proteins, derivatives thereof, and combinations thereof. In certain embodiments, the biodegradable polymer is a biodegradable cellulose ester that is different from the biodegradable mixed cellulose esters described herein, such as cellulose acetate.

[0065] In one class of this embodiment, or in combination with any other embodiments, classes or subclasses of this fourth aspect, the composition comprises two or more biodegradable polymers.

[0066] In a class of this embodiment, or in combination with any other embodiments, classes or subclasses of this fourth aspect, the composition comprises biodegradable polymer in an amount of 0.1 to 60%, or 0.1 to 50%, or 0.1 to 40%, or 0.1 to 30%, or 0.1 to 20%, or 0.1 to 15%, or 0.1 to 10%, or 0.1 to 5%, or 1 to 40%, or 1 to 30%, or 1 to 25%, or 1 to 20%, or 1 to 10%, or 1 to 5%, or 5 to 40%, or 5 to 30%, or 5 to 25%, or 5 to 20%, or 5 to 10% by weight, based on the total weight of the composition.

[0067] In one embodiment, or in combination with any other embodiment, class or subclass of this fourth aspect, the composition further comprises at least one of a filler, an additive, a stabilizer, and / or a fragrance modifier.

[0068] In a class of this embodiment, or in combination with any other embodiment, class or subclass of this fourth aspect, the filler is of a type, and present in an amount, that enhances biodegradability and / or compostability.

[0069] In one class of this embodiment, or in combination with any other embodiments, classes, or subclasses of this fourth aspect, the composition comprises at least one filler selected from carbohydrates (sugars and salts), cellulosic and organic fillers (wood flour, wood fiber, hemp, carbon, coal particles, graphite, starch), mineral and inorganic fillers (calcium carbonate, talc, silica, titanium dioxide, glass fiber, glass spheres, boron nitride, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, alumina, clay), food waste or by-products (eggshells, distillers' grains, coffee grounds), desiccants (e.g., calcium sulfate, magnesium sulfate, magnesium oxide, calcium oxide), alkaline fillers (e.g., Na2CO3, MgCO3), or combinations (e.g., mixtures) of these fillers.

[0070] In one class of this embodiment, or in combination with any other embodiment, class, or subclass of this fourth aspect, the composition can include at least one filler that also functions as a colorant additive. In a subclass of this class, or in combination with any other embodiment, class, or subclass of this fourth aspect, the colorant additive filler can be selected from carbon, graphite, titanium dioxide, opacifiers, dyes, pigments, toners, and combinations thereof.

[0071] In combination with one class of this embodiment, or any other embodiment, class or subclass of this fourth aspect, the composition may include at least one filler that also functions as a stabilizer or flame retardant.

[0072] In a class of this embodiment, or in combination with any other embodiment, class or subclass of this fourth aspect, the composition may contain from 1 to 60% by weight, or from 5 to 55% by weight, or from 5 to 50% by weight, or from 5 to 45% by weight, or from 5 to 40% by weight, or from 5 to 35% by weight, or from 5 to 30% by weight, or from 5 to 25% by weight, or from 10 to 55% by weight, or from 10 to 50% by weight, or from 10 to 45% by weight, or from 10 to 40% by weight, or from 10 to or 35% by weight, or 10 to 30% by weight, or 10 to 25% by weight, or 15 to 55% by weight, or 15 to 50% by weight, or 15 to 45% by weight, or 15 to 40% by weight, or 15 to 35% by weight, or 15 to 30% by weight, or 15 to 25% by weight, or 20 to 55% by weight, or 20 to 50% by weight, or 20 to 45% by weight, or 20 to 40% by weight, or 20 to 35% by weight, or 20 to 30% by weight.

[0073] In one class of this embodiment, or in combination with any other embodiments, classes, or subclasses of this fourth aspect, the stabilizer is at least one of an ultraviolet absorber, an antioxidant (e.g., ascorbic acid, BHT, BHA), an acid or radical scavenger, an epoxidized oil (e.g., epoxidized soybean oil), or a combination thereof.

[0074] In one class of this embodiment, or in combination with any other embodiments, classes or subclasses of this fourth aspect, the stabilizer comprises one or more secondary antioxidants.

[0075] In one class of this embodiment or in combination with other embodiments, classes or subclasses of this fourth aspect, 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, citric acid, or a combination thereof.

[0076] In a class of this embodiment, or in combination with other embodiments, classes, or subclasses of this fourth aspect, the additive is an organic acid, a salt, a wax, a compatibilizer, a biodegradation accelerator, a dye, a pigment, a colorant, a gloss modifier, a lubricant, an antioxidant, a viscosity modifier, an antifungal agent, an antifog agent, an impact modifier, an antibacterial agent, a softener, a mold release agent, or a combination thereof. It is noted that the same type of compound or material may be identified or included as multiple categories of components in the 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. Specifically, a low molecular weight PEG may function as an additive that has a plasticizing effect, and a high molecular weight PEG may function as an additive that functions as a hydrophilic polymer but does not have a plasticizing effect.

[0077] Antioxidants can be divided into several classes, including primary and secondary antioxidants. Primary antioxidants are generally known to function essentially as free radical quenchers (scavengers). Secondary antioxidants are generally known to decompose 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 a synergistic inhibitory effect, while secondary antioxidants are used to extend the life of phenolic primary antioxidants.

[0078] A "primary antioxidant" is an antioxidant that acts to react with peroxide radicals via hydrogen transfer, quenching the radical. Primary antioxidants generally contain reactive hydroxy or amino groups, such as sterically hindered phenols or secondary aromatic amines. Examples of primary antioxidants include BHT, Irganox® 1010, 1076, 1726, 245, 1098, 259, 1425, Ethanox® 310, 376, 314, 330, Evernox® 10, 76, 1335, 1330, 3114, MD 1024, 1098, 1726, 120, 2246, and 565; Anox® 20, 29, 330, 70, IC-14, and 1315; 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, 1076 CP, 1135 LQ, 1290 PW, 1330 FF, 1330 PW, 2590 PW, and 3114 FF; and ADK Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330.

[0079] "Secondary antioxidants" are often called hydroperoxide decomposers. They work by reacting with hydroperoxides and breaking them down into non-radical, non-reactive, thermally stable products. They are often used in conjunction with primary antioxidants. Examples of secondary antioxidants include organophosphorus compounds (phosphites, phosphonates, etc.) and organosulfur compounds. The phosphorus and sulfur atoms of these compounds react with peroxides, converting them into alcohols. Examples of secondary antioxidants include Ultranox 626, Ethanox® 368, 326, 327; Doverphos® LPG11, LPG12, DP S-680, 4, 10, S480, S-9228, S-9228T; Evernox® 168, 626; Irgafos® 126 and 168; Weston® DPDP, DPP, EHDP, PDDP, TDP, TLP and TPP; Mark® CH 302, CH 55, TNPP, CH66, CH 300, CH 301, CH 302, CH 304 and CH 305; 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® 1680 FF, 1680 PW, and 6280 FF.

[0080] In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the aroma modifier may be selected from vanillin, Pennyroyal M-1178, almond, cinnamyl, spices, spice extracts, volatile organic compounds or small molecule compounds, and Plastidor.In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the aroma modifier is vanillin.

[0081] In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the fragrance modulating agent is present in an amount 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 fragrance modulating additive can include masking, scavenging, complementing, or combinations thereof.

[0082] In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the compatibilizer is a non-reactive compatibilizer or a reactive compatibilizer. The compatibilizer can enhance the ability of the MCE or another component to achieve a desired small particle size to improve dispersion of the selected component in the composition.

[0083] In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the compatibilizer is present in an amount of about 1 to about 40% by weight, or about 1 to about 30% by weight, or about 1 to about 20% by weight, or about 1 to about 10% by weight, or about 5 to about 20% by weight, or about 5 to about 10% by weight, or about 10 to about 30% by weight, or about 10 to about 20% by weight, based on the weight of the composition.

[0084] In a subclass of this class, or in combination with other embodiments, classes, or subclasses of this fourth aspect, the salt is an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal carbonate, an alkali metal carbonate, an alkali metal bicarbonate, ZnO, and basic Al2O3. In a subclass of this class, or in combination with other embodiments, classes, or subclasses of this fourth aspect, the salt is MgO, Mg(OH)2, MgCO3, CaO, Ca(OH)2, CaCO3, NaHCO3, Na2CO3, K2CO3, ZnO, KHCO3, or basic Al2O3.

[0085] In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the organic acid is acetic acid, propionic acid, butyric acid, valeric acid, citric acid, tartaric acid, oxalic acid, malic acid, benzoic acid, formate, acetate, propionate, butyrate, valerate, citrate, tartrate, oxalate, malate, maleic acid, malate, phthalic acid, phthalate, benzoate, and combinations thereof.

[0086] In a subclass of this class, or in combination with any other embodiment, class or subclass of this fourth aspect, the biodegradation-promoting agent may include glycols, polyglycols, polyethers, and polyalcohols, or other biodegradable polymers such as polyglycolic acid, polylactic acid, polyethylene glycol, polypropylene glycol, polydioxanes, polyoxalates, poly(α-hydroxy esters), polycarbonates, polyanhydrides, polyacetals, polycaprolactones, polyorthoesters, polyamino acids, aliphatic polyesters such as polybutylene succinate, polyethylene succinate, starch, regenerated cellulose, or aliphatic-aromatic polyesters such as PBAT.

[0087] In a subclass of this class, or in combination with any other embodiment, class or subclass of this fourth aspect, colorants include, for example, carbon black, iron oxides, such as red or blue iron oxide, titanium dioxide, silicon dioxide, red cadmium, calcium carbonate, kaolin clay, aluminum hydroxide, barium sulfate, zinc oxide, aluminum oxide, and organic pigments, such as azo, diazo and triazo pigments, condensed azo, azo lakes, naphthol pigments, anthrapyrimidines, benzimidazolones, carbazoles, diketopyrrolopyrroles, flavanthrones, indigoid pigments, isoindolites, and the like. These include nones, isoindolines, isoviolanthrones, metal complex pigments, oxazines, perylenes, perinones, pyranthrones, pyrazoloquinazolones, quinophthalones, triarylcarbonium pigments, triphendioxazines, xanthenes, thioindigo, indanthrones, isoindanthrones, anthanthrones, anthraquinones, isodibenzanthrones, triphendioxazines, quinacridones, phthalocyanine series, especially copper phthalocyanine and its nuclear halogenated derivatives, as well as acid, basic and mordant dye lakes, isoindolinone pigments, vegetable and vegetable dyes, and other available colorants and dyes.

[0088] In a subclass of this class, or in combination with any other embodiment, class or subclass of this fourth aspect, the gloss control agent can include silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate, and the like.

[0089] In a subclass of this class, or in combination with any other embodiment, class or subclass of this fourth aspect, the antifungal and / or antibacterial agents include polyene antifungals (e.g., natamycin, rimocidin, filipin, nystatin, amphotericin B, candicin, and hamycin), imidazole antifungals such as miconazole (commercially available as MICATIN® from WellSpring Pharmaceutical Corporation), ketoconazole (commercially available as NIZORAL® from McNeil consumer Healthcare), clotrimazole (commercially available as LOTRAMIN® and LOTRAMIN® from Merck), and the like. AF®, also available from Bayer as CANESTEN®), econazole, omoconazole, bifonazole, butoconazole, fenticonazole, isoconazole, oxiconazole, sertaconazole (available from OrthoDematologics as ERTACZO®), sulconazole, and tioconazole; triazole antifungals (such as fluconazole, itraconazole, isavuconazole, ravuconazole, posaconazole, voriconazole, terconazole, albaconazole, etc.), thiazole antifungals (e.g., abafungin), arylamine antifungals (such as terbinafine (available from Novartis Consumer Health as LAMISIL®), naftifine (available from Merz Pharmaceuticals as NAFTIN®), butenafine (available from Merck as LOTRAMIN®), ULTRA®), echinocandin antifungals (e.g., anidulafungin, caspofungin, and micafungin), polygodial, benzoic acid, ciclopirox, tolnaftate (e.g., available from MDS Consumer Care, Inc. as TINACTIN®), undecylenic acid, flucytosine, 5-fluorocytosine, griseofulvin, haloprogin, caprylic acid, and any combination thereof.

[0090] Viscosity modifiers having the purpose of modifying the melt flow index or viscosity of the composition that may be used in a subclass of this class, or in combination with any other embodiment, class or subclass of this fourth aspect, include polyethylene and polypropylene glycols, and glycerin.

[0091] In a subclass of this class, or in combination with other embodiments, classes or subclasses of this fourth aspect, the composition may include release agents or lubricants (e.g., fatty acids, ethylene glycol distearate), antiblock or slip agents (e.g., fatty acid esters, metal stearates (e.g., zinc stearate), and waxes), antifog 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.

[0092] Comparison of decomposition and biodegradation Decomposition is generally measured by measuring parameters such as DOC (dissolved organic carbon), CO2 production, and oxygen uptake. The main methods used to study the biodegradation of substances are the Sturm method, respirometry, and radiolabeling. 14 There are three C-atom testing methods: the Sturm method, which precisely measures the evolution of carbon dioxide by changes in pressure; the respirometry method, which precisely measures oxygen consumption over a 60-day period; and the last radioactive labeling method. 14 The C atom test method is 14 From C 14 Measure the conversion to CO2. With the appropriate equipment, all three methods can be used in aquatic or composting conditions.

[0093] Freshwater Modified Sturm Test (OECD 301B) - The amount of carbon dioxide (CO2) produced as a percentage of theoretical yield (based on total organic carbon analysis) is used as the basis for assessing whether a material will biodegrade. CO2 is measured by sodium hydroxide capture. The test is run for a minimum of 28 days and will be continued if at the end of the 28 days the CO2 yield shows signs of increasing.

[0094] Biodegradation test - oxygen consumption (OECD 301F) can be used to monitor the biodegradation of polymeric materials. OECD 301F is an aquatic aerobic biodegradation test that measures oxygen consumption to determine the biodegradability of a material. OECD 301F is most often used for insoluble or volatile substances that are difficult to measure with OECD 301B. The purity or proportion of the main components of the test material is important to determine the theoretical oxygen demand (ThOD). As with other OECD 301 test methods, the standard test period for OECD 301F is a minimum of 28 days and allows the determination of ready or inherent biodegradability. A solution or suspension of the test substance in a mineral medium is inoculated and incubated in the dark or under diffuse light under aerobic conditions. A reference compound (usually sodium acetate or sodium benzoate) is incubated in parallel to check the operation of the procedure.

[0095] Biodegradability is classified into three categories: readily biodegradable, inherently biodegradable, and non-biodegradable. Materials are readily biodegradable if they reach at least 60% of their theoretical oxygen demand within 28 days. Inherently biodegradable materials also reach the 60% level, but only after the 28-day window has elapsed. Materials that are readily biodegradable are usually tested for 28 days, but the testing period can be extended if they are classified as inherently biodegradable.

[0096] The OxiTop method is a modified Sturm method for analyzing biodegradation, which reports biodegradation as oxygen consumption, and converts the pressure from the CO2 generated during the test into BOD (Biological Oxygen Demand). OxiTop provides accurate measurements in an easy-to-use format for aquatic biodegradation. Biological Oxygen Demand (BOD) was measured over time using an OxiTop® Control OC 110 Respirometer System. This is accomplished by measuring the negative pressure generated when oxygen is consumed in a closed bottle system. To capture the CO2 released when O2 is consumed, NaOH tablets are added to the system. The CO2 and NaOH react to form Na2CO3, drawing CO2 out of the gas phase and creating a measurable negative pressure. The OxiTop measuring head records the value of this negative pressure and wirelessly communicates the information to a controller, which converts the CO2 produced into 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. Oxytop can be used to screen materials for ready or inherent biodegradability.

[0097] Beads and molded articles formed from mixed cellulose ester compositions The present application also discloses, as a fifth aspect, an article comprising any one of the mixed cellulose esters disclosed above.

[0098] The present application also discloses, as a sixth aspect, biodegradable beads comprising any one of the mixed cellulose esters (i.e., the first aspect, the second aspect, and / or the third aspect) or cellulose ester compositions (i.e., the fourth aspect) disclosed above.

[0099] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the biodegradable beads may be produced by (i) forming a dope comprising any one of the mixed cellulose esters and / or mixed cellulose ester compositions disclosed above; (ii) contacting at least a portion of the dope with an aqueous mixture under stirring, thereby forming a reaction mixture comprising a plurality of biodegradable beads; and (iii) recovering at least a portion of the biodegradable beads from the reaction mixture. An exemplary bead formation procedure is described in EP0750007A1, the disclosure of which is incorporated by reference in its entirety.

[0100] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the dope may further comprise an alkanol (eg, methanol, ethanol, and / or propanol).

[0101] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the dope may further comprise a compound comprising a carboxyl, a first C1-C3 alkyl, and a second C1-C2 alkyl. In such an embodiment, the compound may be an alkyl acetate.

[0102] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the dope may further comprise an alkyl acetate, such as methyl acetate.

[0103] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the dope may further comprise water, an alkanol, and an alkyl acetate, such as ethyl acetate.

[0104] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the aqueous mixture may include an alkyl acetate (eg, ethyl acetate) and / or methylcellulose.

[0105] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the aqueous mixture may comprise water, an alkyl acetate (eg, ethyl acetate), a surfactant, and methylcellulose.

[0106] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the biodegradable beads may be recovered from the reaction mixture via one or more centrifugation steps and / or one or more filtration steps.

[0107] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the forming and contacting steps may occur at a temperature in the range of 5° C. to 40° C. (e.g., room temperature) and a pressure of less than 3 atmospheres (e.g., atmospheric pressure).

[0108] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the formed beads may be subjected to a drying treatment after the recovery step at a temperature ranging from 75° C. to 150° C. for a period of from 4 hours to 24 hours.

[0109] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the biodegradable beads exhibit at least 40% biodegradability in 56 days according to OECD test method 301F.

[0110] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads exhibit at least 40% biodegradability, or at least 45% biodegradability, or at least 50% biodegradability, or at least 55% biodegradability, or at least 60% biodegradability, or at least 65% biodegradability, or at least 70% biodegradability, or at least 75% biodegradability, or at least 80% biodegradability, or at least 85% biodegradability according to OECD 301F test method.

[0111] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads may comprise at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95, or at least 99% by weight, based on the total weight of the bead, of one or more of the biodegradable mixed cellulose esters described herein. Additionally or alternatively, the biodegradable beads may comprise less than 99%, less than 95%, less than 90%, less than 85%, less than 80%, less than 75%, or less than 70% by weight, based on the total weight of the bead, of one or more of the biodegradable mixed cellulose esters described herein.

[0112] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads can comprise 60% to 99% by weight, based on the total weight of the beads, of one or more of the biodegradable mixed cellulose esters described herein.

[0113] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads may comprise at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95, or at least 99% by weight of the biodegradable mixed cellulose ester compositions described herein, based on the total weight of the bead. Additionally or alternatively, the biodegradable beads may comprise less than 99%, less than 95%, less than 90%, less than 85%, less than 80%, less than 75%, or less than 70% by weight of one or more of the biodegradable mixed cellulose ester compositions described herein, based on the total weight of the bead.

[0114] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads can comprise from 60% to 99% by weight, based on the total weight of the beads, of one or more of the biodegradable mixed cellulose ester compositions described herein.

[0115] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads comprise (1) any of the mixed cellulose esters described herein; and (2) an average degree of substitution of acetyl substituents (DS Ac ) is 1.5 to 2.6, and the average degree of substitution of the hydroxyl substituents (DS OH ) is 0.4 to 1.5.

[0116] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads may comprise 55% to 99%, 60% to 99%, 65% to 99%, 70% to 99%, 75% to 99%, 80% to 99%, or 85% to 99% by weight of one or more mixed cellulose esters described herein, and 1% to 15%, 1% to 20%, 1% to 25%, 1% to 30%, 1% to 35%, 1% to 40%, or 1% to 45% by weight of biodegradable cellulose acetate, based on the total weight of the bead.

[0117] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the beads have a diameter of 0.5 to 100 microns, or 0.5 to 50 microns, or 0.5 to 40 microns, or 0.5 to 30 microns, or 0.5 to 20 microns, or 0.5 to 10 microns, or 1 to 100 microns, or 1 to 70 microns, or 1 to 60 microns, or 1 to 50 microns, or 1 to 52 microns, or 1 to 40 microns, or 1 to 30 microns, or 1 to 20 microns, or 1 to 10 microns.

[0118] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the beads exhibit a sphericity of 50 to 100%, or 60 to 100%, or 70 to 100%, or 80 to 100%, or 90 to 100%, or 50 to 90%, or 50 to 80%, or 50 to 70%, or 60 to 90%, or 60 to 80%, or 60 to 70%, or 70 to 90%, or 70 to 80%, or 80 to 90%, or at least 70%, or at least 80%, or at least 90%. Sphericity can be determined according to the procedures disclosed in U.S. Patent Publication No. 2020 / 0299488.

[0119] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the beads exhibit an oil absorption of at least 30 mL per 100 g, or 35 mL per 100 g, or 40 mL per 100 g, or 45 mL per 100 g, or 50 mL per 100 g, or 55 mL per 100 g, or 60 mL per 100 g, as measured by test method ASTM D281, where mineral oil is used instead of castor oil.

[0120] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the biodegradable beads have a bulk density in the range of 0.2 to 0.7, 0.2 to 0.6, 0.3 to 0.6, or 0.3 to 0.7.

[0121] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the biodegradable beads have a molecular weight of at least 0.1, at least 0.5, at least 1, at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10 m 2 Additionally or alternatively, the biodegradable beads have an average surface area of ​​less than 20, less than 19, less than 18, less than 17, less than 16, less than 15, less than 14, less than 13, less than 12, less than 11, or less than 10 m 2 / g.

[0122] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the biodegradable beads have (i) an average particle size of from 1 micron to 60 microns; (ii) a bulk density of from 0.2 to 0.7; (iii) a bulk density of from 0.1 m 2 / g to 10 m 2 / g average surface area, or (iv) a sphericity of between 70% and 100%.

[0123] In one embodiment, or in combination with any other embodiment, class or subclass of this sixth aspect, the beads further comprise cellulose acetate, which has an average degree of substitution (DS Ac In one class of this embodiment, DS Ac is 1.8 to 2.2, or 1.5 to 2.0, or 1.8 to 2.0, or 2.0 to 2.2.

[0124] In one embodiment, or in combination with other embodiments, classes or subclasses of this sixth aspect, the beads exhibit an oil absorption of at least 30 mL per 100 g, or 35 mL per 100 g, or 40 mL per 100 g, or 45 mL per 100 g, or 50 mL per 100 g, or 55 mL per 100 g, or 60 mL per 100 g, as measured by ASTM D281 test method using mineral oil instead of castor oil.

[0125] The present application also discloses, as a seventh aspect, a composition comprising a plurality of beads as disclosed hereinabove.

[0126] The present application also discloses, as an eighth aspect, a film comprising any one of the mixed cellulose esters disclosed above.

[0127] The present application also discloses, as a ninth aspect, a film prepared from any one of the compositions or mixed cellulose esters disclosed above.

[0128] In one embodiment, or in combination with other embodiments, classes or subclasses of this ninth aspect, the composition further comprises 1 to 40 wt. % cellulose acetate, the cellulose acetate exhibiting an average degree of substitution of acetyl substituents from 1.5 to 2.6. In a class of this embodiment, DS Ac is 1.8 to 2.2, or 1.5 to 2.0, or 1.8 to 2.0, or 2.0 to 2.2.

[0129] The present application also discloses, as a tenth aspect, cellulose ester particles formed from a cellulose ester composition comprising (I) a mixed cellulose ester (MCE) and a cellulose acetate (CA). The mixed cellulose ester comprises (1) a plurality of acetyl substituents, (2) a plurality of (C 2-3 ) alkyl-CO-substituents, and (3) multiple hydroxyl substituents, the MCE of which ranges from 0.6 to 2.4 acetyl substituents (DS Ac) and the MCE is from 0.1 to 1.1 (C 2-3 ) Alkyl-CO-substituent (DS AkCO ) with an average degree of substitution of hydroxyl substituents (DS OH (II) Cellulose acetate contains multiple acetyl and multiple hydroxyl substituents, and CA has an average degree of substitution (DS) of acetyl substituents of 1.5 to 2.6. Ac ) and CA has an average degree of substitution (DS) of hydroxyl substituents of 0.4 to 1.5. OH ).

[0130] In one embodiment or in combination with any other embodiment, class or subclass of this tenth aspect, 2-3 In one embodiment, or in combination with any other embodiment, class or subclass of this tenth aspect, (C 2-3 ) Alkyl-CO- is butyryl.

[0131] In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 60% to 99% by weight and the CA is present at 1% to 40% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 55% to 99% by weight and the CA is present at 1% to 45% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 65% to 99% by weight and the CA is present at 1% to 35% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 70% to 99% by weight and the CA is present at 1% to 30% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 75% to 99% by weight and the CA is present at 1% to 25% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 80% to 99% by weight and the CA is present at 1% to 20% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this tenth aspect, the MCE is present at 85% to 99% by weight and the CA is present at 1% to 25% by weight, based on the total weight of the cellulose ester composition.

[0132] In one embodiment, or in combination with any other embodiment, class or subclass of this tenth aspect, the cellulose ester particles have (i) an average particle size of from 1 micron to 60 microns; (ii) a bulk density of from 0.2 to 0.7; (iii) a bulk density of from 0.1 m 2 / g to 10 m 2 / g average surface area; or (iv) a sphericity of between 70% and 100%.

[0133] The present application also discloses, as an eleventh aspect, a dope composition comprising (A) a cellulose ester composition and (B) a solvent. The cellulose ester composition comprises (I) a mixed cellulose ester (MCE) and (II) a cellulose acetate. The mixed cellulose ester comprises (1) a plurality of acetyl substituents, (2) a plurality of (C 2-3 ) alkyl-CO-substituents, and (3) multiple hydroxyl substituents, the MCE of which ranges from 0.6 to 2.4 acetyl substituents (DS Ac ) and the MCE is from 0.1 to 1.1 (C 2-3 ) Alkyl-CO-substituent (DS AkCO ), and the MCE has an average degree of substitution of 0.55 to 1.5 hydroxyl substituents (DS OH The cellulose acetate (CA) contains a plurality of acetyl substituents and a plurality of hydroxyl substituents, and the CA has an average degree of substitution (DS) of the acetyl substituents of 1.5 to 2.6. Ac ) and CA has 0.4 to 1.5 hydroxyl substituents (DS OH The solvent is selected from the group consisting of (1) water, (2) acetic acid (C 1-2 ) alkyl, and (3) (C 1-5 ) alkanol, and the dope composition exhibits a viscosity in the range of 3000 to 9000 cP.

[0134] In one embodiment or in combination with any other embodiment, class or subclass of this eleventh aspect, 2-3 In one embodiment or in combination with any other embodiment, class or subclass of this eleventh aspect, (C 2-3 ) Alkyl-CO- is butyryl.

[0135] In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the MCE is present at 60% to 99% by weight and the CA is present at 1% to 40% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the MCE is present at 55% to 99% by weight and the CA is present at 1% to 45% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the MCE is present at 65% to 99% by weight and the CA is present at 1% to 35% by weight, based on the total weight of the cellulose ester composition. In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the MCE is present at 70% to 99% by weight and the CA is present at 1% to 30% by weight, based on the total weight of the cellulose ester composition. In one embodiment, or in combination with other embodiments, classes, or subclasses of this eleventh aspect, the MCE is present at 75% to 99% by weight and the CA is present at 1% to 25% by weight, based on the total weight of the cellulose ester composition. In one embodiment, or in combination with other embodiments, classes, or subclasses of this eleventh aspect, the MCE is present at 80% to 99% by weight and the CA is present at 1% to 20% by weight, based on the total weight of the cellulose ester composition. In one embodiment, or in combination with other embodiments, classes, or subclasses of this eleventh aspect, the MCE is present at 85% to 99% by weight and the CA is present at 1% to 25% by weight, based on the total weight of the cellulose ester composition.

[0136] In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the cellulose ester composition is present at 5 wt% to 20 wt% and the solvent is present at 80 wt% to 95 wt% based on the total weight of the dope composition. In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the cellulose ester composition is present at 5 wt% to 15 wt% and the solvent is present at 85 wt% to 95 wt% based on the total weight of the dope composition. In one embodiment or in combination with other embodiments, classes or subclasses of this eleventh aspect, the cellulose ester composition is present at 5 wt% to 10 wt% and the solvent is present at 90 wt% to 95 wt% based on the total weight of the dope composition.

[0137] The present invention is further described by the following example embodiments; it will be understood that these example embodiments are included for illustrative purposes only and are not intended to limit the scope of the invention, unless specifically stated. EXAMPLES

[0138] Experimental section Abbreviation collection Ac2O is acetic anhydride, AcOH is acetic acid, Biodeg is biodegradable, CA-398-3 is Eastman cellulose acetate 398-3, CA-398-6 is Eastman cellulose acetate 398-6, CA-398-10 is Eastman cellulose acetate 398-10, CA-398-30 is Eastman cellulose acetate 398-30, CA-394-60LF is Eastman cellulose acetate 394-60LF, CE is cellulose ester, CEx is comparative example, °C is degrees Celsius, CAB is cellulose acetate butyrate, CA is cellulose acetate, DS is average degree of substitution, Ex is example, DS Ac is the average degree of acetyl substitution, DS Bu is the average degree of substitution of butyryl groups, DS OH is the average degree of substitution of hydroxyl groups, g is grams, h is hours, kg is kilograms, Mg(OAc)2 is magnesium acetate, min is minutes (s), mL is milliliters, Mw is the weight average molecular weight, OAc is acetic acid, PrO is propionic anhydride, PrOH is propionic acid, rt is room temperature, soln is solution, T g is the glass transition temperature.

[0139] Cellulose acetate butyrate (Ex 1) (DS Ac = 1.1, DS Pr = 1.12, DS OH = 0.78, M w = 153777)

[0140] The activated cellulose mixture (cellulose (7.1 parts) and PrOH (11.0 parts)) was cooled to 15°C in a vessel with overhead stirring. A solution of sulfuric acid (0.2 parts), Ac2O (11.3 parts) and Pr2O (13.3 parts) (acylation solution) cooled to 15°C was then added to the cooled activated cellulose mixture with stirring. The resulting reaction mixture was warmed to 23°C and stirred at 23°C for 60 minutes. The reaction mixture was then heated to 63°C over 45 minutes at which point a solution of PrOH (32.3 parts) and H2O (11.3 parts) was added. The mixture was then stirred at 71°C for 600 minutes. The mixture was treated with a solution of Mg(OAc)2·4H2O (0.45 parts) in AcOH (7.3 parts) and H2O (5.6 parts), the mixture was stirred for 30 minutes, cooled to rt and the mixture was filtered. The cellulose ester was precipitated from the filtrate with water, stirred in a commercial mixer, filtered, collected, and the solid was washed with running water and dried in a vacuum oven set at 60°C until dry to obtain the desired product.

[0141] The preparation procedure for cellulose acetate propionate 1 was applied to prepare the cellulose esters in Table 1 below.

[0142] [Table 1]

[0143] Table 2 shows the properties of the cellulose esters prepared above. [Table 2]

[0144] Cellulose acetate butyrate (Ex 6) (DS Ac = 2.17, DS Bu = 0.21, D.S. OH = 0.62, M w = 80,000 to 105,000) The activated cellulose mixture (cellulose (5.4 parts) and AcOH (21.5 parts)) was added with sulfuric acid and cooled to 32°C with stirring. A mixture of Ac2O (11.3 parts) and Bu2O (7.3 parts) was then added and the mixture was cooled to approximately 9°C with stirring. A total of 0.4 parts of sulfuric acid was added and the resulting reaction mixture was warmed to 55°C. A mixture of AcOH (23.3 parts) and H2O (9.0 parts) was added to the reaction mixture. The mixture was then stirred at 68°C for 495 minutes, after which a mixture of Mg(OAc)2 (0.26 parts), BuOH (8.7 parts), AcOH (0.06 parts) and H2O (3.8 parts) was added. After a sufficient time, the mixture was fully neutralized with a solution of Mg(OAc)2 (0.37 parts), BuOH (1.9 parts), AcOH (0.09 parts) and H2O (6.7 parts). The mixture was then precipitated in water, washed in the usual manner, and dried.

[0145] [Table 3]

[0146] [Table 4]

[0147] biodegradable The biodegradability of CE was evaluated in an aqueous aerobic biodegradation test according to ISO 14851 or OECD 301F method. The total test period was approximately 56 days. The test was carried out at 21°C ± 2°C. The biodegradation test used Eastman wastewater treatment sludge as inoculum.

[0148] In this test, CE was dispersed in a chemically defined mineral medium containing no other organic carbon sources and inoculated with microorganisms from wastewater sludge. As the microorganisms biodegrade the test material in the aqueous medium, oxygen is consumed by the microorganisms and the carbon in the test material is converted to carbon dioxide. The carbon dioxide generated during this process is captured by the NaOH in the bottle (NaOH placed in a quiver inside the closed test bottle) and causes a pressure drop in the headspace. This pressure drop corresponds directly to the oxygen consumed and therefore to the biodegradation of the test material.

[0149] Biodegradability is determined from oxygen consumption and calculated as the ratio of the reference-corrected BOD (biological oxygen demand) to the theoretical oxygen demand of the test article. A substance is considered biodegradable if it has reached at least 90% of the reference substance (according to ISO 14851) or 90% after 56 days. In addition, ECHA's proposal for microplastics states that a substance is considered biodegradable if it has reached at least 60% biodegradation after 60 days.

[0150] [Table 5]

[0151] Preparation of microbeads Preparation Step 1 Procedure 1 is based on the procedure disclosed in EP0750007 (EP'007).

[0152] Cellulose Acetate Butyrate Microbeads 7 (Step 1) Ex 6 (40 g), EtOAc (185 g) and EtOH (25 g) were used in the oil phase, while Benecel A4M (1.5 g), Tween 28 (4.5 g), water (350 g) and EtOAc (50 mL) were used in the aqueous phase. The aqueous phase was premixed with a rotostator at 9000 rpm for 5 min, and then the oil phase was added to the aqueous phase over 20 min. The oil emulsion formed was stirred for 50 min, filtered through a 200 mesh sieve and placed in water (2500 mL) under stirring for 5 min. The resulting mixture was stirred for 1 h and the formed microparticles were filtered. The resulting microparticles were washed with water and centrifuged at 10,000 for 10 min to separate the particles from the aqueous phase (repeated 3 times). The final microparticles were mixed at 100° C. for 10 min to obtain a final microparticle size of 1.5 μm. 10 is 1.21 microns, D 50 4.96 microns, D 90 The diameter was 12 microns and the polydispersity was 0.646, as measured by light scattering. 10 , D 50 , and D. 90 are the particle size values ​​that contain 10%, 50%, and 90% of the material, respectively.

[0153] Cellulose Acetate Butyrate Microbeads 17 Cellulose acetate butyrate microbeads 17 were synthesized by applying the procedure for the preparation of cellulose acetate butyrate microbeads 7. Ex 10 was used instead of Ex 6. Benecel was replaced by carboxymethylcellulose, and Tween 28 was replaced by Tergitol 15 S-40, glycerol stearate and PEG-100 stearate (1:0.5:0.5 ratio). The particle size of cellulose acetate butyrate microbeads 17 is 11 microns and the bulk density is 0.296 g / mL.

[0154] Preparation Step 2 Dope The cellulose ester mixture (90 g) was diluted with ethyl acetate, (C 2-3A dope of the cellulose ester mixture was prepared by adding 547.7 g of an alkanol / water mixture (80:13:7) with stirring at 250 rpm. The resulting mixture was stirred at room temperature (approximately 30 minutes). Preparation of cellulose acetate butyrate / cellulose acetate dope

[0155] Table 4 shows the cellulose acetate used to prepare the representative dopes in Ex 6. Table 5 shows which cellulose acetate butyrate / cellulose acetate dopes are possible from ethyl acetate, ethanol, and aqueous systems. The dopes were prepared by mixing CAB / CA (6.0 g) in the solvent (37.0 g (EA:EtOH:water = 80:13:7)).

[0156] [Table 6]

[0157] Table 7 shows dopes made from either Ex 6, various cellulose acetates, or blends of Ex 6 and various cellulose acetates according to the dope procedure in Preparation Procedure 2. Only certain cellulose acetates could be blended with Ex 6 to form dopes in the EA:EtOH:water solvent system, and none of the cellulose acetates used were able to form dopes in the EA:EtOH:water solvent system. Ex 6 readily formed dopes in the EA:EtOH:water solvent system.

[0158] [Table 7]

[0159] aqueous mixture The aqueous mixture used to prepare the emulsion is prepared by mixing ethyl acetate (124.6 g) and methylcellulose (6.8 g) with a two-stage pitched blade agitator (250 rpm) until a dispersion is formed. Water (1280 g) and Tween-28 (13.5 g) are then added. The resulting aqueous mixture is stirred for approximately 30 minutes to form a solution.

[0160] Emulsification / dispersion method for bead formation The dope (637.7 g) was dosed into the aqueous mixture (1424.3 g) at 15 mL / min with stirring (250 rpm) for approximately 45 min, and the resulting mixture was then recirculated at 200 mL / min through a MagicLab in-line high shear mixer (6000 rpm) with stirring at 250 rpm for 30 min.

[0161] The mixture was added to water (5625 g) at 200 mL / min while stirring, and the mixture was stirred at room temperature for 2 h. The mixture was centrifuged (3000 rpm, 15 min) to separate the beads. The beads were washed with water and recentrifuged (3000 rpm, 15 min) (twice). The resulting beads were dried in an oven at 100 °C and 150 mmHg (16 h).

[0162] Table 8 provides microbeads made according to procedure 2 using blends of Ex 6 with several cellulose acetates at various weight percentages.

[0163] [Table 8]

[0164] Oil uptake measurement Mineral oil was used in place of castor oil to measure the absorption or oil uptake properties using the test method ASTM D281 "Standard Test Method for Oil Absorption of Pigments by Spatula." Mineral oil (product number ELL-MIOL-01) was obtained from MakingCosmetics.com, Inc.

[0165] Mineral oil is added dropwise to a known amount of raw powder and stirred with a spatula until a solid, dry paste is formed. Once a solid, dry paste is formed, the mineral oil is no longer absorbed. Once the amount of oil is determined, calculate the oil content using the following formula: OT = (100 × V oil ) / m sanple OT: oil uptake (mL / 100 g); V oil: Amount of oil used (mL); m sanple : mass of sample (g) The results are shown in Table 9.

[0166] [Table 9]

[0167] The foregoing description of various embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Numerous modifications or variations are possible in light of the above teachings. The embodiments discussed have been chosen and described to provide the best explanation of the principles of the invention and its practical application, thereby enabling those skilled in the art to utilize the invention in various embodiments and with various modifications suited to the particular applications contemplated. All such modifications and variations are within the scope of the invention, as determined by the appended claims, when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.

Claims

1. 1. Biodegradable beads comprising mixed cellulose esters, the biodegradable beads exhibit an oil absorption capacity of at least 30 mL per 100 g as measured in accordance with ASTM D281; The mixed cellulose ester is (a) acetyl substituents and an average degree of substitution ("DS") of acetyl substituents of less than 2.3 Ａｃ "), (b) an average degree of substitution ("DS") of propionyl substituents of at least 0.1 Ｐｒ ") or the average degree of substitution of the butyryl substituents ("DS Ｂｕ "), and (c) an average degree of substitution ("DS") of hydroxyl substituents of at least 0.6 ＯＨ "), biodegradable beads.

2. Said DS ＯＨ 2. The biodegradable beads of claim 1, wherein is in the range of 0.7 to 1.

4.

3. Said DS Ａｃ 3. Biodegradable beads according to claim 1, wherein the ρ is in the range of 0.9 to 2.

2.

4. Said DS Ｐｒ 3. Biodegradable beads according to claim 1, wherein the ρ is in the range of 0.1 to 0.

9.

5. Said DS Ｂｕ 3. Biodegradable beads according to claim 1, wherein the ρ is in the range of 0.1 to 1.

1.

6. 3. The biodegradable beads according to any one of claims 1 to 2, wherein the biodegradable beads exhibit at least 40% biodegradability in 56 days according to OECD 301F test method.

7. 3. The biodegradable beads of any one of claims 1 to 2, wherein the mixed cellulose ester exhibits at least 45% biodegradability in 56 days according to OECD 301F test method.

8. 3. The biodegradable beads of claim 1, wherein the mixed cellulose ester has a weight average molecular weight in the range of 5,000 to 100,000 Da.

9. (i) a diameter of 1 to 40 microns; (ii) a sphericity in the range of 50 to 100%, and (iii) Biodegradable beads according to any one of claims 1 to 2, having a bulk density in the range of 0.2 to 0.

7.

10. Biodegradable beads comprising mixed cellulose esters and additional biodegradable cellulose esters. the biodegradable beads exhibit an oil absorption capacity of at least 30 mL per 100 g as measured in accordance with ASTM D281; The mixed cellulose ester is (a) the average degree of substitution ("DS") of acetyl substituents ranging from 0.9 to 2.3; Ａｃ "), (b) the average degree of substitution ("DS") of butyryl substituents ranging from 0.1 to 1.1; Ｂｕ "), and (c) Hydroxyl substituents in the range of 0.7 to 1.4 ("DS ＯＨ ") biodegradable beads.

11. Said DS ＯＨ The biodegradable bead of claim 10, wherein is in the range of 0.7 to 1.

0.

12. Said DS Ａｃ 12. Biodegradable beads according to any one of claims 10 to 11, wherein is in the range of 0.9 to 2.

2.

13. Said DS Ｂｕ 12. Biodegradable beads according to any one of claims 10 to 11, wherein is in the range of 0.2 to 1.

1.

14. the biodegradable beads exhibit at least 40% biodegradability in 56 days according to OECD 301F test method; 12. The biodegradable beads of any one of claims 10 to 11, wherein the mixed cellulose ester exhibits at least 45% biodegradability in 56 days according to OECD 301F test method.

15. 12. The biodegradable beads of claim 10, wherein the mixed cellulose ester has a weight average molecular weight in the range of 5,000 to 100,000 Da.

16. The biodegradable beads (i) a diameter of 1 to 40 microns; (ii) a sphericity in the range of 50 to 100%, and (iii) Biodegradable beads according to any one of claims 10 to 11, comprising a bulk density in the range of 0.2 to 0.

7.

17. 1. A method of forming biodegradable beads, comprising: (a) forming a dope comprising mixed cellulose esters; (b) contacting at least a portion of the dope with an aqueous mixture under agitation to form a reaction mixture comprising a plurality of biodegradable beads; and (c) recovering at least a portion of the biodegradable beads from the reaction mixture; The mixed cellulose ester (i) acetyl substituents and an average degree of substitution ("DS") of acetyl substituents of less than 2.3 Ａｃ "), (ii) an average degree of substitution ("DS") of propionyl substituents of at least 0.1 Ｐｒ ") or the average degree of substitution of the butyryl substituents ("DS Ｂｕ "), and (iii) an average degree of substitution ("DS") of hydroxyl substituents of at least 0.6 ＯＨ ") The biodegradable beads have a molecular weight of at least 30 per 100 g as measured according to ASTM D281. A method for forming biodegradable beads that exhibit an oil absorption capacity in mL.

18. 18. The method of claim 17, wherein the dope comprises an alkanol.

19. 19. The method of any one of claims 17 to 18, wherein the dope comprises an alkyl acetate.

20. 19. The method of any one of claims 17 to 18, wherein the aqueous mixture comprises alkyl acetate and / or methylcellulose.