Butyl methyl terephthalate compositions useful as plasticizers

Abstract

The mixed ester methyl butyl terephthalate has been synthesized and shown to be a compatible plasticizer for cellulose esters. In particular, methyl butyl terephthalate is an effective plasticizer for cellulose acetate. This is the first example of a terephthalate ester being an effective plasticizer for cellulose acetate. Dimethyl terephthalate and dibutyl terephthalate are incompatible with Eastman Cellulose Acetate CA 398-30, and physical blends of the two are also incompatible.

Description

[0001] BUTYL METHYL TEREPHTHALATE COMPOSITIONS USEFUL AS PLASTICIZERS

[0002] BACKGROUND OF THE INVENTION

[0003] Cellulose acetate finds the widest commercial use of the cellulose organic esters. Plasticizers are used with cellulose acetate in some applications to improve adhesion, rheological properties, stability, and / or to adjust mechanical properties. The glass transition temperatures (Tg) of commercial grades of cellulose acetate are relatively high, 160-180°C or more. The required melt processing temperatures can cause discoloration, and degradation of the polymer, unless efficient plasticizers are used to reduce these temperatures.

[0004] Compared to polyvinyl chloride (PVC) and to other cellulose esters such as cellulose acetate propionate and cellulose acetate butyrate, there are relatively few effective plasticizers for cellulose acetate. C.R. Fordyce and L.W.A. Meyer, Industrial and Engineering Chemistry, 32 (8), 1053-1060. Triacetin is widely used with fibers, such as in bonding, and in other applications. Though an efficient plasticizer for cellulose acetate, triacetin has enough water solubility and vapor pressure to render undesirably low permanence for some applications. Some lower citrate plasticizers, such as triethyl citrate, can have good compatibility but with similar limitations. Other plasticizers, such as phosphates, sulfonamides, tartrates, and other esters suffer from technical limitations, health and safety concerns, and / or high cost.

[0005] Ortho-phthalates (hereinafter referred to as phthalates) have been the dominant plasticizers used in cellulose acetate thermoplastics. Only the lower phthalates show compatibility - dimethyl, diethyl, dipropyl, and at low levels dibutyl phthalate. Although dimethyl and dibutyl phthalate are used in some applications, the workhorse plasticizer for cellulose acetate plastics is diethyl phthalate. Diethyl phthalate has historically been readily available and relatively inexpensive. The lower volatility and water solubility leads to it being a less fugitive plasticizer than triacetin, though diethyl phthalate is fugitive enough as to lead to efforts seeking improvement. Plasticizer levels can be varied to yield very hard and stiff cellulose acetate plastic grades, such as those used in playing cards, to very tough grades such as used in chisels.

[0006] In recent years phthalate plasticizers, for many years the highest volume plasticizers by far with particular use in PVC, have come under heightened health, safety, and environmental concerns in much of the world. These concerns are particularly acute in children’s items, such as milk bottles and toys. Among those phthalates whose use has been either been banned in some applications or whose use has otherwise been restricted include di-2- ethylhexyl phthalate, dibutyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, and dicyclohexyl phthalate. Fewer concerns have been identified with dimethyl and diethyl phthalate. The concerns and perceptions which have developed over “phthalates” though have raised interest in non-phthalate alternative plasticizers for cellulose acetate.

[0007] Terephthalate plasticizers have become the leading alternative plasticizers to phthalates in PVC, owing to their health and safety profile, performance, price, and availability. Di-2-ethylhexyl terephthalate (DEHT) has by far the largest volume of the terephthalate plasticizers. Like its analog di-2- ethylhexyl phthalate, DEHT is not a compatible plasticizer for cellulose acetate. Terephthalate plasticizers which are compatible with cellulose acetate have not been found prior to this study. Dibutyl terephthalate (DBT) has been shown to be incompatible with cellulose acetate, leading to film haziness and only small depression in the Tg. Dimethyl terephthalate (DMT) is a crystalline solid with a melting point of 141 °C. It has been found that DMT levels up to 15wt% can depress the Tgof cellulose acetate. Cast films of cellulose acetate containing as little as 5wt% up to 25wt% by weight DMT exhibit haze and / or crystals though. There are no records of diethyl terephthalate, di-n-propyl terephthalate, diisopropyl terephthalate, bis- hydroxyethyl terephthalate (BHET), or any other terephthalate diesters, mixed or symmetrical, comprising methyl, ethyl, hydroxyethyl, and any isomers of propyl or butyl radicals, having been evaluated as plasticizers for cellulose acetate. Heretofore unknown compounds within this set include methyl / sec- butyl terephthalate, n-propyl / isopropyl terephthalate, n-propyl / isobutyl terephthalate, isopropyl / n-butyl terephthalate, and isopropyl / isobutyl terephthalate.

[0008] Terephthalate esters have the further benefit of potential for including recycled content, for example, from waste plastics. The chemical depolymerization of PET yields its monomers, predominantly ethylene glycol (EG) and terephthalic acid. Depending on the specific reaction, possible intermediates and products of polyester recycling include terephthalic acid (TPA) and the esters dimethyl terephthalate (DMT) and bis-hydroxyethyl terephthalic acid (BHET). The TPA, DMT or BHET formed can be used as raw materials for “renewed” polyesters as well as for small molecule plasticizer esters. The use of recycled building blocks to make plasticizers lowers the carbon footprint for the plasticizer itself and contributes to the sustainability of a plasticized polymer formulation.

[0009] Cellulose acetate is a bio-based and biodegradable polymer, so is considered sustainable from both a beginning-of-life and end-of-life perspective. The acetyl fraction of CA may be derived from waste plastics using molecular recycling technology, adding another dimension to the sustainability of CA. Plasticizers are typically needed to melt-process CA and can be present as a substantial fraction of an article made from a thermoplastic CA formulation. To capitalize on the sustainability of formulated CA, it would be desirable to use a plasticizer that may also be derived from waste plastic. It would be even more advantageous if the plasticizer for CA exhibited low volatility and low migration or leaching from formed articles. The plasticizer for CA should also contribute to a sustainable end-of-life fate for the formed article, such as disintegration in compost.

[0010] SUMMARY OF THE INVENTION

[0011] The present application discloses a composition, comprising:

[0012] (i) greater than 15 weight percent (“wt%”) of n-butyl methyl terephthalate (“MBT”); and

[0013] (ii) greater than 1wt% of at least one plasticizer, wherein the at least one plasticizer is different than MBT, wherein the wt% of each is based on the total weight of the composition.

[0014] The present application also discloses a method for plasticizing a polymeric composition, comprising: (i) admixing a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) with the polymeric composition.

[0015] The present application discloses a use of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) as a plasticizer for a polymeric composition.

[0016] The present application also discloses plasticized cellulose ester composition, comprising:

[0017] (i) a cellulose ester; and

[0018] (ii) at least 1wt% of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”), based on the total weight of the plasticized cellulose ester composition. The present application finally discloses articles comprising the plasticized cellulose ester compositions.

[0019] DETAILED DESCRIPTION OF THE INVENTION

[0020] Definitions

[0021] The present invention may be understood more readily by reference to the following detailed description of the invention and the examples provided therein. It is to be understood that this invention is not limited to the specific methods, formulations, and conditions described, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects of the invention only and is not intended to be limiting.

[0022] Values may be expressed as “about” or “approximately” a given number. Similarly, ranges may be expressed herein as from “about” one particular value and / or to “about” or 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, by use of the antecedent “about,” it will be understood that the particular value forms another aspect.

[0023] As used herein, the terms “a,” “an,” and “the” mean one or more.

[0024] As used herein, the term “and / or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

[0025] As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

[0026] As used herein, the terms “having,” “has,” and “have” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0027] As used herein, the terms “including,” “includes,” and “include” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

[0028] “Degree of Substitution” is used to describe the average substitution level of the substituents per anhydroglucose unit (“AGU”). Generally, conventional cellulose contains three hydroxyl groups in each AGU that can be substituted. Therefore, the DS can have a value between 0 and 3. However, low molecular weight cellulose mixed esters can have a total degree of substitution slightly above 3 from end group contributions. Low molecular weight cellulose mixed esters are discussed in more detail subsequently in this disclosure. Because DS is a statistical mean value, a value of 1 does not assure that every AGU has a single substituent. In some cases, there can be unsubstituted anhydroglucose units, some with two and some with three substituents, and more often than not the value will be a noninteger. Total DS is defined as the average number of all of substituents per anhydroglucose unit. The degree of substitution per AGU can also refer to a particular substituent, such as, for example, hydroxyl, acetyl, butyryl, or propionyl. Additionally, the degree of substitution can specify a given hydroxyl based on the carbon unit of the anhydroglucose unit.

[0029] When the degree of substitution refers to hydroxyl, i.e, DSOH, the reference is to the average hydroxyl groups per anhydroglucose that are not substituted. As a result, DSOH is not used in the calculation of the total degree of substitution.

[0030] “Admixing” means mixing. In the context of forming a plasticized polymeric composition, admixing means to mix the polymeric composition with the plasticizer composition. The admixing can occur, for example, by spraying the plasticizer composition onto the polymeric composition or by simply pouring plasticizer composition onto the polymeric composition followed by mixing. In one embodiment or in combination with any other embodiment disclosed herein, the admixing occurs in an extruder. The polymeric composition is added to the extruder, and the plasticizer composition is fed into the extruder. The two materials will be admixed in the extruder.

[0031] Numerical Ranges

[0032] The present description uses numerical ranges to quantify certain parameters relating to the invention. It should be understood that when numerical ranges are provided, such ranges are to be construed as providing literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of 10 to 100 provides literal support for a claim reciting “greater than 10” (with no upper bounds) and a claim reciting “less than 100” (with no lower bounds).

[0033] The present description uses specific numerical values to quantify certain parameters relating to the invention, where the specific numerical values are not expressly part of a numerical range. It should be understood that each specific numerical value provided herein is to be construed as providing literal support for a broad, intermediate, and narrow range. The broad range associated with each specific numerical value is the numerical value plus and minus 60 percent of the numerical value, rounded to two significant digits. The intermediate range associated with each specific numerical value is the numerical value plus and minus 30 percent of the numerical value, rounded to two significant digits. The narrow range associated with each specific numerical value is the numerical value plus and minus 15 percent of the numerical value, rounded to two significant digits. For example, if the specification describes a specific temperature of 62 °F, such a description provides literal support for 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 be applied not only to the specific values, but should also be applied to differences between these specific values. Thus, if the 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 ranges for the pressure difference between these two streams would be 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi, respectively.

[0034] Throughout this application, where patents or publications are referenced, the disclosures of these references in their entireties are intended to be incorporated by reference into this application, to the extent they are not inconsistent with the present invention, in order to more fully describe the state of the art to which the invention pertains.

[0035] Terephthalate-based plasticizer

[0036] The terephthalate-based plasticizer may have two alkyl groups bound to a diester group, wherein each alkyl group has 4 to 10 carbon atoms, preferably 6 to 9 carbon atoms, and more preferably 7 to 9 carbon atoms. The terephthalate-based plasticizer is the most useful plasticizer that can substitute for a phthalate-based plasticizer, exhibits the same levels of basic mechanical properties as compared with a conventional phthalate-based plasticizer, and therefore can be applied as an eco-friendly plasticizer.

[0037] In addition, each of the two alkyl groups bound to the diester group of the terephthalate-based plasticizer may be, for example, a normal butyl group, an isobutyl group, a normal pentyl group, an isopentyl group, a normal hexyl group, a normal heptyl group, an isoheptyl group, a normal octyl group, an isooctyl group, a 2-ethylhexyl group, a normal nonyl group, an isononyl group, a 2-propylheptyl group or an isodecyl group, and preferably, a normal butyl group, an isopentyl group, an isoheptyl group, a 2-ethylhexyl group, an isononyl group, a 2-propylheptyl group or an isodecyl group.

[0038] Specifically, for example, the terephthalate-based plasticizer may be dibutyl terephthalate (DBTP), diisopentyl terephthalate (DIPTP), dihexyl terephthalate (DHxTP), diisoheptyl terephthalate (DIHTP), di(2-ethylhexyl) terephthalate (DEHTP), diisononyl terephthalate (DINTP), di(2-propylheptyl) terephthalate (DPHTP), diisodecyl terephthalate (DIDTP), (2- ethylhexyl)isononyl terephthalate (EHINTP), (2-ethylhexyl)(2-propylheptyl) terephthalate, isononyl(2-propylheptyl) terephthalate, isodecyl isononyl terephthalate, (2-ethylhexyl)isodecyl terephthalate, isodecyl(2-propylheptyl) terephthalate, butyl(2-ethylhexyl) terephthalate, isoheptyl (2-ethylhexyl) terephthalate, isopentyl isononyl terephthalate, isopentyl(2-ethylhexyl) terephthalate, isopentyl(2-propylheptyl) terephthalate or butyl isoheptyl terephthalate.

[0039] Regarding the preparation method, the terephthalate-based plasticizer maybe prepared by direct esterification of terephthalic acid and one or more alcohols, or trans-esterification of a dialkyl terephthalate and an alcohol.

[0040] That is, the alcohol is a primary alcohol, in which an alkyl group may be selected from the group consisting of a normal butyl group, an isobutyl group, a normal pentyl group, an isopentyl group, a normal hexyl group, a normal heptyl group, an isoheptyl group, a normal octyl group, an isooctyl group, a 2- ethylhexyl group, a normal nonyl group, an isononyl group, a 2-propylheptyl group or an isodecyl group as described above. When one type of alcohol is applied to direct esterification, a single terephthalate may be applied, or when a mixture of two or more alcohol is applied to direct esterification or subjected to trans-esterification, a mixture of two or more types of terephthalates may be applied.

[0041] Specifically, when the trans-esterification is performed and a terephthalate mixture-based plasticizer is applied, the terephthalates may be included at a specific composition ratio in the terephthalate mixture-based plasticizer. For example, the terephthalate mixture may be prepared through transesterification using di(alkyl A) terephthalate having alkyl A as an alkyl group and (alkyl B) alcohol having alkyl B as an alkyl group as reactants, in which 3.0 to 99.0 mol% of di(alkyl A)terephthalate, 0.5 to 96.5 mol% of (alkyl A)(alkyl B)terephthalate and 0.5 to 96.5 mol% of di(alkyl B)terephthalate are included.

[0042] The composition ratio may be a mixing composition ratio produced by esterification, or a composition ratio intentionally determined by additionally mixing a specific compound(s), and the composition ratio may be properly adjusted according to a desired physical property.

[0043] Cellulose Esters

[0044] The cellulose ester of the present invention may be generally described to include cellulose esters of one or more carboxylic acids and are described for example in U.S. Patent No. 5,929,229, assigned to the assignee of the present invention, the contents and disclosure of which are incorporated herein by reference. Non limiting examples of cellulose esters include cellulose acetate, cellulose propionate, cellulose butyrate, so-called mixed acid esters such as cellulose acetate propionate and cellulose acetate butyrate and combinations thereof. In one or more embodiments, the cellulose ester is chosen from the group consisting of cellulose acetate, cellulose acetate propionate, or cellulose acetate butyrate and combinations thereof. In one or more embodiments, the cellulose ester includes, consists essentially of or consists of cellulose acetates.

[0045] Cellulose esters that may be useful for the present invention generally comprise repeating units of the structure:

[0046] wherein R1, R2, and R3are selected independently from the group consisting of hydrogen, acetyl, butyryl, propionyl, or combinations thereof. For cellulose esters, the substitution level is usually expressed in terms of degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups in each AGU unit that cellulose esters be substituted; therefore, DS cellulose ester have a value between zero and three. Native cellulose is a large polysaccharide with a degree of polymerization from 250 - 5,000 even after pulping and purification, and thus the assumption that the maximum DS is 3.0 is approximately correct. Because DS is a statistical mean value, a value of 1 does not assure that every AGU has a single substituent. The cellulose esters can be unsubstituted anhydroglucose units, some with two and some with three substituents, and typically the value will be a non-integer. Total DS is defined as the average number of all of substituents per anhydroglucose unit. The degree of substitution per AGU cellulose esters also refer to a particular substituent, such as, for example, hydroxyl, acetyl, butyryl, propionyl, or combinations thereof. In embodiments, n is an integer in a range from 25 to 250, or 25 to 200, or 25 to 150, or 25 to 100, or 25 to 75. Cellulose esters useful in embodiments of the present invention cellulose esters have a degree of substitution in the range of from 1 .0 to 2.5. In some embodiments, the cellulose esters 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 not 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. In some embodiments, the cellulose esters may have an average degree of substitution of from 0.7 to 2.9, or from 1 .1 to 2.7, or from 1 .1 to 2.6, or from 1 .1 to 2.5, or from 2.0 to 2.6, or from 1 .7 to 2.6.

[0047] In embodiments of the invention, the cellulose esters have at least 2 anhydroglucose rings and have between at least 50 and up to 5,000 anhydroglucose rings, or at least 50 and less than 150 anhydroglucose rings. The number of anhydroglucose units per molecule is defined as the degree of polymerization (DP) of the cellulose esters. In embodiments, cellulose esters may have an inherent viscosity (IV) of about 0.2 to about 3.0 deciliters / gram, or about 0.5 to about 1 .8, or about 1 to about 1 .5, as measured at a temperature of 25°C for a 0.25-gram sample in 100 ml of a 60 / 40 by weight solution of phenol / tetrachloroethane. In embodiments, cellulose esters useful in some embodiments 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 substituting ester is acetyl, butyryl, propionyl or combinations thereof.

[0048] Cellulose esters useful in the present invention, and particularly cellulose acetates, may be biodegradable. The term “biodegradable” generally refers to the biological conversion and consumption of organic molecules. Biodegradability is an intrinsic property of the material itself, and the material cellulose acetate exhibit different degrees of biodegradability, depending on the specific conditions to which it is exposed. The term “disintegrable” refers to the tendency of a material to physically decompose into smaller fragments when exposed to certain conditions. Disintegration depends both on the material itself, as well as the physical size and configuration of the article being tested. Ecotoxicity measures the impact of the material on plant life, and the heavy metal content of the material is determined according to the procedures laid out in a standard test method. The melt-processable compositions and the melts of the present invention, in one or more embodiments, may be biodegradable.

[0049] Cellulose esters of the present invention may be produced by any method known in the art. Examples of processes for producing cellulose esters generally are taught in Kirk-Othmer, Encyclopedia of Chemical Technology, 5th Edition, Vol. 5, Wiley-lnterscience, New York (2004), pp. 394- 444. Cellulose, the starting material for producing cellulose esters, may be obtained in different grades and sources such as from cotton linters, softwood pulp, hardwood pulp, corn fiber and other agricultural sources, and bacterial cellulose, among others.

[0050] One method of producing cellulose esters is esterification of the cellulose by mixing cellulose with the appropriate organic acids, acid anhydrides, and cellulose catalysts. Cellulose is then converted to a cellulose triester. Ester hydrolysis is then performed by adding a water-acid mixture to the cellulose triester, which the cellulose ester 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 may then be washed with water to remove reaction by-products followed by dewatering and drying.

[0051] The cellulose triesters to be hydrolyzed have three acyl substituents. These cellulose esters may be prepared by a number of methods known to those skilled in the art. For example, cellulose esters may be prepared by heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a cellulose catalyst such as H2SO4. Cellulose triesters may also be prepared by the homogeneous acylation of cellulose dissolved in an appropriate solvent such as LiCI / DMAc or LiCI / NMP.

[0052] Those skilled in the art will understand that the commercial term of cellulose triesters also encompasses cellulose esters that are not completely substituted with acyl groups. For example, cellulose triacetate commercially available from Eastman Chemical Company, Kingsport, TN, U.S.A., typically has a DS from about 2.85 to about 2.99.

[0053] After esterification of the cellulose to the triester, part of the acyl substituent may be removed by hydrolysis or by alcoholysis to give a secondary cellulose ester. As noted previously, depending on the particular method employed, the distribution of the acyl substituents may be random or non-random. Secondary cellulose esters may also be prepared directly with no hydrolysis by using a limiting amount of acylating reagent. This process is particularly useful when the reaction is conducted in a solvent that will dissolve cellulose. All of these methods yield cellulose esters that are useful in this invention.

[0054] In one embodiment or in combination with any of the mentioned embodiments, or in combination with any of the mentioned embodiments, the cellulose desters may have a polystyrene equivalent number average molecular weight (Mn) from about 10,000 to about 100,000 as measured by gel permeation chromatography (GPC) using NMP as solvent and polystyrene equivalent Mn according to ASTM D6474. In other aspects or embodiments, the cellulose esters have a polystyrene equivalent number average molecular weights (Mn) from 10,000 to 90,000; or 10,000 to 80,000; or 10,000 to 70,000; or 10,000 to 60,000; or 10,000 to less than 60,000; or 10,000 to less than 55,000; or 10,000 to 50,000; or 10,000 to less than 50,000; or 10,000 to less than 45,000; or 10,000 to 40,000; or 10,000 to 30,000; or 20,000 to less than 60,000; or 20,000 to less than 55,000; or 20,000 to 50,000; or 20,000 to less than 50,000; or 20,000 to less than 45,000; or 20,000 to 40,000; or 20,000 to 35,000; or 20,000 to 30,000; or 30,000 to less than 60,000; or 30,000 to less than 55,000; or 30,000 to 50,000; or 30,000 to less than 50,000; or 30,000 to less than 45,000; or 30,000 to 40,000; or 30,000 to 35,000; as measured by gel permeation chromatography (GPC) using NMP as solvent and according to ASTM D6474. In embodiments, the cellulose esters may have a number average molecular weight (Mn) of not more than 100,000, or not more than 90,000, measured using gel permeation chromatography with a polystyrene equivalent and using N-methyl-2-pyrrolidone (NMP) as the solvent.

[0055] The most common commercial secondary cellulose esters are prepared by initial acid catalyzed heterogeneous acylation of cellulose to form the cellulose triester. After a homogeneous solution in the corresponding carboxylic acid of the cellulose triester is obtained, 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 roughly equal.

[0056] In embodiments of the invention, the cellulose ester may be prepared by converting cellulose to a cellulose ester with reactants that are obtained from recycled materials, e.g., a recycled plastic content syngas source. In embodiments, such reactants may be cellulose reactants that include organic acids and / or acid anhydrides used in the esterification or acylation reactions of the cellulose, e.g., as discussed herein.

[0057] Composition

[0058] The present application, in a first aspect, disclosed a composition, comprising: (i) greater than 15 weight percent (“wt%”) of n-butyl methyl terephthalate (“MBT”); and (ii) greater than 1wt% of at least one plasticizer, wherein the at least one plasticizer is different than MBT, wherein the wt% of each is based on the total weight of the compositions.

[0059] In one embodiment or in combination with any other embodiment in the first aspect, the at least one plasticizer is biodegradable. In one class of this embodiment, the at least one plasticizer is biodegradable according to OECD 301 F.

[0060] In one embodiment or in combination with any other embodiment in the first aspect, the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly(alkyl succinate) plasticizer, an adipate- based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4-trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof. In one class of this embodiment, the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof. In one class of this embodiment, the composition is a liquid.

[0061] In one embodiment or in combination with any other embodiment in the first aspect, the composition is a liquid.

[0062] In one embodiment or in combination with any other embodiment in the first aspect, the MBT is present at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%. In one embodiment or in combination with any other embodiment in the first aspect, the MBT is present at from 15-99wt%, or from 15-95wt%, or from 15-90wt%, or from 15-85wt%, or from 15-80wt%, or from 15-70wt%, or from 15-60wt%, or from 15-50wt%, or from 15-40wt%, or from 15-30wt%, or from 15-20wt%, or from 20-99wt%, or from 20-95wt%, or from 20-90wt%, or from 20-85wt%, or from 20-80wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-30wt%, or from 30-99wt%, or from 30-95wt%, or from 30-90wt%, or from 30-85wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-99wt%, or from 40-95wt%, or from 40-90wt%, or from 40-85wt%, or from 40-80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-99wt%, or from 50-95wt%, or from 50-90wt%, or from 50-85wt%, or from 50-80wt%, or from 50-70wt%, or from 50-60wt%, or from 60-99wt%, or from 60-95wt%, or from 60-90wt%, or from 60-85wt%, or from 60-80wt%, or from 60-70wt%, or from 70-99wt%, or from 70-95wt%, or from 70-90wt%, or from 70-85wt%, or from 70-80wt%, or from 80-99wt%, or from 80-95wt%, or from 80-90wt%, or from 90-99wt%, or from 90-95wt%.

[0063] In one embodiment or in combination with any other embodiment in the first aspect, the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than 15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%.

[0064] In one embodiment or in combination with any other embodiment in the first aspect, the at least one plasticizer is present from 1 -85wt%, or from 1 - 80wt%, or from 1 -75wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 - 50wt%, or from 1 -40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 - 15wt%, or from 1 -1 Owt%, or from 1 -5wt%, or from 1 -2wt%, or from 2-85wt%, or from 2-80wt%, or from 2-75wt%, or from 2-70wt%, or from 2-60wt%, or from 2-50wt%, or from 2-40wt%, or from 2-30wt%, or from 2-20wt%, or from 2-15wt%, or from 2-1 Owt%, or from 2-5wt%, or from 5-85wt%, or from 5- 80wt%, or from 5-75wt%, or from 5-70wt%, or from 5-60wt%, or from 5- 50wt%, or from 5-40wt%, or from 5-30wt%, or from 5-20wt%, or from 5- 15wt%, or from 5-1 Owt%, or from 10-85wt%, or from 10-80wt%, or from 10- 75wt%, or from 10-70wt%, or from 10-60wt%, or from 10-50wt%, or from 10- 40wt%, or from 10-30wt%, or from 10-20wt%, or from 10-15wt%, or from 15- 85wt%, or from 15-80wt%, or from 15-75wt%, or from 15-70wt%, or from 15- 60wt%, or from 15-50wt%, or from 15-40wt%, or from 15-30wt%, or from 15- 20wt%, or from 20-85wt%, or from 20-80wt%, or from 20-75wt%, or from 20- 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20- 30wt%, or from 30-85wt%, or from 30-80wt%, or from 30-75wt%, or from 30- 70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40- 85wt%, or from 40-80wt%, or from 40-75wt%, or from 40-70wt%, or from 40- 60wt%, or from 40-50wt%, from 50-85wt%, or from 50-80wt%, or from 50- 75wt%, or from 50-70wt%, or from 50-60wt%, or from 60-85wt%, or from 60- 80wt%, or from 60-75wt%, or from 60-70wt%, from 70-85wt%, or from 70- 80wt%, or from 80-85wt%.

[0065] Method for Plasticizing a Polymeric Composition

[0066] The present application, in a second aspect, discloses a method for plasticizing a polymeric composition, comprising: (i) admixing a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) with the polymeric composition.

[0067] In one embodiment or in combination with any other embodiment in the second aspect, the MBT is present in the plasticizer composition at 100wt%, or less than 99wt%, or less than 95wt%, or less than 90wt%, or less than 80wt%, or less than 70wt%, or less than 60wt%, or less than 50wt%, or less than 40wt%, or less than 30wt%, or less than 20wt%, or less than 15wt%, or less than 10wt%, or less than 5wt%, or less than 2wt%, or from 5-99wt%, or from 5-95wt%, or from 5-90wt%, or from 5-80wt%, or from 5-70wt%, or from 5-60wt%, or from 5-50wt%, of rom 5-40wt%, of from 5-30wt%, of from 5- 20wt%, or from 5-15wt%, or from 5-10wt%, or from 10-99wt%, or from 10- 95wt%, or from 10-90wt%, or from 10-80wt%, or from 10-70wt%, or from 10-

[0068] 60wt%, or from 10-50wt%, of from 10-40wt%, or from 10-30wt%, of from 10-

[0069] 20wt%, or from 10-15wt%, or from 15-99wt%, or from 15-95wt%, or from 15-

[0070] 90wt%, or from 15-80wt%, or from 15-70wt%, or from 15-60wt%, or from 15-

[0071] 50wt%, of from 15-40wt%, or from 15-30wt%, or from 15-20wt%, or from 20-

[0072] 99wt%, or from 20-95wt%, or from 20-90wt%, or from 20-80wt%, or from 20-

[0073] 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, of from 20-

[0074] 30wt%, or from 30-99wt%, or from 30-95wt%, or from 30-90wt%, or from 30-

[0075] 80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-

[0076] 40wt%, or from 40-99wt%, or from 40-95wt%, or from 40-90wt%, or from 40-

[0077] 80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-

[0078] 99wt%, or from 50-95wt%, or from 50-90wt%, or from 50-80wt%, or from 50-

[0079] 70wt%, or from 50-60wt% or from 60-99wt%, or from 60-95wt%, or from 60- 90wt%, or from 60-80wt%, or from 60-70wt%, or from 70-99wt%, or from 70-

[0080] 95wt%, or from 70-90wt%, or from 70-80wt%, or from 80-99wt%, or from 80-

[0081] 95wt%, or from 80-90wt%, or from 90-99wt%, or from 90-95wt%, based on the total weight of the plasticizer composition.

[0082] In one embodiment or in combination with any other embodiment in the second aspect, the plasticizer composition further comprises at least 1wt% of an at least one plasticizer that is different than MBT.

[0083] In one class of this embodiment, or in combination with any other embodiment or class of the second aspect, the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than 15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%.

[0084] In one class of this embodiment, or in combination with any other embodiment or class of the second aspect, the at least one plasticizer is present from 1 -85wt%, or from 1 -80wt%, or from 1 -75wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 -50wt%, or from 1 -40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 -15wt%, or from 1 -1 Owt%, or from 1 -5wt%, or from 1 - 2wt%, or from 2-85wt%, or from 2-80wt%, or from 2-75wt%, or from 2-70wt%, or from 2-60wt%, or from 2-50wt%, or from 2-40wt%, or from 2-30wt%, or from 2-20wt%, or from 2-15wt%, or from 2-10wt%, or from 2-5wt%, or from 5- 85wt%, or from 5-80wt%, or from 5-75wt%, or from 5-70wt%, or from 5- 60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5- 20wt%, or from 5-15wt%, or from 5-10wt%, or from 10-85wt%, or from 10- 80wt%, or from 10-75wt%, or from 10-70wt%, or from 10-60wt%, or from 10- 50wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 10- 15wt%, or from 15-85wt%, or from 15-80wt%, or from 15-75wt%, or from 15- 70wt%, or from 15-60wt%, or from 15-50wt%, or from 15-40wt%, or from 15- 30wt%, or from 15-20wt%, or from 20-85wt%, or from 20-80wt%, or from 20- 75wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20- 40wt%, or from 20-30wt%, or from 30-85wt%, or from 30-80wt%, or from 30- 75wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30- 40wt%, or from 40-85wt%, or from 40-80wt%, or from 40-75wt%, or from 40- 70wt%, or from 40-60wt%, or from 40-50wt%, from 50-85wt%, or from 50-

[0085] 80wt%, or from 50-75wt%, or from 50-70wt%, or from 50-60wt%, or from 60-

[0086] 85wt%, or from 60-80wt%, or from 60-75wt%, or from 60-70wt%, from 70-

[0087] 85wt%, or from 70-80wt%, or from 80-85wt%.

[0088] In one embodiment or in combination with any other embodiment in the second aspect, the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly(alkyl succinate) plasticizer, an adipate- based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4-trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof. In one class of this embodiment, the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof. In one class of this embodiment, the composition is a liquid.

[0089] In one embodiment or in combination with any other embodiment in the second aspect, the MBT is present in the plasticizer composition at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%, based on the total weight of the plasticizer composition. In one embodiment or in combination with any other embodiment in the second aspect, the MBT is present in the plasticizer composition at from 15- 99wt%, or from 15-95wt%, or from 15-90wt%, or from 15-85wt%, or from 15-

[0090] 80wt%, or from 15-70wt%, or from 15-60wt%, or from 15-50wt%, or from 15-

[0091] 40wt%, or from 15-30wt%, or from 15-20wt%, or from 20-99wt%, or from 20-

[0092] 95wt%, or from 20-90wt%, or from 20-85wt%, or from 20-80wt%, or from 20-

[0093] 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-

[0094] 30wt%, or from 30-99wt%, or from 30-95wt%, or from 30-90wt%, or from 30-

[0095] 85wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-

[0096] 50wt%, or from 30-40wt%, or from 40-99wt%, or from 40-95wt%, or from 40-

[0097] 90wt%, or from 40-85wt%, or from 40-80wt%, or from 40-70wt%, or from 40-

[0098] 60wt%, or from 40-50wt%, or from 50-99wt%, or from 50-95wt%, or from 50-

[0099] 90wt%, or from 50-85wt%, or from 50-80wt%, or from 50-70wt%, or from 50-

[0100] 60wt%, or from 60-99wt%, or from 60-95wt%, or from 60-90wt%, or from 60-

[0101] 85wt%, or from 60-80wt%, or from 60-70wt%, or from 70-99wt%, or from 70-

[0102] 95wt%, or from 70-90wt%, or from 70-85wt%, or from 70-80wt%, or from 80-

[0103] 99wt%, or from 80-95wt%, or from 80-90wt%, or from 90-99wt%, or from 90-

[0104] 95wt%, based on the total weight of the plasticizer composition.

[0105] In one embodiment or in combination with any other embodiment in the second aspect, the polymeric composition comprises a cellulose ester, a polyester, a polyvinyl chloride, a polyethylene terephthalate, an acrylonitrile butadiene styrene, or combinations thereof.

[0106] In one embodiment or in combination with any other embodiment in the second aspect, the polymeric composition comprises a cellulose ester. In one class of this embodiment, the cellulose ester is a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate propionate, a cellulose acetate propionate, or a cellulose butyrate propionate. In one class of this embodiment, the cellulose ester is a cellulose acetate. In one class of this embodiment, the cellulose ester is a cellulose propionate. In one class of this embodiment, the cellulose ester is a cellulose butyrate. In one class of this embodiment, the cellulose ester is a cellulose acetate propionate. In one class of this embodiment, the cellulose ester is a cellulose acetate butyrate. In one class of this embodiment, the cellulose ester is a cellulose butyrate propionate.

[0107] In one embodiment or in combination with any other embodiment in the second aspect, the polymeric composition is in the form of a particulate material. In one class of this embodiment, the particulate material is a powder, grandules, or pellets.

[0108] In one embodiment or in combination with any other embodiment in the second aspect, the admixing occurs in an extruder.

[0109] Use of butyl methyl terephthalate (“MBT”) as a plasticizer

[0110] The present application, in a third aspect, discloses a use of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) as a plasticizer for a polymeric composition.

[0111] In one embodiment or in combination with any other embodiment in the third aspect, the MBT is present in the plasticizer composition at 100wt%, or less than 99wt%, or less than 95wt%, or less than 90wt%, or less than 80wt%, or less than 70wt%, or less than 60wt%, or less than 50wt%, or less than 40wt%, or less than 30wt%, or less than 20wt%, or less than 15wt%, or less than 10wt%, or less than 5wt%, or less than 2wt%, or from 5-99wt%, or from 5-95wt%, or from 5-90wt%, or from 5-80wt%, or from 5-70wt%, or from 5- 60wt%, or from 5-50wt%, of rom 5-40wt%, of from 5-30wt%, of from 5-20wt%, or from 5-15wt%, or from 5-1 Owt%, or from 10-99wt%, or from 10-95wt%, or from 10-90wt%, or from 10-80wt%, or from 10-70wt%, or from 10-60wt%, or from 10-50wt%, of from 10-40wt%, or from 10-30wt%, of from 10-20wt%, or from 10-15wt%, or from 15-99wt%, or from 15-95wt%, or from 15-90wt%, or from 15-80wt%, or from 15-70wt%, or from 15-60wt%, or from 15-50wt%, of from 15-40wt%, or from 15-30wt%, or from 15-20wt%, or from 20-99wt%, or from 20-95wt%, or from 20-90wt%, or from 20-80wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, of from 20-30wt%, or from 30-99wt%, or from 30-95wt%, or from 30-90wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-99wt%, or from 40-95wt%, or from 40-90wt%, or from 40-80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-99wt%, or from 50-95wt%, or from 50-90wt%, or from 50-80wt%, or from 50-70wt%, or from 50-60wt% or from 60-99wt%, or from 60-95wt%, or from 60-90wt%, or from 60-80wt%, or from 60-70wt%, or from 70-99wt%, or from 70-95wt%, or from 70-90wt%, or from 70-80wt%, or from 80-99wt%, or from 80-95wt%, or from 80-90wt%, or from 90-99wt%, or from 90-95wt%, based on the total weight of the plasticizer composition.

[0112] In one embodiment or in combination with any other embodiment in the third aspect, the plasticizer composition further comprises at least 1wt% of an at least one plasticizer that is different than MBT.

[0113] In one class of this embodiment, or in combination with any other embodiment or class of the third aspect, the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than 15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%.

[0114] In one class of this embodiment, or in combination with any other embodiment or class of the third aspect, the at least one plasticizer is present from 1 -85wt%, or from 1 -80wt%, or from 1 -75wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 -50wt%, or from 1 -40wt%, or from 1 -30wt%, or from 1 - 20wt%, or from 1 -15wt%, or from 1 -1 Owt%, or from 1 -5wt%, or from 1 -2wt%, or from 2-85wt%, or from 2-80wt%, or from 2-75wt%, or from 2-70wt%, or from 2-60wt%, or from 2-50wt%, or from 2-40wt%, or from 2-30wt%, or from 2-20wt%, or from 2-15wt%, or from 2-10wt%, or from 2-5wt%, or from 5- 85wt%, or from 5-80wt%, or from 5-75wt%, or from 5-70wt%, or from 5-

[0115] 60wt%, or from 5-50wt%, or from 5-40wt%, or from 5-30wt%, or from 5-

[0116] 20wt%, or from 5-15wt%, or from 5-10wt%, or from 10-85wt%, or from 10-

[0117] 80wt%, or from 10-75wt%, or from 10-70wt%, or from 10-60wt%, or from 10-

[0118] 50wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 10-

[0119] 15wt%, or from 15-85wt%, or from 15-80wt%, or from 15-75wt%, or from 15-

[0120] 70wt%, or from 15-60wt%, or from 15-50wt%, or from 15-40wt%, or from 15-

[0121] 30wt%, or from 15-20wt%, or from 20-85wt%, or from 20-80wt%, or from 20-

[0122] 75wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-

[0123] 40wt%, or from 20-30wt%, or from 30-85wt%, or from 30-80wt%, or from 30-

[0124] 75wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-

[0125] 40wt%, or from 40-85wt%, or from 40-80wt%, or from 40-75wt%, or from 40-

[0126] 70wt%, or from 40-60wt%, or from 40-50wt%, from 50-85wt%, or from 50-

[0127] 80wt%, or from 50-75wt%, or from 50-70wt%, or from 50-60wt%, or from 60-

[0128] 85wt%, or from 60-80wt%, or from 60-75wt%, or from 60-70wt%, from 70-

[0129] 85wt%, or from 70-80wt%, or from 80-85wt%.

[0130] In one embodiment or in combination with any other embodiment in the third aspect, the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly(alkyl succinate) plasticizer, an adipate- based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4-trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof. In one class of this embodiment, the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof. In one class of this embodiment, the composition is a liquid.

[0131] In one embodiment or in combination with any other embodiment in the third aspect, the MBT is present in the plasticizer composition at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%, based on the total weight of the plasticizer composition. In one embodiment or in combination with any other embodiment in the second aspect, the MBT is present in the plasticizer composition at from 15-99wt%, or from 15-95wt%, or from 15-90wt%, or from 15-85wt%, or from 15-80wt%, or from 15-70wt%, or from 15-60wt%, or from 15-50wt%, or from 15-40wt%, or from 15-30wt%, or from 15-20wt%, or from 20-99wt%, or from 20-95wt%, or from 20-90wt%, or from 20-85wt%, or from 20-80wt%, or from 20-70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-30wt%, or from 30-99wt%, or from 30-95wt%, or from 30-90wt%, or from 30-85wt%, or from 30-80wt%, or from 30-70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-99wt%, or from 40-95wt%, or from 40-90wt%, or from 40-85wt%, or from 40-80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-99wt%, or from 50-95wt%, or from 50-90wt%, or from 50-85wt%, or from 50-80wt%, or from 50-70wt%, or from 50-60wt%, or from 60-99wt%, or from 60-95wt%, or from 60-90wt%, or from 60-85wt%, or from 60-80wt%, or from 60-70wt%, or from 70-99wt%, or from 70-95wt%, or from 70-90wt%, or from 70-85wt%, or from 70-80wt%, or from 80-99wt%, or from 80-95wt%, or from 80-90wt%, or from 90-99wt%, or from 90-95wt%, based on the total weight of the plasticizer composition.

[0132] In one embodiment or in combination with any other embodiment in the third aspect, the polymeric composition comprises a cellulose ester, a polyester, a polyvinyl chloride, a polyethylene terephthalate, an acrylonitrile butadiene styrene, or combinations thereof.

[0133] In one embodiment or in combination with any other embodiment in the third aspect, the polymeric composition comprises a cellulose ester. In one class of this embodiment, the cellulose ester is a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate propionate, a cellulose acetate propionate, or a cellulose butyrate propionate. In one class of this embodiment, the cellulose ester is a cellulose acetate. In one class of this embodiment, the cellulose ester is a cellulose propionate. In one class of this embodiment, the cellulose ester is a cellulose butyrate. In one class of this embodiment, the cellulose ester is a cellulose acetate propionate. In one class of this embodiment, the cellulose ester is a cellulose acetate butyrate. In one class of this embodiment, the cellulose ester is a cellulose butyrate propionate.

[0134] In one embodiment or in combination with any other embodiment in the third aspect, the polymeric composition is in the form of a particulate material. In one class of this embodiment, the particulate material is a powder, grandules, or pellets.

[0135] Plasticized Cellulose Ester Composition

[0136] The present application, in a fourth aspect, discloses a plasticized cellulose ester composition, comprising: (i) a cellulose ester; and (ii) at least 1wt% of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”), based on the total weight of the plasticized cellulose ester composition.

[0137] In one embodiment or in combination with any other embodiment in the fourth aspect, the plasticized cellulose ester composition is biodegradable according to OECD 301 F.

[0138] In one embodiment or in combination with any other embodiment in the fourth aspect, the plasticizer composition is biodegradable. In one class of this embodiment, the plasticizer is biodegradable according to OECD 301 F.

[0139] In one embodiment or in combination with any other embodiment in the fourth aspect, the plasticizer composition further comprises an at least one plasticizer that is different than MBT. In one class of this embodiment, the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly (alkyl succinate) plasticizer, an adipate-based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4-trimethylpentane-1 ,3- diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof. In one class of this embodiment, the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof. In one class of this embodiment, the composition is a liquid.

[0140] In one embodiment or in combination with any other embodiment in the fourth aspect, the composition is a liquid.

[0141] In one embodiment or in combination with any other embodiment in the fourth aspect, the MBT is present at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%. In one embodiment or in combination with any other embodiment in the fourth aspect, the MBT is present at from 15-99wt%, or from 15-95wt%, or from 15- 90wt%, or from 15-85wt%, or from 15-80wt%, or from 15-70wt%, or from 15-

[0142] 60wt%, or from 15-50wt%, or from 15-40wt%, or from 15-30wt%, or from 15-

[0143] 20wt%, or from 20-99wt%, or from 20-95wt%, or from 20-90wt%, or from 20-

[0144] 85wt%, or from 20-80wt%, or from 20-70wt%, or from 20-60wt%, or from 20-

[0145] 50wt%, or from 20-40wt%, or from 20-30wt%, or from 30-99wt%, or from 30-

[0146] 95wt%, or from 30-90wt%, or from 30-85wt%, or from 30-80wt%, or from 30-

[0147] 70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-

[0148] 99wt%, or from 40-95wt%, or from 40-90wt%, or from 40-85wt%, or from 40-

[0149] 80wt%, or from 40-70wt%, or from 40-60wt%, or from 40-50wt%, or from 50-

[0150] 99wt%, or from 50-95wt%, or from 50-90wt%, or from 50-85wt%, or from 50-

[0151] 80wt%, or from 50-70wt%, or from 50-60wt%, or from 60-99wt%, or from 60-

[0152] 95wt%, or from 60-90wt%, or from 60-85wt%, or from 60-80wt%, or from 60-

[0153] 70wt%, or from 70-99wt%, or from 70-95wt%, or from 70-90wt%, or from 70-

[0154] 85wt%, or from 70-80wt%, or from 80-99wt%, or from 80-95wt%, or from 80-

[0155] 90wt%, or from 90-99wt%, or from 90-95wt%.

[0156] In one embodiment or in combination with any other embodiment in the fourth aspect, the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than 15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%.

[0157] In one embodiment or in combination with any other embodiment in the fourth aspect, the at least one plasticizer is present from 1 -85wt%, or from 1 - 80wt%, or from 1 -75wt%, or from 1 -70wt%, or from 1 -60wt%, or from 1 - 50wt%, or from 1 -40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 - 15wt%, or from 1 -1 Owt%, or from 1 -5wt%, or from 1 -2wt%, or from 2-85wt%, or from 2-80wt%, or from 2-75wt%, or from 2-70wt%, or from 2-60wt%, or from 2-50wt%, or from 2-40wt%, or from 2-30wt%, or from 2-20wt%, or from 2-15wt%, or from 2-10wt%, or from 2-5wt%, or from 5-85wt%, or from 5- 80wt%, or from 5-75wt%, or from 5-70wt%, or from 5-60wt%, or from 5- 50wt%, or from 5-40wt%, or from 5-30wt%, or from 5-20wt%, or from 5- 15wt%, or from 5-1 Owt%, or from 10-85wt%, or from 10-80wt%, or from 10- 75wt%, or from 10-70wt%, or from 10-60wt%, or from 10-50wt%, or from 10-

[0158] 40wt%, or from 10-30wt%, or from 10-20wt%, or from 10-15wt%, or from 15-

[0159] 85wt%, or from 15-80wt%, or from 15-75wt%, or from 15-70wt%, or from 15-

[0160] 60wt%, or from 15-50wt%, or from 15-40wt%, or from 15-30wt%, or from 15-

[0161] 20wt%, or from 20-85wt%, or from 20-80wt%, or from 20-75wt%, or from 20-

[0162] 70wt%, or from 20-60wt%, or from 20-50wt%, or from 20-40wt%, or from 20-

[0163] 30wt%, or from 30-85wt%, or from 30-80wt%, or from 30-75wt%, or from 30-

[0164] 70wt%, or from 30-60wt%, or from 30-50wt%, or from 30-40wt%, or from 40-

[0165] 85wt%, or from 40-80wt%, or from 40-75wt%, or from 40-70wt%, or from 40-

[0166] 60wt%, or from 40-50wt%, from 50-85wt%, or from 50-80wt%, or from 50- 75wt%, or from 50-70wt%, or from 50-60wt%, or from 60-85wt%, or from 60- 80wt%, or from 60-75wt%, or from 60-70wt%, from 70-85wt%, or from 70- 80wt%, or from 80-85wt%.

[0167] In one embodiment or in combination with any other embodiment in the fourth aspect, the cellulose ester is a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate propionate, a cellulose acetate propionate, or a cellulose butyrate propionate. In one class of this embodiment, the cellulose ester is a cellulose acetate. In one class of this embodiment, the cellulose ester is a cellulose propionate. In one class of this embodiment, the cellulose ester is a cellulose butyrate. In one class of this embodiment, the cellulose ester is a cellulose acetate propionate. In one class of this embodiment, the cellulose ester is a cellulose acetate butyrate. In one class of this embodiment, the cellulose ester is a cellulose butyrate propionate.

[0168] In one embodiment or in combination with any other embodiment in the fourth aspect, the plasticized cellulose ester composition is in the form of a particulate material. In one class of this embodiment, the particulate material is a powder, granules, or pellets.

[0169] Articles

[0170] The present application, in a fifth aspect, discloses articles comprising the plasticized cellulose ester compositions disclosed herein.

[0171] In one embodiment or in combination with any other embodiment in the fifth aspect, the article is a film, a sheet, a food container, a foam, or an utensil.

[0172] In one embodiment or in combination with any other embodiment in the fifth aspect, the article is biodegradable according to OECD 301 F.

[0173] Specific Embodiments

[0174] Embodiment 1 . A composition, comprising:

[0175] (i) greater than 15wt% of n-butyl methyl terephthalate (“MBT”); and

[0176] (ii) greater than 1wt% of at least one plasticizer, wherein the at least one plasticizer is different than MBT, wherein the wt% of each is based on the total weight of the composition.

[0177] Embodiment 2. The composition of Embodiment 1 , wherein the at least one plasticizer is biodegradable according to OECD 301 F.

[0178] Embodiment 3. The composition of any one of Embodiments 1 -2, wherein the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly(alkyl succinate) plasticizer, an adipate-based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4- trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof.

[0179] Embodiment 4. The composition of any one of Embodiments 1 -3, wherein the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof.

[0180] Embodiment 5. The composition of any one of Embodiments 1 -4, wherein the composition is a liquid.

[0181] Embodiment 6. The composition of any one of Embodiments 1 -5, wherein the MBT is present at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%.

[0182] Embodiment 7. The composition of any one of Embodiments 1 -6, wherein the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than 15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%.

[0183] Embodiment 8. A method for plasticizing a polymeric composition, comprising: (i) admixing a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) with the polymeric composition.

[0184] Embodiment 9. Use of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) as a plasticizer for a polymeric composition.

[0185] Embodiment 10. The method or use of any one of Embodiments 8-9, wherein the polymeric composition comprises a cellulose ester. Embodiment 11 . The method or use of Embodiment 10, wherein the cellulose ester is a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate butyrate, a cellulose acetate propionate, or a cellulose butyrate propionate.

[0186] Embodiment 12. The method or use of Embodiment 11 , wherein the cellulose ester is a cellulose acetate.

[0187] Embodiment 13. The method or use of any one of Embodiments 8-12, wherein the polymeric composition is in the form of a particulate material. Embodiment 14. The method or use of any one of Embodiments 8-13, wherein the plasticizer composition is in the form of a liquid.

[0188] Embodiment 15. The method of any one of Embodiments 8, 10-14, wherein the admixing occurs in an extruder.

[0189] Embodiment 16. The method or use of any one of Embodiments 8-15, wherein the plasticizer composition is 100wt% of MBT.

[0190] Embodiment 17. The method or use of any one of Embodiments 8-16, wherein the plasticizer composition comprises at least 15wt% of MBT. Embodiment 18. The method or use of any one of Embodiments 8-17, wherein the plasticizer composition further comprises at least on plasticizer that is different than MBT.

[0191] Embodiment 19. The method or use of any one of Embodiments 8-18, wherein the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly(alkyl succinate) plasticizer, an adipate- based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4-trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof. Embodiment 20. The method or use of any one of Embodiments 8-19, wherein the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof.

[0192] Embodiment 21 . A plasticized cellulose ester composition, comprising:

[0193] (i) a cellulose ester; and

[0194] (ii) at least 1wt% of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”), based on the total weight of the plasticized cellulose ester composition. Embodiment 22. The plasticized cellulose ester composition of Embodiment 21 , wherein the plasticizer composition further comprises at least one plasticizer, wherein the at least one plasticizer is different than MBT. Embodiment 23. The plasticized cellulose ester composition of any one of Embodiments 21 -22, wherein the at least one plasticizer is biodegradable according to OECD 301 F.

[0195] Embodiment 24. The plasticized cellulose ester composition of any one of Embodiments 21 -23, wherein the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly (alkyl succinate) plasticizer, an adipate-based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4-trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof.

[0196] Embodiment 25. The plasticized cellulose ester composition of any one of Embodiments 21 -24, wherein the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof.

[0197] Embodiment 26. The plasticized cellulose ester composition of any one of Embodiments 21 -25, wherein the composition is a liquid.

[0198] Embodiment 27. The plasticized cellulose ester composition of any one of Embodiments 21 -26, wherein the MBT is present at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%, or is 100wt%, based on the total weight of the plasticizer composition. Embodiment 28. The plasticized cellulose ester composition of any one of Embodiments 21 -27, wherein the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than 15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%, or greater than 80wt%, or greater than 85wt%, or greater than 90wt%, or greater than 95wt%, based on the total weight of the plasticizer composition. Embodiment 29. The plasticized cellulose ester composition of any one of Embodiments 21 -28, wherein the cellulose ester is a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate propionate, a cellulose acetate propionate, or a cellulose butyrate propionate.

[0199] Embodiment 30. The plasticized cellulose ester composition of any one of Embodiments 21 -29, wherein the cellulose ester is a cellulose acetate. Embodiment 31 . The plasticized cellulose ester composition of any one of Embodiments 21 -30, wherein the plasticizer composition is present at at least 2wt%, or at least 5wt%, or at least 10wt%, or at least 15wt%, or at least 20wt%, or at least 30wt%, or from 1 -40wt%, or from 2-40wt%, or from 5- 40wt%, or from 10-40wt%, or from 15-40wt%, or from 20-40wt%, or from 30- 40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 -15wt%, or from 1 - 10wt%, or from 1 -5wt%, or from 1 -2wt%, or from 2-40wt%, or from 2-30wt%, or from 2-20wt%, or from 2-15wt%, or from 2-10wt%, or from 2-5wt%, or from 5-10wt%, or from 5-30wt%, or from 5-20wt%, or from 5-15wt%, or from 5- 10wt%, or from 10-40wt%, or from 10-30wt%, or from 10-20wt%, or from 10- 15wt%, or from 20-40wt%, or from 20-30wt%, or from 30-40wt%, based on the total weight of the plasticized cellulose ester composition.

[0200] Embodiment 32. An article comprising the plasticized cellulose ester composition of any one of Embodiments 21 -31 . Embodiment 33. The article of Embodiment 32, wherein the article is a film, a sheet, a food container, a foam, or a utensil.

[0201] EXAMPLES

[0202] Abbreviations

[0203] Aq is aqueous; BuOH is n-butanol; CA 398-30 is Eastman cellulose acetate CA-398-30; CA is cellulose acetate; Cryst is crystallized; °C is degree(s) Celsius; d is day(s); Comp is comparative; CEx or Comp Ex is comparative example(s); DBT is di-n-butyl terephthalate; DMT is dimethyl terephthalate; DSC is differential scanning calorimetry; Ex is example(s); G is gram(s); GC is gas chromatography; h is hour(s); L is liter(s); Liq is liquid; MBT is methyl n- butyl terephthalate; MeOH is methanol; min is minute(s); TIPT is titanium tetraisopropoxide; mL is milliliter; Pz is plasticizer; rt is room temperature; rxn is reaction; s is second(s); soln is solution; temp is temperature; TA is triacetin; Tg is glass transition temperature;

[0204] Example 1 : Synthesis of MBT from DMT

[0205] To a 500mL, 3-necked round bottomed flask equipped with a magnetic stirrer, an electronically controlled heating mantle, reflux condenser, and a takeoff for removal of MeOH were added DMT (194.1 g), BuOH (148.2g), and TIPT (0.07g). The mixture was heated to an initial pot temperature of 108°C, at which point MeOH began to condense and be removed overhead. The pot temp was gradually raised to 145°C throughout the reaction time of 2h, at which point MeOH (55mL) had been removed. GC analysis of the crude reaction mixture at that point (GC area %) indicated 71 .8% DBT, 21 .0% MBT, 5.8% BuOH, and 1 .4% DMT. The reaction mixture was cooled to 90°C and washed with 10OmL of 2% aq NaOH for 30 min. The aqueous layer was separated, and the organic layer was washed in the same manner twice more.

[0206] The organic layer from the washing steps was returned to a 500 mL, 3- necked round bottomed flask equipped with a magnetic stirrer and an electronically controlled heating mantle. One neck was plugged off and not used, one neck had a thermocouple to monitor and control the base temperature, and the center neck was extended to an 8” packed jacketed column. At the top of this column was attached a magnetic controlled vapor dividing head connected to a Friedrich condenser, fraction cutter, and receiver. n-BuOH was first removed overhead from the mixture under a vacuum atmosphere of 40 mmHg and an increasing pot temperature; BuOH (1 1 mL) was collected. The remaining mixture was then heated to 186°C under 3 mmHg vacuum and 75% reflux. After 1 h condensate from the fractional distillation was collected as Cut 1 . The pot temperature was raised to 195°C and held for 1 h, during which a Cut 2 and a Cut 3 was collected. The composition of Cuts 1 , 2, and 3 (GC area %) are shown in Table 1 .

[0207] Table 1 : Distillation Cuts of MBT Produced from Transesterification of DMT with Butanol

[0208] Example 2: Synthesis of MBT from DBT

[0209] A 2L 4-necked round bottomed flask was equipped with a magnetic stirrer and an electronically controlled heating mantle. One neck of the flask was dedicated to extracting samples, one neck was equipped with a thermocouple to monitor and control base temperature, one neck was arranged to receive a methanol feed from a master flex pump and the center neck was extended to a fractionating column. The fractionating column was fitted with a takeoff plate to remove butanol / methanol via a separate master flex pump, then continued to an 8” packed jacketed column. At the top of this column was attached a magnetic controlled vapor dividing head connected to a Friedrich condenser, fraction cutter, and another receiver for pure methanol.

[0210] To the flask were added DBT (500g), TIPT (0.3g), and MeOH (200mL). The mixture was heated to an initial pot temperature of 150°C for one h. MeOH vaporized in the reaction was returned to the flask. Upon initiation of methanol evolution, the flask setpoint was raised to 178°C and was held for 1 h, during which time BuOH evolution began. The reaction temp was then raised to 205°C and held for 1 .5h during which time BuOH evolution continued, along with MeOH which was recycled back to the flask. After that time GO analysis of the crude rxn mixture at that point (GO area %) indicated the rxn mixture consisted of DBT (77%), MBT (21%), and DMT (1.3%).The reaction was held for an additional h, after which time the reaction mixture consisted of DBT (62%), MBT (33%), and DMT (4%). Heating was continued for 1 h, after which time the rxn mixture consisted of DBT (50%), MBT (42%), and DMT (8%). The rxn was cooled to 30°C and filtered using a glass fiber filter paper and diatomaceous earth filter aid in a Buchner funnel. The filtrate was heated to 90°C and washed with 150 mL of 2% aq NaOH with brine (50 mL). The aq layer was separated, and the washing step was repeated in the same manner twice.

[0211] The organic layer from the washing steps was returned to a 2L 4- necked round bottomed flask equipped with a magnetic stirrer and an electronically controlled heating mantle. Two necks were plugged off and not used, one neck had a thermocouple to monitor and control the base temperature, and the center neck was extended to a fractionating column. The fractionating column was fitted with a 15” packed jacketed column. At the top of this column was attached a magnetic controlled vapor dividing head connected to a Friedrich condenser, fraction cutter, and receiver. The mixture was heated to 181 °C under 2 mmHg vacuum. After 1 h 20min condensate from the fractional distillation was collected as Cut 1 . The pot temp was raised to 185°C and held for 3h, during which a Cut 2 was collected. The pot temp was then raised to 188°C and held for an additional 1 .5h, after which a Cut 3 was collected. The composition of Cuts 1 , 2, and 3 (GC area %) are shown in Table 2. Table 2: Distillation Cuts of MBT Produced from Transesterification of DBT with Methanol

[0212] Example 3. Volatility of plasticizers

[0213] Volatility of plasticizers and blends was determined by thermogravimetric analysis (TGA). About 8-10 mg of material was placed in an open pan in the instrument, and the temp was ramped up from 25°C to 220°C at 20°C / min under an air flow of 50 mL / min. The temp was then held at 220°C for 10min, with an air flow of 50 mL / min. The percentages of material remaining after 2, 5, and 10min at 220°C were determined and are listed in Table 3. TA is a good plasticizer for CA, but its high volatility is demonstrated by the fact that after 2min at 220°C, virtually all has evaporated. In contrast, after 2min at 220°C, about 64-66% of MBT or a blend of MBT and DBT remained, attesting to its lower volatility. The MBT-based materials did entirely evaporate with enough time (10min), but much more slowly than TA.

[0214] Table 3: Volatility of plasticizers at 220°C, as determined by TGA.

[0215] Example 4. Liquid plasticizer blends

[0216] It is preferable for a plasticizer to be liquid at ambient temperatures to facilitate addition during compounding. Pure MBT is a solid at rt; DBT is a liquid at rt. Blends of MBT and DBT were heated to 70 °C to ensure that all material was melted and well mixed, then allowed to sit at rt (20°C) to watch for crystallization. It was found that blends with at least 20% DBT remained liquid (Table 4). A similar experiment was done with blends of MBT and TA; it was found that blends with at least 30wt% TA remained liquid (Table 5).

[0217] Table 4: Physical state of blends of MBT and DBT at 20°C.

[0218] Table 5: Physical state of blends of MBT and TA at 20°C.

[0219] Example 5. Tg suppression in solvent-cast films

[0220] A solution of 15wt% plasticizer in 12wt% CA-398-30 acetone dope was made (20g of 12wt% solids dope + 0.42g test plasticizer). The soln was poured into a shallow aluminum pan (-8.5g) and covered to make a -10 mil film after solvent evaporation over 16g. Tgof cast or molded films was estimated by DSC. The first heat did not exceed 200°C.

[0221] Bis-2-ethylhexyl terephthalate and DBT did not plasticize CA. DMT has limited miscibility with CA and does not make transparent films. In contrast, MBT and BHET both act as plasticizers for CA-398-30, as shown in Table 6.

[0222] Table 6: Tg of solvent cast films with plasticizer (15wt%).

[0223] No Tg = a distinct Tg was not detected in the DSC thermogram

[0224] Example 6. Tg Suppression in Compression Molded Films

[0225] Dry blends were made for compression molding. Plasticizer was added to CA-398-30 powder, and the blend was mixed in a coffee grinder to disperse the plasticizer evenly. Each complete dry blend was pre-weighed (5.5 g) into aluminum pans and dried for 24h at 60°C. Films were pressed for a total of 4 min on a heated press with the upper and lower platens pre-heated to 425°F (218°C). The pre-dried CA / plasticizer blend was applied to the center of a 4- inch square, 10 mil thick frame between a top and bottom layer of aluminum foil, all between two steel plates. The assembly was placed in the press and heated for 1 min before applying pressure to dry and pre-melt the blend. The assembly was then pressed for 1 min at 12,000 PHI, the pressure was increased over ~30 seconds, and the assembly finally was held for 1 .5min at 20,000 PHI (Ram force in pounds). Tg of molded films was estimated by DSC. The first heat did not exceed 200°C. Both MBT and BHET suppress Tg in compression molded CA films in a dose-dependent manner, as shown in Table 7. The pressed films are transparent.

[0226] Table 7: Tg suppression in compression-molded films (10 mil).

[0227] Comp Example 6: Blends of DMT and DBT

[0228] Compression molded films were made according to the previously disclosed procedure for preparation of compression films (Ex 6). The composition of MBT was approximated by simply blending DMT and DBT. The approximate composition of the pure mixed ester was mimicked by blending DBT and DMT at a ratio of DBT :DMT (1 :1 ) by weight. Other blend ratios were also included as indicated in Table 8. In contrast to the MBT mixed ester compression films in Table 7, none of the films with DBT, DMT or blends were clear. While DMT alone can lower the Tg of a cast CA film, the films are not transparent. DBT alone was an inefficient plasticizer for CA in compression molded films.

[0229] Table 8: Tg of Compression molded films, 10 mil from dry blends. Example 7: Solvent-cast films plasticized with blends of MBT and DBT

[0230] Pure MBT is a solid at 20°C but will remain a liquid when blended with DBT, as in Ex 4. MBT was blended with DBT at the ratios shown in Table 9. The blends were added at 15% to a CA dope, and films were cast (10 mil after solvent evaporation) for DSC. The relationship between Tg suppression and % MBT in the blend is linear (y = -0.3522x + 155.56; R2= 0.9744). To function as a miscible plasticizer for CA, the minimum % MBT in the MBT / DBT blend is between 25 and 33%.

[0231] Table 9: Appearance and Tg of cast films plasticized with MBT and blends (15wt% plasticizer)

[0232] Example 8: Compression molding films from dry blends

[0233] Dry blends were made for compression molding. Plasticizer was added to CA-398-30 powder, and the blend was mixed in a coffee grinder to disperse the plasticizer evenly. Each complete dry blend was preweighed (5.5g) into aluminum pans and dried for 24h at 70°C.

[0234] Films were pressed for a total of 4 min on a heated press with the upper and lower platens preheated to 425°F (218°C). The pre-dried CA / plasticizer blend was applied to the center of a 4-inch square, 10 mil thick frame between a top and bottom layer of aluminum foil, all between two steel plates. The assembly was placed in the press and heated for 1 min before applying pressure to dry and pre-melt the blend. The assembly was then pressed for 1 min at 12,000 PHI, the pressure was increased over ~30s, and the assembly was finally held for 1 .5min at 20,000 PHI (Ram force in pounds).

[0235] Loadings of 10-30wt% plasticizer were used, and the results are shown in Table 10. TA forms clear, flexible films at all loadings from 10-30wt%. MBT was used only at 20% loading and formed a clear, flexible film. An MBT:DBT (8:2) blend was brittle at 10wt% loading but flexible at 15-30wt% loading. The blend was clear at 10-15wt% loading; slightly hazy at 20wt% loading, and hazy white at 25-30wt% loading. Hence, the preferred loading for the MBT:DBT blend would be ~15wt%.

[0236] Table 10: Appearance and flexibility of pressed films. Example 9: Aqueous leaching

[0237] When articles made from plasticized CA are exposed to water, plasticizer has the potential to leach out over time. Aqueous leaching of additives was measured gravimetrically using compression-molded films (10 mil) with 20wt% plasticizer. Film samples were immersed in excess de-ionized water at 50°C for 2h or 24h and the relative weight loss from the films over time is presented in Table 11. Compared to a 20wt% TA control film, both DMT and the MBT mixed ester had an even lower leaching rate in warm water. In contrast, BHET had a higher rate of additive leaching than TA.

[0238] Table 11 : Gravimetric additive leaching from pressed films with 20wt% plasticizer (De-ionized water, 50°C)

[0239] Example 10: Aqueous leaching

[0240] Pressed films made as described above (nominally 10 mil, but some were up to 20 mil thick) were cut into 3.0 x 1 .5 cm rectangles. The films were dried for 2h in a convection oven at 70°C and the dry weight of the film was recorded. The films were fully immersed in a scintillation vial containing 15 mL water at 70°C for 2h, then removed. The films were dried in a convection oven at 70°C, and the dry weight was recorded after 2h and again overnight, to ensure that the film was fully dry.

[0241] The percentage of plasticizer leaching out of the film was determined from the weight loss of the film, assuming that all weight loss was due to plasticizer migration. Each film was run in duplicate and the average is recorded. As a control, a pressed film of CA-398-30 without plasticizer was run and showed negligible weight loss. TA readily leaches out of the films; weight loss corresponding to 12- 31 % of the TA was observed. In contrast, MBT or an MBT:DBT blend leaches much less readily; weight loss of 1 -4% was observed, depending on the loading (Table 12).

[0242] Table 12: Leaching of plasticizer from a film immersed in water at 70°C for 2 hours.

[0243] Example 11. Disintegration in compost

[0244] Compression molded films were cut into 1 -inch squares and subjected to a standardized lab test for disintegration in compost according to ISO 20200 (12 weeks at 58°C). Test samples pass if at least 90% of the dry weight has disintegrated at the end of the 12-week test period. Compression molded films of 16-18 mil thickness plasticized with either MBT or a blend of MBT and DBT passed the screening test for disintegration in industrial compost, with >90 wt% of the film screened out as fragments after 12 weeks (Table 13). At 16 to 18 mil, all test films easily passed, and so the thickness limit for disintegration is most likely even greater than the thicknesses tested.

[0245] Table 13: Disintegration of molded films in ISO 20200

Claims

CLAIMSWhat is claimed is:1 . A composition, comprising:(i) greater than 15wt% of n-butyl methyl terephthalate (“MBT”); and(ii) greater than 1wt% of at least one plasticizer, wherein the at least one plasticizer is different than MBT, wherein the wt% of each is based on the total weight of the composition.

2. A method for plasticizing a polymeric composition, comprising: (i) admixing a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) with the polymeric composition.

3. Use of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”) as a plasticizer for a polymeric composition.

4. The method or use of any one of claims 2-3, wherein the polymeric composition comprises a cellulose ester.

5. The method or use of any one of claims 2-4, wherein the polymeric composition is in the form of a particulate material.

6. The method or use of any one of claims 2-5, wherein the plasticizer composition is in the form of a liquid.

7. The method of any one of claims 2, or 4-6, wherein the admixing occurs in an extruder.

8. The method or use of any one of claims 2-7, wherein the plasticizer composition is 100wt% of MBT.

9. The method or use of any one of claims 2-8, wherein the plasticizer composition comprises at least 15wt% of MBT.

10. The method or use of any one of claims 2-9, wherein the plasticizer composition further comprises at least on plasticizer that is different than MBT.11 . A plasticized cellulose ester composition, comprising:(i) a cellulose ester; and(ii) at least 1wt% of a plasticizer composition comprising n-butyl methyl terephthalate (“MBT”), based on the total weight of the plasticized cellulose ester composition.

12. The composition, method or use of any one of claims 1 -11 , wherein the plasticizer composition further comprises at least one plasticizer, wherein the at least one plasticizer is different than MBT.

13. The composition, method, or use of any one of claims 1 -12, wherein the at least one plasticizer is biodegradable according to OECD 301 F.

14. The composition, method, or use of any one of claims 1 -13, wherein the at least one plasticizer is di-n-butyl terephthalate (“DBT”), dimethyl terephthalate (“DMT”), triacetin, polyethylene glycol) with a molecular weight of from 300 to 600 (“PEG MW 300-600”), triethyl citrate, acetylated triethyl citrate, acetyl tributyl citrate, tripropionin, polyethylene glycol succinate, diisobutyl adipate, polyvinyl pyrollidone, glycol tribenzoate, a benzoate-based plasticizer, a poly(alkyl succinate) plasticizer, an adipate-based plasticizer, a soybean oil epoxide plasticizer, sucrose-based plasticizer, dibutyl sebacate, tributyrin, a glycolate-based plasticizer, triphenyl phosphate, 2,2,4- trimethylpentane-1 ,3-diyl bis(2-methylpropanoate), a polycaprolactone, or combinations thereof.

15. The composition, method or use of any one of claims 1 -14, wherein the at least one plasticizer is DBT, DMT, triacetin, PEG MW 300-600, or combinations thereof.

16. The composition, method, or use of any one of claims 1 -15, wherein the composition is a liquid.

17. The composition, method, or use of any one of claims 1 -16, wherein the MBT is present at greater than 20wt%, or greater than 25wt%, or greater than 30wt, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 80wt%, or greater than 90wt%, or greater than 95wt%, or greater than 98wt%, or is 100wt%, based on the total weight of the plasticizer composition.

18. The composition, method or use of any one of claims 1 -17, wherein the at least one plasticizer is greater than 2wt%, or greater than 3wt%, or greater than 4wt%, or greater than 5wt%, or greater than 10wt%, or greater than15wt%, or greater than 20wt%, or greater than 25wt%, or greater than 30wt%, or greater than 40wt%, or greater than 50wt%, or greater than 60wt%, or greater than 70wt%, or greater than 75wt%, or greater than 80wt%, or greater than 85wt%, or greater than 90wt%, or greater than 95wt%, based on the total weight of the plasticizer composition.

19. The composition, method, or use of any one of claims 1 -18, wherein the cellulose ester is a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate propionate, a cellulose acetate propionate, or a cellulose butyrate propionate.

20. The composition, method, or use of any one of claims 1 -19, wherein the cellulose ester is a cellulose acetate.21 . The composition, method, or sue of any one of claims 1 -20, wherein the plasticizer composition is present at at least 2wt%, or at least 5wt%, or at least 10wt%, or at least 15wt%, or at least 20wt%, or at least 30wt%, or from 1 -40wt%, or from 2-40wt%, or from 5-40wt%, or from 10-40wt%, or from 15- 40wt%, or from 20-40wt%, or from 30-40wt%, or from 1 -30wt%, or from 1 -20wt%, or from 1 -15wt%, or from 1 -10wt%, or from 1 -5wt%, or from 1 -2wt%, or from 2-40wt%, or from 2-30wt%, or from 2-20wt%, or from 2-15wt%, or from 2-10wt%, or from 2-5wt%, or from 5-10wt%, or from 5-30wt%, or from 5- 20wt%, or from 5-15wt%, or from 5-10wt%, or from 10-40wt%, or from 10- 30wt%, or from 10-20wt%, or from 10-15wt%, or from 20-40wt%, or from 20-30wt%, or from 30-40wt%, based on the total weight of the plasticized cellulose ester composition.

22. An article comprising the plasticized cellulose ester composition of any one of claims 1 , 4-22.

23. The article of claim 22, wherein the article is a film, a sheet, a food container, a foam, or a utensil.

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