2-Ethylhexanoyl substituted cellulose esters

Abstract

The present application discloses regioselectively substituted cellulose esters containing 2-ethylhexanoyl substituents that have desirable mechanical properties, allowing the cellulose esters to be stretched into larger and thinner films while still maintaining their optical properties.

Description

[Technical field]

[0001] Cellulose esters, such as cellulose triacetate ("CTA" or "TAC"), cellulose acetate propionate ("CAP"), and cellulose acetate butyrate ("CAB"), are used in a wide variety of films for the liquid crystal display ("LCD") and organic LED display ("OLED") industries. Most notable is their use as protective and compensation films used in combination with polarizer sheets. These films are typically made by solution casting and then laminated to either side of an oriented iodized polyvinyl alcohol ("PVOH") polarizing film to protect the PVOH layer from scratching and moisture ingress while also enhancing structural robustness. When used as compensation films (aka waveplates), they may be laminated with the polarizer stack or otherwise included between the polarizer and the liquid crystal / OLED layers. Waveplates can act to improve the contrast ratio, wide viewing angle, and color shifting performance of LCD / OLEDs. Although significant progress has been made in LCD / OLED technology, improvements are still needed. Summary of the Invention [Problem to be solved by the invention]

[0002] There is a need for larger and thinner cellulose ester films that have good mechanical properties for large display applications and still maintain the optical properties useful in display.Applicants have found that the regioselectively substituted cellulose esters with novel 2-ethylhexanoyl substituents are useful because of desirable mechanical properties other than optical properties, allowing them to be stretched into thinner and larger size films. [Means for solving the problem]

[0003] This application is (i) multiple 2-ethylhexanoyl ("2EH") substituents; (ii) Multiple (C 1~6 ) alkyl-CO- ("AkCO") substituents; (iii) multiple hydroxy ("OH") substituents, and (iv) Multiple R 1 -CO- (“ChCO”) substituent A cellulose ester comprising: During the ceremony, R 1 teeth, (1)(C 10~20 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by (2) 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by (3)

[0004] [ka]

[0005] wherein aryl is (C 1-6 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by or (4)

[0006] [ka]

[0007] wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O or S, wherein heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by and Each R 2are nitro, cyano, (C 1~6 ) alkyl, halo(C 1~6 ) alkyl; (C 6~20 )aryl-CO2-, (C 6~20 ) aryl, (C 1~6 ) alkoxyl, halo(C 1~6 ) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from alkoxyl, halo, N, O or S; or

[0008] [ka]

[0009] Disclosed is a cellulose ester independently selected from: The present application also relates to a regioselectively substituted cellulose ester, (i) a plurality of 2-ethylhexanoyl ("2EH") substituents, where the cellulose ester has a 2EH degree of substitution ("DS") of 0.1 to 1.0. 2EH ") (ii) Multiple (C 1~6 ) alkyl-CO- ("AkCO") substituents, where the cellulose ester has an AkCO degree of substitution ("DS AkCO ") (iii) a plurality of hydroxy ("OH") substituents, wherein the cellulose ester has a degree of OH substitution ("DS") of less than 0.8. OH ") (iv) Multiple R 1 -CO- ("ChCO") substituents, where the cellulose ester has a ChCO degree of substitution ("DS ChCO ") Including, During the ceremony, R 1 teeth, (1)(C 10~20 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by (2) 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by (3)

[0010] [ka]

[0011] wherein aryl is (C 1~6 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by or (4)

[0012] [ka]

[0013] wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O or S, wherein heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by and Each R 2 are nitro, cyano, (C 1~6 ) alkyl, halo(C 1~6 ) alkyl; (C 6~20 )aryl-CO2-, (C 6~20 ) aryl, (C 1~6 ) alkoxyl, halo(C 1~6 ) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from alkoxyl, halo, N, O or S; or

[0014] [ka]

[0015] are independently selected from The cellulose ester has a C2 substitution degree of AkCO substituents in the range of 0.2 to 0.3 ("C2DS AkCO " ), and the C3 substitution degree of AkCO substituents in the range of 0.2 to 0.4 (" C3DS AkCO " ), and the C6 substitution degree of the AkCO substituent in the range of 0.5 to 0.7 (" C6DS AkCO ") Regioselectively substituted cellulose esters are also disclosed.

[0016] The present application relates to a regioselectively substituted cellulose ester, (i) a plurality of 2-ethylhexanoyl ("2EH") substituents, where the cellulose ester has a 2EH degree of substitution ("DS") of 0.1 to 1.0. 2EH ") (ii) Multiple (C 1~6 ) alkylCO ("AkCO") substituents, where the cellulose ester has an AkCO degree of substitution ("DS AkCO ") (iii) a plurality of hydroxy ("OH") substituents, wherein the cellulose ester has a degree of OH substitution ("DS") of less than 0.8. OH ") (iv) Multiple R 1 -CO- ("ChCO") substituents, where the cellulose ester has a ChCO degree of substitution ("DS ChCO ") Including, During the ceremony, R 1 is phenyl, where phenyl is unsubstituted or has 1 to 5 R 2 is replaced by Each R 2 are nitro, cyano, (C 1~6 ) alkyl, halo(C 1~6 ) alkyl; (C 6~20 )aryl-CO2-, (C 6~20 ) aryl, (C 1~6 ) alkoxyl, halo(C 1~6) alkyloxyl, halo, 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, or

[0017] [ka]

[0018] are independently selected from The cellulose ester has a C2 substitution degree of AkCO substituents in the range of 0.2 to 0.3 ("C2DS AkCO " ), and the C3 substitution degree of AkCO substituents in the range of 0.2 to 0.4 (" C3DS AkCO " ), and the C6 substitution degree of the AkCO substituent in the range of 0.5 to 0.7 (" C6DS AkCO ") is disclosed.

[0019] The present application also discloses films prepared from the cellulose esters disclosed herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present invention can be more readily understood by referring to the following "Description of the Invention" and the "Examples" presented therein. It will be understood that the present invention is not limited to the specific methods, formulations and conditions described, which may vary as such. It will also be understood that the terms used herein are only for the purpose of describing specific embodiments of the present invention, and are not intended to be limiting. definition In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings.

[0021] 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 embodiment 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 embodiment.

[0022] As used herein, the terms "a," "an," and "the" mean one or more. As used herein, the term "and / or," when used in a list of two or more terms, means that any one of the listed terms can be used by itself, or any combination of two or more of the listed items can be used. 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 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.

[0023] As used herein, the terms "comprising," "comprises," and "comprise" are open-ended transitional terms used to link the subject matter listed before the term to one or more elements listed after the term, where the element or elements listed after the transitional term are not necessarily the only elements making up the subject matter.

[0024] As used herein, the terms "having," "has," and "have" have the same open-ended meaning as "comprising," "comprises," and "comprise" set forth above.

[0025] As used herein, the terms "including," "includes," and "include" have the same open-ended meaning as "comprising," "comprises," and "comprise" set forth above.

[0026] "Degree of substitution" refers to the average number of substituents per anhydroglucose monomer of the cellulose ester. The degree of substitution refers to the average number of substituents, such as acyl groups (e.g., DS acyl The degree of substitution can also refer to the number of free or unsubstituted hydroxy groups on the anhydroglucose monomer, denoted as DSOH. The total degree of substitution includes the total degree of substitution for the acyl substituents. In determining the total degree of substitution, the DS OH are not included in the calculation. The degree of substitution can be specified at the position on the anhydroglucose monomer. For example, the degree of substitution can be specified at the C2, C3 or C6 position of the anhydroglucose monomer (e.g., C2DS, C3DS, C6DS):

[0027] [ka]

[0028] may apply. "Degree of polymerization" refers to the number of glucose units that make up one polymer molecule. 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 about 10 to about 50.

[0029] As used herein, the term "acyl substituent" refers to a group having the structure:

[0030] [ka]

[0031] This means that the substituent has the following structure: For example, the acyl substituent can be (C 1~6 ) alkyl-CO- or R 1 Such acyl substituents in cellulose esters are generally attached to the pyranose ring of cellulose via an ester bond (i.e., through an oxygen atom).

[0032] As used herein, the term "alkyl-CO," an acyl substituent, is meant to indicate an acyl substituent in which "R" is an alkyl group. As used herein, the term "alkyl" is meant to denote a univalent group formed by removing a hydrogen atom from a non-aromatic hydrocarbon and which may contain heteroatoms. Alkyl groups suitable for use herein can be linear, branched or cyclic. Alkyl groups suitable for use herein include any (C 1~20 ), (C 1~12 ), (C 1~5 ) or (C 1~3 In various embodiments, the alkyl group is 1~5 It can be a straight or branched chain alkyl group. In yet other embodiments, the alkyl group is 1~3 It can be a straight or branched chain alkyl group. Specific examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl and cyclohexyl groups. Examples of alkyl-acyl or alkyl-CO- groups include acetyl, propionyl, butyroyl, etc.

[0033] As used herein, the term "aryl-CO-" is meant to indicate an acyl substituent where "R" is an aryl group. As used herein, the term "aryl" refers to a monovalent group formed by removing a hydrogen atom from a ring carbon in an arene (i.e., a monocyclic or polycyclic aromatic hydrocarbon). In some cases, the aryl-acyl group is preceded by a carbon unit, e.g., (C 5~6 ) aryl-acyl, (C 6~12 ) aryl-acyl or (C 6-20 ) aryl-acyl. Examples of aryl groups suitable for use in the various embodiments include, but are not limited to, phenyl, benzyl, tolyl, xylyl, and naphthyl. Such aryl groups may be substituted or unsubstituted.

[0034] As used herein, the term "heteroaryl-CO" is meant to indicate an acyl substituent where "R" is a heteroaryl group. As used herein, the term "heteroaryl" refers to an aryl group in which one or more ring carbons are replaced with heteroatoms such as nitrogen, oxygen, and / or sulfur. In some cases, the heteroaryl-CO- group is defined by the amount of atoms making up the heteroaryl ring, e.g., 5-10 membered ring. The heteroaryl-CO- group can also be defined by the number of possible heteroatoms in the ring system, e.g., 1-4 N, O, or S heteroatoms. Examples of heteroaryl groups suitable for use for the various embodiments include, but are not limited to, furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pipridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl. Such heteroaryl groups can be substituted or unsubstituted.

[0035] "Haloalkyl" refers to an alkyl substituent in which at least one hydrogen has been replaced with a halogen group. The carbon units in the haloalkyl group are often included, e.g., halo(C 1~6) alkyl. Haloalkyl groups can be straight or branched. Non-limiting examples of haloalkyl include chloromethyl, trifluoromethyl, dibromomethyl, and the like.

[0036] "Alkenyl" refers to an alkyl group of at least two carbon units containing at least one double bond. The carbon units in the alkenyl group are often included, for example, (C 2~6 ) alkenyl. Alkenyl groups can be straight or branched. Non-limiting examples of alkenyl include ethenyl, allyl, 1-butenyl, and the like.

[0037] "Cycloalkyl" refers to a cyclic alkyl group having at least three carbon units. The carbon units in the cycloalkyl group are often included, for example (C 3~8 ) cycloalkyl. Non-limiting examples of alkyl include cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, and the like.

[0038] "Alkoxy" refers to alkyl-O- or an alkyl group terminally attached to oxygen. It often contains carbon units, e.g., (C 1~6 ) alkoxy. Non-limiting examples of alkoxy include methoxy, ethoxy, propoxy, and the like.

[0039] "Haloalkoxy" refers to an alkoxy in which at least one of the hydrogens is replaced with a halogen. It often contains a carbon unit, such as halo(C 1~6 )alkoxy. Non-limiting examples of haloalkoxy include trifluoromethoxy, bromomethoxy, 1-bromo-ethoxy, and the like.

[0040] "Halo" means halogen, for example fluoro, chloro, bromo, or iodo. As used herein, the term "substantially" means within 5%. For example, "substantially perpendicular" means in the range of 84.5° to 94.5°. "Substantially consumed" means at least 95% or more consumed.

[0041] This description uses numerical ranges to quantify certain parameters related to the present invention. When numerical ranges are given, it should be understood that such ranges are to be interpreted as providing textual support for claim limitations that recite only the lower values ​​of the range, and for claim limitations that recite only the higher values ​​of the range. For example, a disclosed numerical range of 10 to 100 provides textual support for claims that recite "greater than 10" (no upper bound) and claims that recite "less than 100" (no lower bound).

[0042] The present description uses specific numerical values ​​to quantify certain parameters related to the present invention, where the specific numerical values ​​are not explicitly part of a numerical range. It should be understood that each specific numerical value given herein is to be interpreted as giving textual support for a broad, intermediate and narrow range. The broad range associated with each specific numerical value is a numerical value of ±60 percent of the numerical value rounded to two significant figures. The intermediate range associated with each specific numerical value is a numerical value of ±30 percent of the numerical value rounded to two significant figures. The narrow range associated with each specific numerical value is a numerical value of ±15 percent of the numerical value rounded to two significant figures. For example, if a specification recites a specific temperature of 16.67°C (62°F), such recitation provides textual support for a broad numerical range of -3.89°C (25°F) to 37.22°C (99°F) (16.67°C (62°F) ± 2.78°C (37°F)), a mid-range numerical range of 6.11°C (43°F) to 27.22°C (81°F) (16.67°C (62°F) ± -7.22°C (19°F)), and a narrow numerical range of 11.67°C (53°F) to 21.67°C (71°F) (16.67°C (62°F) ± -12.78°C (9°F)). These broad, mid-range and narrow numerical ranges should not only apply to the specific values, but should also apply to the differences between these specific values. So, if the specification states a first pressure of 758.4 kPa (110 psia) and a second pressure of 331 kPa (48 psia) (a difference of 427.5 kPa (62 psi)), then a wide range for the pressure difference between these two streams would be 172.4 to 682.6 kPa (25 to 99 psi), a medium range would be 296.5 to 558.5 kPa (43 to 81 psi), and a narrow range would be 365.4 to 489.5 kPa (53 to 71 psi).

[0043] The cellulose ester prepared by the method of the present invention is useful in various applications.Those skilled in the art will understand that specific applications will depend on the specific type of factors such as acyl substituent, DS, MW type and the type of cellulose ester copolymer, which will substantially affect the physical properties of cellulose ester.Prog.Polym.Sci.2001,26,1605-1688.

[0044] The cellulose esters thus prepared generally have the structure:

[0045] [ka]

[0046] Including, In the formula, R 2 , R 3 and R 6 is hydrogen (with the condition that R 2 , R 3 and R 6 and x cannot simultaneously be hydrogen), alkyl-acyl groups and / or aryl-acyl groups (such as those described above) that are attached to cellulose via ester bonds.

[0047] Throughout this application, wherever 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 this invention pertains.

[0048] Films prepared from cellulose esters can be utilized in liquid crystal displays ("LCD") or organic light emitting diode ("OLED") displays. Generally, LCDs utilize polarizer stacking, including a set of crossed polarizers. Due to the typical set of crossed polarizers used in LCDs, there can be significant light leakage along the diagonal, especially as the viewing angle increases (leading to poor contrast ratios). A variety of optical films can be used to correct or "compensate" for this light leakage. These films can have a certain well-defined birefringence (or retardation) that varies depending on the type of liquid crystal cell used, because the liquid crystal cell itself will also impart a certain degree of undesirable optical retardation that must be corrected. Some of these compensation films are easier to make than others, so a compromise is often made between performance and cost. Also, while most compensation and protective films are made by solution casting, there is a demand for more films to be made by melt extrusion to eliminate the need to handle environmentally unfriendly solvents. Having materials with more controllable optical retardation that can be made by both solvent casting and melt casting allows for greater flexibility in the creation of these films.

[0049] Optical films are commonly quantified in terms of birefringence, which in turn is related to the refractive index, n. The refractive index can typically be in the range of 1.4 to 1.8 for polymers and around 1.46 to 1.50 for cellulose esters. The higher the refractive index, the slower the light waves propagate through a given material.

[0050] For a non-oriented, isotropic material, the index of refraction will be the same regardless of the polarization state entering the light wave. As a material becomes oriented, or otherwise anisotropic, the index of refraction becomes dependent on the material direction. For purposes of this invention, n x、 n y and n zThere are three important refractive indices, denoted as Δ and Δ , which correspond to the machine direction ("MD"), transverse direction ("TD"), and thickness direction, respectively. As a material becomes more anisotropic (e.g., by stretching), the difference between any two refractive indices will increase. This difference is called "birefringence." There are many combinations of material directions to choose from, and therefore correspondingly different birefringence values. The two most common are areal (or "in-plane") birefringence, Δ e , and the thickness birefringence (or "out-of-plane" birefringence) Δ th teeth, (1a)Δ e =n x -n y (1b)Δ th =n z -(n x +n y ) / 2 It is defined as follows.

[0051] Birefringence Δ e is a measure of the relative in-plane orientation between the MD and TD directions, and is dimensionless. In contrast, Δ th gives a measure of the orientation through the thickness relative to the average planar orientation.

[0052] Another term often used in reference to optical films is the optical retardation, R. R is simply the birefringence times the thickness, d, of the film under consideration. Therefore, (2a)R e = Δ e d=(n x -n y )d (2b)R th = Δ th d=[n z -(n x +n y ) / 2]d It is.

[0053] The phase difference is a direct measure of the relative phase shift between two orthogonal light waves and is typically reported in units of nanometers (nm). thThe definition of R, especially in terms of the signs (+ / -), th It should be noted that the amount of the difference varies between several applicants depending on how it is calculated.

[0054] Materials are also known to vary in their birefringence / retardation behavior. For example, most materials when stretched will exhibit a higher refractive index along the stretch direction and a lower refractive index perpendicular to the stretch direction. This follows because, at the molecular level, the refractive index is typically higher along the axis of the polymer chain and lower perpendicular to the chain. These materials are generally referred to as "positively birefringent" and represent most standard polymers, including cellulose esters currently available on the market. It is noted and will be explained later that positively birefringent materials can be used to make either positively birefringent films or waveplates or negatively birefringent films or waveplates.

[0055] To avoid confusion, the birefringence behavior of the polymer molecule itself will be referred to as "intrinsic birefringence" and is a property of the polymer. From the viewpoint of material optics, intrinsic birefringence is a measure of the birefringence that would occur if all chains were perfectly aligned in one direction and the material were fully stretched (for most polymers, there is a logical limit to this, because they cannot be perfectly aligned). For the purposes of this invention, it also gives a measure of the sensitivity of a given polymer to a given amount of chain orientation. For example, during film formation, a sample with high intrinsic birefringence will exhibit higher birefringence than a sample with low intrinsic birefringence, even when the relative stress levels in the film are roughly the same.

[0056] A polymer can have positive, negative or zero intrinsic birefringence. A negative intrinsic birefringence polymer exhibits a higher refractive index perpendicular to the stretching direction (versus the parallel direction). Certain styrenes and acrylics can have negative intrinsic birefringence behavior due to their rather bulky side chains. Depending on the composition, some cellulose esters with aromatic ring structures can also exhibit negative intrinsic birefringence. In contrast, zero intrinsic birefringence is a special case, and represents a material that does not show birefringence with stretching, and therefore has zero intrinsic birefringence. Such materials can be ideal for certain optical applications, because they can be molded, stretched or otherwise stressed without showing any optical retardation or distortion during processing.

[0057] The actual compensation film(s) used in LCDs can take many different forms, including biaxial films, in which all three refractive indices are different and there are two optical axes, and uniaxial films, in which two of the three refractive indices are the same and there is only one optical axis. There are also other classes of compensation films (e.g., disc-shaped films), in which the optical axis is twisted or tilted through the thickness of the film, but these are generally less important. In general, the type of compensation film that can be made is limited by the birefringence properties of the polymer (i.e., positive, negative, or zero intrinsic birefringence). Some examples are described below.

[0058] In the case of uniaxial film, (3a)n x >n y =n z "+A" Optical Film Films with a refractive index such that: x(Lower than θ). This type of film is also referred to as a positive uniaxial crystal structure with the optical axis along the x-direction. Such films can be made by uniaxially stretching a positive intrinsically birefringent material, for example using a film stretcher.

[0059] In contrast, the "-A" uniaxial film has (3b)n x <n y =n z "-A" Optical Film It is defined as where the x-axis refractive index is lower (it is approximately equal) than in the other directions. One way to make -A optical films is by stretching a negative intrinsic birefringent polymer, or by coating a negative (intrinsic) birefringent liquid crystal polymer onto a surface (e.g., by using an underlying etched alignment layer) so that the molecules align in a preferred direction.

[0060] In terms of retardation, the “±A” optical film is (3c): (3c)R th =-R e / 2 "±A" Optical Film As shown in e and R th and

[0061] Another class of uniaxial optical films are C optical films, which can also be "+C" or "-C". The difference between C optical films and A optical films is that in C optical films, the unique index of refraction (or optical axis) is in the thickness direction as opposed to in the plane of the film. Therefore, (4a)n z >n y =n x "+C" Optical Film (4b)n z <n y =n x "-C" Optical Film It is.

[0062] C optical films can be produced by taking advantage of the stress that forms during the solution casting of the film. Tensile stresses are generally created in the plane of the film due to the constraint imposed by the casting belt, which is also naturally stretched equibiaxial. These tend to align the chains in the plane of the film, resulting in -C or +C films for positive and negative intrinsic birefringent materials, respectively. Since many cellulose ester films used in displays are solution cast, and many are inherently positively birefringent, it is clear that solution cast cellulose esters usually only produce -C optical films. These films can also be uniaxially stretched to produce +A optical films (assuming that the initial as-cast retardation is very low).

[0063] Besides uniaxial optical films, it is also possible to use biaxially oriented films. Biaxial films have three refractive indices, n x , n y and n z In general, n x ≠ n y ≠ n z It is.

[0064] One particular type of biaxially oriented film has unique optical properties that compensate for light leakage in a pair of crossed polarizers or in-plane switching ("IPS") mode liquid crystal displays. The optical film has a parameter Nz in the range of about 0.4 to about 0.9, or equal to about 0.5, where Nz is (5) Nz = (n x -n z ) / (n x -n y ) It is defined as follows:

[0065] This parameter gives the effective out-of-plane birefringence relative to the in-plane birefringence. Nz can be chosen to be about 0.5 when used as a compensation film for a pair of crossed polarizers. When Nz is about 0.5, the corresponding out-of-plane retardation R th is approximately equal to 0.0 nm.

[0066] To illustrate the compensation effect of the optical film, the following light transmission or light leakage of a pair of crossed polarizers with and without compensation films are calculated by computer simulation. composition This application relates to compounds having (i) multiple 2-ethylhexanoyl ("2EH") substituents, (ii) multiple (C 1~6 ) alkyl-CO ("AkCO") substituents, (iii) multiple hydroxy ("OH") substituents, and (iv) multiple R 1 cellulose esters containing -CO- ("ChCO") substituents, In the formula, R 1 (1)(C 10~20 ) aryl, where aryl is unsubstituted or contains 1 to 5 R 2 (2) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or substituted with 1-5 R 2 (3) is replaced by

[0067] [ka]

[0068] wherein aryl is (C 1~6 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 or (4)

[0069] [ka]

[0070] wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O or S, wherein heteroaryl is unsubstituted or has 1-5 R 2 is replaced by, and each R 2 are nitro, cyano, (C 1~6 ) alkyl, halo(C 1~6 ) alkyl; (C 6~20 )aryl-CO2-, (C 6~20 ) aryl, (C 1~6 ) alkoxyl, halo(C 1~6 ) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from alkoxyl, halo, N, O or S; or

[0071] [ka]

[0072] Disclosed is a cellulose ester independently selected from: In one embodiment, R 1 is (C 10~20 ) aryl, wherein aryl is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is naphthyl, which is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is naphthyl, which is unsubstituted. In one class of this embodiment, R 1 is naphthyl, which is one to five R 2 has been replaced by

[0073] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0074] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0075] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0076] In one embodiment, R 1 (C 10~20 ) aryl, where aryl is unsubstituted. In one embodiment, R 1 (C 10~20 ) aryl, where aryl is 1 to 5 R 2 has been replaced by

[0077] In one embodiment, R 1 is a 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by

[0078] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0079] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0080] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0081] In one class of this embodiment, R 1 furanyl, benzothiophene-yl

[0082] [ka]

[0083] , pyrrolyl, thiophene-yl

[0084] [ka]

[0085] , pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, which is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, wherein each ring is selected from 1 to 5 R 2 In one class of this embodiment, R 1is furanyl, pyrrolyl, benzothiophen-yl, or thiofuranyl, where each ring is 2 In one class of this embodiment, R 1 is furanyl, pyrrolyl, benzothiophen-yl, or thiofuranyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, pyrrolyl, benzothiophen-yl, or thiofuranyl, where each ring is selected from 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, where each ring is 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, which is unsubstituted. In one class of this embodiment, R 1 is furanyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, which is unsubstituted. In one class of this embodiment, R 1 is benzothiophene-yl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrrolyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is thiophenyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1is thiophenyl, which is unsubstituted. In one class of this embodiment, R 1 is thiophenyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridazinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyridazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrimidinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R1 is quinolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is isoquinolinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is isoquinolinyl, which is unsubstituted. In one class of this embodiment, R 1 is isoquinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinoxalinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinazolinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is quinazolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinazolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl, which is unsubstituted. In one class of this embodiment, R 1 is phthalazinyl, and 1 to 5 R 2 has been replaced by

[0086] In one embodiment, R 1 teeth,

[0087] [ka]

[0088] wherein aryl is (C 6-10 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0089] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS2EH") that is 0.3 to 0.5. In one subclass of this class, the cellulose ester has a ChCO degree of substitution ("DS ChCO ").

[0090] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0091] In one class of this embodiment, aryl is unsubstituted. In one class of this embodiment, aryl is selected from 1 to 5 R 2 In one class of this embodiment, aryl is phenyl or naphthyl, and is unsubstituted or substituted with 1-5 R 2 In one class of this embodiment, aryl is phenyl or naphthyl, where each ring is unsubstituted. In one class of this embodiment, aryl is phenyl or naphthyl, where each ring is unsubstituted. In one class of this embodiment, aryl is phenyl or naphthyl, where each ring is unsubstituted. 2In one class of this embodiment, aryl is phenyl, unsubstituted or substituted with 1-5 R 2 In one class of this embodiment, aryl is phenyl and is unsubstituted. In one class of this embodiment, aryl is phenyl and is substituted with 1 to 5 R 2 has been replaced by

[0092] In one embodiment, R 1 teeth,

[0093] [ka]

[0094] wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O, or S, and wherein heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by

[0095] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0096] In one class of this embodiment, the cellulose ester has a degree of 2EH substitution ("DS2EH") from 0.3 to 0.5. In one subclass of this class, the cellulose ester has a degree of ChCO substitution ("DS ChCO ").

[0097] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0098] In one class of this embodiment, heteroaryl is unsubstituted. In one class of this embodiment, heteroaryl is selected from 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl or phthalazinyl, which is unsubstituted or 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, wherein each ring is selected from 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, or thiofuranyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, or thiofuranyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, or thiofuranyl, where each ring is 2 In one class of this embodiment, R 1 is furanyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl and is unsubstituted. In one class of this embodiment, R 1is furanyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, which is unsubstituted. In one class of this embodiment, R 1 is benzothiophene-yl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrrolyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is thiophene-yl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is thiophene-yl and is unsubstituted. In one class of this embodiment, R 1 is thiophene-yl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrazinyl, and 1 to 5 R2 In one class of this embodiment, R 1 is pyridazinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyridazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl and is unsubstituted. In one class of this embodiment, R 1 is pyrimidinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 isoquinolinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is isoquinolinyl and is unsubstituted. In one class of this embodiment, R 1 is isoquinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinoxalinyl, and 1 to 5 R 2In one class of this embodiment, R 1 is quinazolinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is quinazolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinazolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl and is unsubstituted. In one class of this embodiment, R 1 is phthalazinyl, and 1 to 5 R 2 In one embodiment, R 1 is naphthyl, benzothiophene-yl, furanyl or

[0099] [ka]

[0100] In one embodiment, R 1 is naphthyl, furanyl or

[0101] [ka]

[0102] It is. In one embodiment, the cellulose ester has a hydroxy substituent degree of substitution ("DS OH In one class of this embodiment, DS OH In one class of this embodiment, DSH is 0.90 or less. In one class of this embodiment, DSH is 0.95 or less. OH In one class of this embodiment, DS OH In one class of this embodiment, DSOH In one class of this embodiment, DS OH is less than 0.70.

[0103] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH is 0.3 to 0.5.

[0104] In one embodiment, the cellulose ester has an R 1 -CO-degree of substitution (“DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO is 0.5 to 1.0.

[0105] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and the cellulose ester has a degree of hydroxyl substitution ("DS OH "), and the cellulose ester has an Akacyl substitution degree ("DS Akacyl ").

[0106] In one embodiment, the cellulose ester has a glass transition temperature ("T"), determined according to ASTM E1356-03, that is less than 170°C. g In one embodiment, the cellulose ester has a glass transition temperature ("T") that is less than 165°C, as determined according to ASTM E1356-03. g In one embodiment, the cellulose ester has a glass transition temperature ("T") that is less than 160°C, as determined according to ASTM E1356-03. g ").

[0107] In one embodiment, the cellulose ester has a breaking strain greater than 3%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 3.5%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 4%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 4.5%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 5%, as determined according to ASTM D882-18. Regioselectively Substituted Compositions The present application also relates to a regioselectively substituted cellulose ester, (i) a plurality of 2-ethylhexanoyl ("2EH") substituents, where the cellulose ester has a 2EH degree of substitution ("DS") of 0.1 to 1.0. 2EH ") (ii) Multiple (C 1~6 ) alkyl-CO- ("AkCO") substituents, where the cellulose ester has an AkCO degree of substitution ("DS AkCO ") (iii) a plurality of hydroxy ("OH") substituents, wherein the cellulose ester has a degree of OH substitution ("DS") of less than 0.8. OH ") (iv) Multiple R 1-CO- ("ChCO") substituents, where the cellulose ester has a ChCO degree of substitution ("DS ChCO ") Including, During the ceremony, R 1 teeth, (1)(C 10~20 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by (2) 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by (3)

[0108] [ka]

[0109] wherein aryl is (C 1~6 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by or (4)

[0110] [ka]

[0111] wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O or S, wherein heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by and Each R 2 are nitro, cyano, (C 1~6 ) alkyl, halo(C 1~6 ) alkyl; (C 6~20 )aryl-CO2-, (C 6~20 ) aryl, (C 1~6 ) alkoxyl, halo(C1~6 ) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from alkoxyl, halo, N, O or S; or

[0112] [ka]

[0113] The cellulose ester is independently selected from the group consisting of cellulose esters having a C2-position substitution degree of AkCO substituents ("C2DS AkCO " ), and the C3 substitution degree of AkCO substituents in the range of 0.2 to 0.4 (" C3DS AkCO " ), and the C6 substitution degree of the AkCO substituent in the range of 0.5 to 0.7 (" C6DS AkCO ") Regioselectively substituted cellulose esters are disclosed.

[0114] In one embodiment, Akacyl is acetyl, propyl, butyryl, isobutyryl, pentanoyl, 3-methylbutanoyl, 2-methylbutanoyl, hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, or 4-methylpentanoyl. In one class of this embodiment, Akacyl is acetyl. In one class of this embodiment, Akacyl is propyl. In one class of this embodiment, Akacyl is butyryl. In one class of this embodiment, Akacyl is isobutyryl. In one class of this embodiment, Akacyl is pentanoyl. In one class of this embodiment, Akacyl is 3-methylbutanoyl. In one class of this embodiment, Akacyl is 2-methylbutanoyl. In one class of this embodiment, Akacyl is hexanoyl. In one class of this embodiment, Akacyl is 2-methylpentanoyl. In one class of this embodiment, Akacyl is 3-methylpentanoyl. In a class of this embodiment, Akacyl is 4-methylpentanoyl.

[0115] In one embodiment, Akacyl is acetyl, propyl, butyryl, or isobutyryl. In one embodiment, R 1 (C 10~20 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by

[0116] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0117] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS2EH") that is 0.3 to 0.5. In one subclass of this class, the cellulose ester has a ChCO degree of substitution ("DS ChCO ").

[0118] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0119] In one class of this embodiment, R 1 is naphthyl, which is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is naphthyl, which is unsubstituted. In one class of this embodiment, R 1 is naphthyl, which is one to five R 2 In one embodiment, R 1 (C 10~20 ) aryl, where aryl is unsubstituted. In one embodiment, R 1 (C 10~20 ) aryl, where aryl is 1 to 5 R 2 has been replaced by

[0120] In one embodiment, R 1 is a 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by

[0121] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0122] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0123] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0124] In one class of this embodiment, R 1 furanyl, benzothiophene-yl

[0125] [ka]

[0126] , pyrrolyl, thiophene-yl

[0127] [ka]

[0128] , pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, which is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, wherein each ring is selected from 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, pyrrolyl, benzothiophen-yl, or thiofuranyl, where each ring is 2 In one class of this embodiment, R 1 is furanyl, pyrrolyl, benzothiophen-yl, or thiofuranyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, pyrrolyl, benzothiophen-yl, or thiofuranyl, where each ring is 2 In one class of this embodiment, R 1 is furanyl, where each ring is selected from 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, which is unsubstituted. In one class of this embodiment, R 1 is furanyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, where each ring is unsubstituted or has 1 to 5 R 2In one class of this embodiment, R 1 is benzothiophene-yl, which is unsubstituted. In one class of this embodiment, R 1 is benzothiophene-yl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrrolyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is thiophenyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is thiophenyl, which is unsubstituted. In one class of this embodiment, R 1 is thiophenyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridazinyl, where each ring is unsubstituted or has 1 to 5 R2 In one class of this embodiment, R 1 is pyridazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrimidinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is isoquinolinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is isoquinolinyl, which is unsubstituted. In one class of this embodiment, R 1 is isoquinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinoxalinyl, and 1 to 5 R 2 In one class of this embodiment, R 1is quinazolinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is quinazolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinazolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl, which is unsubstituted. In one class of this embodiment, R 1 is phthalazinyl, and 1 to 5 R 2 has been replaced by

[0129] In one embodiment, R 1 teeth,

[0130] [ka]

[0131] wherein aryl is (C 6~10 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0132] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0133] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0134] In one class of this embodiment, aryl is unsubstituted. In one class of this embodiment, aryl is selected from 1 to 5 R 2 In one class of this embodiment, aryl is phenyl or naphthyl, and is unsubstituted or substituted with 1-5 R 2 In one class of this embodiment, aryl is phenyl or naphthyl, where each ring is unsubstituted. In one class of this embodiment, aryl is phenyl or naphthyl, where each ring is unsubstituted. In one class of this embodiment, aryl is phenyl or naphthyl, where each ring is unsubstituted. 2 In one class of this embodiment, aryl is phenyl, unsubstituted or substituted with 1-5 R 2 In one class of this embodiment, aryl is phenyl and is unsubstituted. In one class of this embodiment, aryl is phenyl and is substituted with 1 to 5 R 2 has been replaced by

[0135] In one embodiment, R 1 teeth,

[0136] [ka]

[0137] wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O, or S, and wherein heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by

[0138] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EHIn one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0139] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one subclass of this class, the cellulose esters have a degree of substitution ChCO ("DS ChCO ").

[0140] In one class of this embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0141] In one class of this embodiment, heteroaryl is unsubstituted. In one class of this embodiment, heteroaryl is selected from 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl or phthalazinyl, which is unsubstituted or 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, thiophen-yl, pyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, or phthalazinyl, wherein each ring is selected from 1 to 5 R 2In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, or thiofuranyl, where each ring is unsubstituted or has 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, or thiofuranyl, where each ring is unsubstituted. In one class of this embodiment, R 1 is furanyl, benzothiophen-yl, pyrrolyl, or thiofuranyl, where each ring is 2 In one class of this embodiment, R 1 is furanyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is furanyl and is unsubstituted. In one class of this embodiment, R 1 is furanyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is benzothiophene-yl, which is unsubstituted. In one class of this embodiment, R 1 is benzothiophene-yl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyrrolyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrrolyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is thiophene-yl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1is thiophene-yl and is unsubstituted. In one class of this embodiment, R 1 is thiophene-yl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyridinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyrazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyrazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyridazinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyridazinyl, which is unsubstituted. In one class of this embodiment, R 1 is pyridazinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is pyrimidinyl and is unsubstituted. In one class of this embodiment, R 1 is pyrimidinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is quinolinyl, which is unsubstituted. In one class of this embodiment, R1 is quinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 isoquinolinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is isoquinolinyl and is unsubstituted. In one class of this embodiment, R 1 is isoquinolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is quinoxalinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinoxalinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is quinazolinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is quinazolinyl, which is unsubstituted. In one class of this embodiment, R 1 is quinazolinyl, and 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl, unsubstituted or 1 to 5 R 2 In one class of this embodiment, R 1 is phthalazinyl and is unsubstituted. In one class of this embodiment, R 1 is phthalazinyl, and 1 to 5 R 2 In one embodiment, R 1 is naphthyl, benzothiophene-yl, furanyl or

[0142] [ka]

[0143] In one embodiment, R 1 is naphthyl, furanyl or

[0144] [ka]

[0145] It is. In one embodiment, the regioselectively substituted cellulose ester has a C2-substitution degree of 2EH substituents ("C2DS 2EH "), the degree of substitution of 2EH substituents at the C3 position ("C3DS2 EH " ), and the degree of substitution at the C6 position of the 2EH substituent (" C6DS 2EH In one class of this embodiment, C6DS 2EH is C2DS 2EH and C3DS 2EH Exceeds the sum of.

[0146] In one embodiment, the cellulose ester has a degree of hydroxy substitution ("DS") of 1.0 or less. OH In one class of this embodiment, DS OH In one class of this embodiment, DSH is 0.90 or less. In one class of this embodiment, DSH is 0.95 or less. OH In one class of this embodiment, DS OH In one class of this embodiment, DS OH In one class of this embodiment, DS OH is less than 0.70.

[0147] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EHIn one class of this embodiment, DS 2EH is 0.3 to 0.5.

[0148] In one embodiment, the cellulose ester has an R 1 -CO-degree of substitution (“DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO is 0.5 to 1.0.

[0149] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and the cellulose ester has a degree of hydroxyl substitution ("DS OH "), and the cellulose ester has an Akacyl substitution degree ("DS Akacyl ").

[0150] In one embodiment, the cellulose ester has a glass transition temperature ("T"), determined according to ASTM E1356-03, that is less than 170°C. g In one embodiment, the cellulose ester has a glass transition temperature ("T") that is less than 165°C, as determined according to ASTM E1356-03. g In one embodiment, the cellulose ester has a glass transition temperature ("T") that is less than 160°C, as determined according to ASTM E1356-03. g ").

[0151] In one embodiment, the cellulose ester has a breaking strain greater than 3%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 3.5%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 4%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 4.5%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 5%, as determined according to ASTM D882-18.

[0152] The present application relates to regioselectively substituted cellulose esters, comprising: (i) a plurality of 2-ethylhexanoyl ("2EH") substituents, wherein the cellulose esters have a degree of 2EH substitution ("DS 2EH "), (ii) a plurality of (C 1~6 ) alkyl-CO- ("AkCO") substituents, where the cellulose ester has an AkCO degree of substitution ("DS AkCO "), (iii) a plurality of hydroxy ("OH") substituents, where the cellulose ester has a degree of OH substitution ("DS") of less than 0.8. OH "), (iv) a plurality of R 1 CO- ("ChCO") substituents, where the cellulose ester has a Ch degree of substitution ("DS ChCO ") Including, In the formula, R 1 is phenyl, where phenyl is unsubstituted or 1 to 5 R 2 is replaced by, and each R 2 are nitro, cyano, (C 1~6 ) alkyl, halo(C 1~6 ) alkyl; (C 6~20 )aryl-CO2-, (C 6~20 ) aryl, (C 1~6 ) alkoxyl, halo(C 1~6 ) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from alkoxyl, halo, N, O or S; or

[0153] [ka]

[0154] The cellulose ester has a C2-position substitution degree of AkCO substituents ("C2DS") in the range of 0.2 to 0.3. AkCO " ), and the C3 substitution degree of the AkCO substituent in the range of 0.2–0.4 (" C3DS AkCO " ), and the C6 substitution degree of the AkCO substituent in the range of 0.5–0.7 (" C6DS AkCO ") is disclosed.

[0155] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one class of this embodiment, the cellulose ester has a ChCO degree of substitution ("DS ChCO ").

[0156] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one class of this embodiment, the cellulose ester has a ChCO degree of substitution ("DS ChCO ").

[0157] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and a degree of OH substitution ("DS OH "), and Akacyl substitution degree ("DS Akacyl ").

[0158] In one embodiment, Akacyl is acetyl, propyl, butyryl, isobutyryl, pentanoyl, 3-methylbutanoyl, 2-methylbutanoyl, hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, or 4-methylpentanoyl. In one class of this embodiment, Akacyl is acetyl. In one class of this embodiment, Akacyl is propyl. In one class of this embodiment, Akacyl is butyryl. In one class of this embodiment, Akacyl is isobutyryl. In one class of this embodiment, Akacyl is pentanoyl. In one class of this embodiment, Akacyl is 3-methylbutanoyl. In one class of this embodiment, Akacyl is 2-methylbutanoyl. In one class of this embodiment, Akacyl is hexanoyl. In one class of this embodiment, Akacyl is 2-methylpentanoyl. In one class of this embodiment, Akacyl is 3-methylpentanoyl. In a class of this embodiment, Akacyl is 4-methylpentanoyl.

[0159] In one embodiment, the regioselectively substituted cellulose ester has a C2-substitution degree of 2EH substituents ("C2DS 2EH "), the degree of substitution of 2EH substituents at the C3 position ("C3DS2 EH " ), and the degree of substitution at the C6 position of the 2EH substituent (" C6DS 2EH In one class of this embodiment, C6DS 2EH is C2DS 2EH and C3DS 2EH Exceeds the sum of.

[0160] In one embodiment, the cellulose ester has a degree of hydroxy substitution ("DS") of 1.0 or less. OH In one class of this embodiment, DS OH In one class of this embodiment, DSH is 0.90 or less. In one class of this embodiment, DSH is 0.95 or less. OH In one class of this embodiment, DS OHIn one class of this embodiment, DS OH In one class of this embodiment, DS OH is less than 0.70.

[0161] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH In one class of this embodiment, DS 2EH is 0.3 to 0.5.

[0162] In one embodiment, the cellulose ester has an R 1 -CO-degree of substitution (“DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO In one class of this embodiment, DS ChCO is 0.5 to 1.0.

[0163] In one embodiment, the cellulose ester has a 2EH degree of substitution ("DS 2EH "), and the cellulose ester has a degree of hydroxyl substitution ("DS OH "), and the cellulose ester has an Akacyl substitution degree ("DS Akacyl ").

[0164] In one embodiment, the cellulose ester has a glass transition temperature ("T"), determined according to ASTM E1356-03, that is less than 170°C. g In one embodiment, the cellulose ester has a glass transition temperature ("T") that is less than 165°C, as determined according to ASTM E1356-03. g In one embodiment, the cellulose ester has a glass transition temperature ("T") that is less than 160°C, as determined according to ASTM E1356-03. g ").

[0165] In one embodiment, the cellulose ester has a breaking strain greater than 3%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 3.5%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 4%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 4.5%, as determined according to ASTM D882-18. In one embodiment, the cellulose ester has a breaking strain greater than 5%, as determined according to ASTM D882-18. film The cellulose ester and regioselectively substituted cellulose ester compositions disclosed in the present application can be fabricated into films.

[0166] Any of the optical films described above can be made by solution casting, melt extrusion, lamination or coating methods.These procedures are generally known in the art.Solution casting, melt extrusion, lamination and coating methods can be found, for example, in US Patent Application Publication No. 2009 / 0050842, US Patent Application Publication No. 2009 / 0054638 and US Patent Application Publication No. 2009 / 0096962, the contents of which are incorporated herein by reference.Further examples of solution casting, melt extrusion, lamination and coating methods for forming films can be found in US Patent Application Publication No. 10-4592885 and US Patent Application Publication No. 7172713, and US Patent Application Publication No. 2005 / 0133953 and US Patent Application Publication No. 2010 / 0055356, the contents of which are incorporated herein by reference.

[0167] To help obtain the desired optical properties of the films described in this invention, the films may be stretched. By adapting the stretching conditions, such as the stretching temperature, the type of stretching (uniaxial or biaxial), the stretch ratio, the time and temperature of preheating, and the time and temperature of kneading after stretching, the desired optical properties may be achieved. The exact stretching conditions may depend on the particular composition of the cellulose ester, the amount and type of plasticizer, and the glass transition temperature of the particular composition. Therefore, the particular stretching conditions may vary widely. In various embodiments, the stretching temperature may be in the range of about 160 to about 200° C. In addition, the stretch ratio based on 1.0 in the machine direction ("MD") may range from about 1.3 to about 2.0 in the transverse direction ("TD"). The preheating time may be in the range of about 10 to about 300 seconds, and the preheating temperature may be the same as the stretching temperature. The post-mixing time can range from about 0 to about 300 seconds, and the post-mixing temperature can range from about 10 to about 40° C. lower than the stretching temperature. The film thickness can depend on the film thickness before stretching and can depend on the stretching conditions. After stretching, the film thickness can be from about 1 μm to about 500 μm, from about 5 μm to about 200 μm, or from about 10 μm to about 120 μm. In one embodiment, the film is a uniaxially or biaxially stretched optical film. In one class of this embodiment, the film is a uniaxially stretched optical film. In one class of this embodiment, the film is a biaxially stretched optical film.

[0168] In one embodiment, the film is a +C film, a -C film, a +A film, or a ±A film. In one class of this embodiment, the film is a +C film. In one class of this embodiment, the film is a +C film. In one class of this embodiment, the film is a 25 -C film. In one class of this embodiment, the film is a +A film. In one class of this embodiment, the film is a -A film. In one class of this embodiment, the film is a ±A film. EXAMPLES

[0169] Abbreviation Int is intermediate, °C is degree Celsius, iPrOH is isopropyl alcohol, DMSO is dimethylsulfoxide, NMR is nuclear magnetic resonance, eq is equivalent, RXN is reaction, temp is temperature, wt% is weight percent, CAP482-20 is Eastman™ CAP482-20, h is time, POH is propionic acid, AcOH is acetic acid, Pyr is pyridine, CP is cellulose propionate, CAP is cellulose acetate propionate, DSOH is the average degree of substitution for the hydroxyl substituents, DS Pr is the average degree of substitution of the propionyl substituents, DMAC is dimethylacetamide, NMI is 1-methylimidazole, min is minutes, PvCl is pivaloyl chloride, CPPv is cellulose pivalate propionate, Pv is pivaloyl or pivalate, L is liters, Dissoln is soluble, wt is weight, 2EH is 2-ethylhexanoyl, 2EHCl is 2-ethylhexanoyl chloride, DS2EH is 2-ethylhexanoyl chloride, is the average degree of substitution for the xanoyl substituent, C2DS is the degree of substitution at the C2 position, C3DS is the degree of substitution at the C3 position, C6DS is the degree of substitution at the C6 position, CP2EHNp is cellulose propionyl 2-ethylhexanoate naphthoate, F is furanoyl or furanoate, FCl is furanoyl chloride, TCA is (E)-2-cyano-3-(p-tolyl)acryloyl, and TCACl is (E)-2-cyano-3-(p-tolyl)acryloyl chloride. Procedures for the synthesis of regioselective cellulose esters and intermediates 1. Cellulose ester intermediates Preparation of intermediate 1CP: To a four-necked 2 L jacketed flask equipped with overhead stirring and bottom valve under nitrogen was added iPrOH (418 g). The jacket was set at 50° C. To the reactor was added Eastman™ CAP482-20 (120.1 g) through a vent funnel and the material was vortexed. The slurry was stirred for 10 min. To the slurry was added AcOH (9.2 g, 0.40 eq) and N2H4·H2O (34.7 g, 1.81 eq) in DMSO (418 g). The reaction mixture was stirred for 12 h. The dope was precipitated by the addition of water to give the product as a white solid. The solid was filtered on a glass frit and washed with copious amounts of water. The product was transferred to an aluminum pan and dried in vacuum at 60° C. for 16 h to give Int1. 1 H NMR, 13 C NMR analysis revealed that DS Pr =1.19, DS OH =1.81, C2DS Pr =0.27, C3DS Pr =0.32, C6DS Pr =0.57 was determined.

[0170] Preparation of intermediate 2 (CP): In a variation on the preparation of Int1, 1.70 eq of hydrazine monohydrate was used. Pyridine replaced iPrOH and DMSO solvent, acetic acid was replaced with propionic acid (0.1 eq), and the reaction temperature was set at 50° C. to give Int2:( 1 H NMR, 13 DS (determined by C NMR) Pr =1.15 and DS OH =1.85 was obtained.

[0171] Table 1 lists the cellulose propionates synthesized along with the equivalent amount of N2H4·H2O, the solvent used, weight percent polymer, acid (acetic acid or propionic acid), reaction duration, and reaction temperature.

[0172] [Table 1]

[0173] Table 2 shows 1 H and 13 1 shows the degree of hydroxyl substitution, and the degree of C2, C3 and C6 substitution with propionyl for Int2-12 as determined by C NMR.

[0174] [Table 2]

[0175] Preparation of intermediate 13 (CPPv): Anhydrous DMAC (6.27 mol) and NMI (1.23 mol) were charged to a 1 L 4-neck jacketed resin kettle reaction flask under nitrogen with overhead mechanical stirring. Int1 (0.288 mol) was added to the mixture with stirring using a vent funnel to bring the powder into a vortex. The mixture was stirred at 30° C. for 90 min to obtain a homogenous mixture. To the dope was added PvCl (0.44 mol eq relative to Int1) in DMAC (0.194 mol) dropwise over 25 min. The reaction mixture was stirred at 35° C. for 5 h. Int13 was precipitated by pouring the reactants into 4 L of water under homogenization to obtain a white solid. The solid was collected in a polypropylene woven bag and washed successively with deionized water for 6 h. The washed product was centrifuged while still in the closed bag to remove excess water, and the product was then transferred to a glass crystallizing dish and dried overnight in vacuum at 55°C. 1 H NMR and 13 C NMR analysis revealed that DS Pr =1.19, DS Pv =0.40 and DS OH =1.41 was determined.

[0176] Preparation of Intermediate 14 (CPPv): In a variation to Intermediate 13, anhydrous DMAC (1.95 mol) and NMI (0.38 mol) were charged to a 1 L four-neck jacketed resin kettle reaction flask equipped with overhead mechanical stirring under nitrogen. To the mixture, Int1 (0.087 mol) was added with stirring using a vent funnel to bring the powder into a vortex. The mixture was stirred at 26° C. for 7 hours to obtain a homogenous mixture. To the dope, neat PvCl (0.39 mol eq relative to Int1) was added dropwise over 60 minutes. The reaction mixture was stirred at 26° C. for 2.5 hours. The Int14 product was precipitated by pouring the reactants into 2 L of water with homogenization to obtain a white solid. The solid was collected in a polypropylene woven bag and washed successively with deionized water for 6 hours. The washed product was centrifuged while still in the closed bag to remove excess water, and the product was then transferred to a glass crystallizing dish and dried overnight in vacuum at 55°C. 1 H NMR and 13 C NMR analysis revealed that DS Pr =1.19, DS Pv =0.35 and DS OH =1.46 was determined.

[0177] Table 3 lists the pivalate propionate cellulose intermediates synthesized along with the amount of solvent and CP intermediate, equivalent amount of PvCl, type of PvCl additive, dissolution and reaction temperature, CP dissolution time, and PvCl reaction time.

[0178] [Table 3]

[0179] Table 4 shows the degree of propionyl and pivaloyl substitution, as well as the degree of substitution at C2, C3 and C6 positions for the hydroxyl group, and 1 H and 13 The total DS for Int15-25 as determined by C NMR is shown.

[0180] [Table 4]

[0181] Preparation of intermediate 26 (CP2EH): Anhydrous DMAC (3.48 mol) and NMI (0.36 mol) were charged to a 1 L 4-neck jacketed resin kettle reaction flask under nitrogen with overhead mechanical stirring. To the mixture, Int1 (0.087 mol) was added with stirring using a vent funnel to bring the powder into a vortex. The mixture was stirred at 30° C. for 90 min to obtain a homogenous mixture. To the dope, 2-ethylhexanoyl chloride (0.44 mol eq relative to Int1) in DMAC (0.184 mol) was added dropwise over 25 min. The reaction mixture was stirred at 30° C. for 255 min. Int26 was precipitated by pouring the reactants into 4 L of water with homogenization to obtain a white solid. The solid was collected in a polypropylene woven bag and washed successively with deionized water for 6 h. The washed product was centrifuged while still in the closed bag to remove excess water, and the product was then transferred to a glass crystallizing dish and dried overnight in vacuum at 55°C. 1 H NMR and 13 C NMR analysis revealed that DS Pr =1.18, DS 2EH =0.41, DS OH = 1.41, C2DS = 0.34, C3DS = 0.37 and C6DS = 0.85.

[0182] Table 5 lists the cellulose propionate 2-ethylhexanoate intermediates that were synthesized along with the amount of solvent and CP intermediate, equivalents of 2EHCl, CP dissolution time, and 2EHCl reaction time.

[0183] [Table 5]

[0184] Table 6 shows the degree of substitution of propionyl and 2-ethylhexanoyl, as well as the degree of substitution of the hydroxyl group at the C2, C3 and C6 positions, and 1 H and13 The total DS for Int27-29 as determined by C NMR is shown.

[0185] [Table 6]

[0186] Preparation of Example 1 (CP2EHNp): To a dry 1 L 4-neck resin kettle equipped with mechanical stirring under nitrogen, DMAC (2.30 mol) and NMI (0.37 mol) were added. To the mixture, Int29 (0.071 mol) was added and the mixture was stirred at 40° C. for 4 hours to obtain a dope. The dope was cooled to 25° C. and NpCl (1.41 mol eq relative to Int29) in DMAC (0.31 mol) was added dropwise over 30 minutes. The mixture was heated to 35° C. and stirred for 16 hours. The dope was homogenized using a high speed homogenizer to provide turbulent mixing. i The product was precipitated by slowly pouring into 2 L of POH, which gave a white solid. The solid was isolated by vacuum filtration, and the bag was then washed with deionized water for 5 hours to give the title compound. The product was dried overnight in vacuum at 55° C. Example 1 1 Analysis by H NMR revealed that DS Pr =1.18, DS 2EH =0.41;DS Np =1.26 and DS OH =0.15 was determined.

[0187] Preparation of Example 2 (CP2EHNp): In a variation to Example 1, to a dry 1 L four-neck resin kettle, DMAC (2.22 mol) and NMI (0.47 mol) were added under nitrogen with mechanical stirring. To the mixture, Int1 (0.104 mol) was added and the mixture was stirred at 32° C. for 4 hours to obtain a dope. To the dope cooled to 26° C., neat 2EHCl (0.44 mol eq. relative to Int1) was added dropwise over 60 minutes and the mixture was stirred at 26° C. for 2 hours. To the reaction mixture, NpCl (1.32 mol eq. relative to Int1) in DMAC (0.304 mol) was added dropwise over 120 minutes. The reaction mixture was stirred for 12 hours. The dope was precipitated by slowly pouring into 2 L of iPOH using a high-speed homogenizer that provided turbulent mixing, thereby obtaining a white solid. The solid was isolated by vacuum filtration and the bag was then washed with deionized water for 5 hours to give the title compound. The product was dried overnight in vacuum at 55° C. 1 H NMR, 13 C NMR analysis revealed that DS Pr =1.18, DS 2EH =0.45;DS Np =1.31;DS OH = 0.06; C2DS = 1.00; C3DS = 0.84; C6DS = 0.90.

[0188] Preparation of Comparative Example 3 (CPPvF): A dry 250 mL Erlenmeyer flask equipped with a magnetic stir bar and capped with a septum was charged with anhydride (1.76 mol) and NMI (0.18 mol). To the mixture was added Int23 (0.038 mol) with stirring. The mixture was stirred at 26° C. for 3 hours to obtain a dope. To the dope was added furanoyl chloride (1.18 mol eq relative to Int23) in DMAC (0.126 mol) over 2 minutes with stirring. The reaction was stirred at 26° C. for 16 hours. The product was precipitated by pouring into 1.2 L of methanol with homogenization to obtain Comparative Example 3 as a white solid. The solid was collected in a polypropylene woven bag and washed with methanol (2×800 mL). The washed product was transferred to a washing station while still in the closed bag and washed successively with deionized water for 6 hours. The product was centrifuged to remove excess water, then the product was transferred to a glass crystallizing dish and dried overnight in vacuum at 55°C. 1 H.N.M., 13 C NMR analysis revealed that DS Pr =1.19, DS Pv =0.45;DS F =1.05;DS OH = 0.31; C2DS = 0.96; C3DS = 0.71; C6DS = 0.89.

[0189] Preparation of Comparative Example 4 (CPPvNp): To a dry 1 L four-neck resin kettle, DMAC (4.60 mol) and NMI (0.96 mol) were added under nitrogen with mechanical stirring. To the mixture, Int1 (0.22 mol) was added and the mixture was stirred at 32° C. for 4 hours to obtain a dope. To the dope cooled to 26° C., neat PvCl (0.43 mol eq relative to Int1) was added dropwise over 1 hour. The mixture was stirred for 1 hour. To the dope, NpCl (1.20 mol eq relative to Int1) in DMAC (0.612 mol) was added dropwise over 2 hours. The mixture was stirred at 26° C. for 16 hours. The dope was precipitated by slowly pouring into 4 L of iPOH using a high speed homogenizer that provided turbulent mixing, thereby obtaining Comparative Example 4 as a solid. The solid was isolated by vacuum filtration and then the bag was washed with deionized water for 5 hours to obtain the title compound. The product was dried overnight in vacuum at 55° C. 1 Analysis by H NMR revealed that DS Pr =1.19, DS Pv =0.40;DS Np =1.20 and DS OH =0.21 was determined.

[0190] Preparation of Comparative Example 5 (CPPvTCA): A dry 500 mL Erlenmeyer flask equipped with a magnetic stir bar and capped with a septum was charged with anhydrous DMAC (3.44 mol) and NMI (0.365 mol). To the mixture was added Int20 (0.077 mol) with stirring. The mixture was stirred at 26° C. for 3 hours to obtain a dope. To the dope was added TCACl (1.00 mol eq with respect to Int20) in DMAC (0.287 mol) over 2 minutes with stirring. The reaction was stirred at 26° C. for 16 hours. The product was precipitated by pouring into 2.2 L of methanol with homogenization to obtain Comparative Example 5. The solid was collected in a polypropylene woven bag and washed with methanol (2×800 mL). The washed product was transferred to a washing station while still in the closed bag and washed successively with deionized water for 6 hours. The product was centrifuged to remove excess water, then the product was transferred to a glass crystallizing dish and dried overnight in a vacuum oven at 55°C. 1 Analysis by H NMR revealed that DS Pr =1.19, DS Pv =0.42;DS TCA =0.89;DS OH =0.50 was determined.

[0191] Preparation of Example 6 (CP2EHTCA): In a variation to Example 5, a dry 500 mL Erlenmeyer flask equipped with a magnetic stir bar and capped with a septum was charged with anhydrous DMAC (1.73 mol) and NMI (0.18 mol). Int29 (0.036 mol) was added to the mixture, and the mixture was stirred at 26° C. for 3 hours to obtain a dope. TCACl (1.0 mol eq relative to Int29) was added to the dope by injecting the powder into the flask over 1 min, and the mixture was stirred at 26° C. for 16 hours. The dope was precipitated by slowly injecting into 1.2 L of MeOH using a high speed homogenizer to provide turbulent mixing, thereby obtaining Example 6. Example 6 was isolated by vacuum filtration, and the bag was then washed with deionized water for 5 hours to obtain the title compound. The product was dried overnight in vacuum at 55° C. 1 Analysis by H NMR revealed that DSPr =1.18, DS 2EH =0.42;DS TCA =0.89;DS OH =0.50 was determined.

[0192] The examples in Tables 7 and 8 were synthesized by adapting the procedures for the synthesis of Examples 1 to 6. Table 7 shows the product ID, moles of cellulose ester intermediate, DMAC and NMI.

[0193] [Table 7]

[0194] Table 8 shows the product ID, mode of addition, and molar equivalents of alkylCOCl (PvCl and 2EHCl) and ChCl (NpCl, TCACl, and FCl).

[0195] [Table 8]

[0196] Table 9 lists the product ID and the alkyl (Pr, Pv and 2EH), Ch (Np, F and TCA), OH substitution degree, and 1 The total substituents as determined by 1 H NMR are shown.

[0197] [Table 9]

[0198] General Procedure for Film Casting Solvents (DCM, 10% MeOH in DCM, 10% DCE in DCM, MEK or MIPK) and regioselective cellulose esters (12 wt%), and optional plasticizers (10 wt%, DEP or TPP) were mixed for 24 hours to make homogeneous dopes. From this dope, for dopes made from MEK, films were cast on glass using a knife applicator and dried at 85°C for 10 minutes in a forced air oven. The cast films were kneaded at 100°C and 120°C for 10 minutes each in a forced air oven. The thickness of the films was measured using a Metricon Prism Coupler 2010 (Metricon Corp.). Birefringence and retardation were measured using an M-2000V Ellipsometer (JA Woollam Co.). Haze and b * Measurements were performed using a HunterLab Ultrascan VIS calorimeter in diffuse transmission mode (1 inch port). In the doped case, a 1 cm path length cell was used. * and for haze, 10 measurements were taken and the average reported.

[0199] Preparation of film 1-1: Using the dope of Example 1 (12 wt%) in MEK, the following optical properties were obtained: Δn=0.0101 (589 nm), R th [450nm] / R th [550nm]=1.11(dispersion);R th = 0.95 (650 nm / 550 nm) was cast into a 7.5 μm thick film.

[0200] Tables 10 and 11 show the optical results for the compounds of this application. In all examples the casting solvent was MEK and there was no added plasticizer.

[0201] [Table 10]

[0202] [Table 11]

[0203] Table 12 shows that cellulose esters regioselectively substituted with 2-ethylhexanoyl have a lower T g It has been shown that the cellulose esters regioselectively substituted with naphthoyl and pivaloyl have higher Young's modulus and breaking strain. In addition, it was found that some of the cellulose esters regioselectively substituted with naphthoyl were too brittle to be tested. On the other hand, it was found that none of the cellulose esters regioselectively substituted with 2-ethylhexanoyl and naphthoyl were brittle. As a result, it is expected that the cellulose esters regioselectively substituted with 2-ethylhexanoyl will exhibit better mechanical properties and can be made into thinner and larger films.

[0204] Table 12 shows the T for selected examples. g , strain at break (%) and Young's modulus are shown.

[0205] [Table 12]

[0206] Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein. It is to be understood that variations and modifications can be made within the spirit and scope of the disclosed embodiments. It is further intended that the specification and examples be considered as representative only, with a true scope and spirit of the disclosed embodiments being indicated by the following claims. The present invention includes the following embodiments. [1] A regioselectively substituted cellulose ester, (i) a plurality of 2-ethylhexanoyl ("2EH") substituents, where the cellulose ester has a 2EH degree of substitution ("DS") of 0.1 to 1.0. 2EH ") (ii) Multiple (C 1~6 ) alkyl-CO- ("AkCO") substituents, where the cellulose ester has an AkCO degree of substitution ("DS AkCO ") (iii) a plurality of hydroxy ("OH") substituents, wherein the cellulose ester has a degree of OH substitution ("DS") of less than 0.8. OH ") (iv) Multiple R 1 -CO- ("ChCO") substituents, where the cellulose ester has a ChCO degree of substitution ("DS ChCO ") Including, During the ceremony, R 1 teeth, (1)(C 10~20 ) aryl, where aryl is unsubstituted or has 1 to 5 R 2 has been replaced by (2) 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R 2 has been replaced by (3)

change

change

change

[10] R 1 is furanyl, pyrrolyl, benzothiophenyl, or thiofuranyl, where each ring is unsubstituted or has 1 to 5 R 2 The regioselectively substituted cellulose ester according to [9], wherein the cellulose ester is substituted by

[11] The regioselectively substituted cellulose ester according to any one of [1] to

[10] , wherein Akacyl is acetyl, propionyl, butanoyl, pentanoyl or hexanoyl.

[12] R 1 is naphthyl, furanyl or

change

[11] to

[13] , wherein

[13] The regioselectively substituted cellulose ester according to

[12] , wherein AkCO is propionyl.

[14] DS 2EH The regioselectively substituted cellulose ester according to any one of [1] to

[13] , wherein m is 0.3 to 0.5.

[15] DS ChCO The regioselectively substituted cellulose ester according to any one of [1] to

[14] , wherein

[16] DS OH The regioselectively substituted cellulose ester according to any one of [1] to

[15] , wherein is less than 0.6.

[17] A glass transition temperature ("T") of less than 170°C, as determined in accordance with ASTM E1356-03. g The regioselectively substituted cellulose ester according to any one of [1] to

[16] , having a structure in which

[18] The regioselectively substituted cellulose ester according to any one of [1] to

[17] , having a break strain greater than 3%, as determined according to ASTM D882-18.

[19] A film comprising the regioselectively substituted cellulose ester according to any one of [1] to

[18] .

Claims

1. A regioselectively substituted cellulose ester comprising: (i) a plurality of 2-ethylhexanoyl ("2EH") substituents, where the cellulose ester has a 2EH degree of substitution ("DS") of 0.1 to 1.

0. ２ＥＨ ") (ii) a plurality of (C １～６ ) alkyl-CO- ("AkCO") substituents, where the cellulose ester has an AkCO degree of substitution ("DS ＡｋＣＯ ") (iii) a plurality of hydroxy ("OH") substituents, wherein the cellulose ester has a degree of OH substitution ("DS") of less than 0.

8. ＯＨ ") (iv) a plurality of R １ -CO- ("ChCO") substituents, where the cellulose ester has a degree of ChCO substitution ("DS ＣｈＣＯ ") Including, During the ceremony, R １ teeth, (1) (C １０～２０ ) aryl, where aryl is unsubstituted or has 1 to 5 R ２ has been replaced by (2) 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R ２ has been replaced by （３） 【Chemistry 1】 wherein aryl is (C 6-10)aryl, where aryl is unsubstituted or has 1-5 R ２ has been replaced by or （４） 【Chemistry 2】 wherein heteroaryl is a 5-10 membered ring having 1-4 heteroatoms selected from N, O or S, where heteroaryl is unsubstituted or has 1-5 R ２ has been replaced by and Each R ２ is nitro, cyano, (C １～６ ) alkyl, halo (C １～６ ) alkyl; (C ６～２０ ) Aryl-CO ２ -, (C ６～２０ ) aryl, (C １～６ ) alkoxyl, halo(C １～６ ) a 5-10 membered heteroaryl having 1-4 heteroatoms selected from alkoxyl, halo, N, O or S; or 【Chemistry 3】 are independently selected from The cellulose ester has a C2-position substitution degree of the AkCO substituent in the range of 0.2 to 0.3 ("C2DS ＡｋＣＯ "), the C3-position substitution degree of the AkCO substituent in the range of 0.2 to 0.4 ("C3DS ＡｋＣＯ "), and the C6 substitution degree of the AkCO substituent in the range of 0.5 to 0.7 ("C6DS ＡｋＣＯ ") Regioselectively substituted cellulose esters.

2. The degree of substitution of the 2EH substituent at the C2 position ("C2DS") is less than 0.

1. ２ＥＨ "), the degree of substitution of 2EH substituents at the C3 position ("C3DS2 ＥＨ "), and the degree of substitution at the C6 position of the 2EH substituent ("C6DS ２ＥＨ 2. The regioselectively substituted cellulose ester of claim 1 having the formula:

3. C6DS ２ＥＨ But C2DS ２ＥＨ and C3DS ２ＥＨ The regioselectively substituted cellulose ester of claim 2 , wherein

4. R １ However, (C １０～２０ ) aryl, where aryl is unsubstituted or has 1 to 5 R ２ The regioselectively substituted cellulose ester of claim 1 , substituted by:

5. R １ However, (C １０～２０ ) aryl, unsubstituted or 1 to 5 R ２ The regioselectively substituted cellulose ester of claim 4 , substituted by:

6. R １ is naphthyl and is unsubstituted or 1 to 5 R ２ The regioselectively substituted cellulose ester of claim 5 , substituted by:

7. R １ is a 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O or S, where the heteroaryl is unsubstituted or has 1-5 R ２ The regioselectively substituted cellulose ester of claim 1 , substituted by:

8. R １ 8. The regioselectively substituted cellulose ester of claim 7, wherein is an unsubstituted 5-10 membered heteroaryl having 1-4 heteroatoms selected from N, O, or S.

9. R １ is furanyl, pyrrolyl, thiophenyl, bipyridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzothiophenyl, or phthalazinyl, wherein each ring is unsubstituted or has 1 to 5 R ２ The regioselectively substituted cellulose ester of claim 8 , substituted by:

10. R １ is furanyl, pyrrolyl, benzothiophenyl, or thiofuranyl, where each ring is unsubstituted or has 1 to 5 R ２ The regioselectively substituted cellulose ester of claim 9 , substituted by:

11. 11. The regioselectively substituted cellulose ester of claim 1, wherein AkCO is acetyl, propionyl, butanoyl, pentanoyl or hexanoyl.

12. R １ is naphthyl, furanyl or 【Chemistry 4】 2. The regioselectively substituted cellulose ester of claim 1, wherein

13. 13. The regioselectively substituted cellulose ester of claim 12, wherein AkCO is propionyl.

14. D.S. ２ＥＨ The regioselectively substituted cellulose ester according to any one of claims 1 to 13, wherein is 0.3 to 0.

5.

15. D.S. ＣｈＣＯ The regioselectively substituted cellulose ester according to any one of claims 1 to 14, wherein is 0.8 to 1.

4.

16. D.S. ＯＨ The regioselectively substituted cellulose ester of claim 1 , wherein is less than 0.

6.

17. A glass transition temperature ("T") of less than 170°C, as determined in accordance with ASTM E1356-03. ｇ 17. The regioselectively substituted cellulose ester of claim 1 having the formula:

18. 18. The regioselectively substituted cellulose ester of any one of claims 1 to 17 having a strain at break, determined according to ASTM D882-18, that is greater than 3%.

19. A film comprising the regioselectively substituted cellulose ester of any one of claims 1 to 18.

Images