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US20200017606A1 - Regioselectively substituted cellulose esters - Google Patents

Regioselectively substituted cellulose esters Download PDF

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Publication number
US20200017606A1
US20200017606A1 US16/492,965 US201816492965A US2020017606A1 US 20200017606 A1 US20200017606 A1 US 20200017606A1 US 201816492965 A US201816492965 A US 201816492965A US 2020017606 A1 US2020017606 A1 US 2020017606A1
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halo
range
alkyl
cellulose ester
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Robert Lin
Michael John Rodig
Robert Jacks Sharpe
Glenn Lewis Shoaf
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Eastman Chemical Co
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Eastman Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C08J2301/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/14—Mixed esters

Definitions

  • This invention relates to the field of cellulose chemistry, cellulose ester compositions, methods of making cellulose ester, and films made from cellulose esters.
  • Cellulose is a ⁇ -1,4-linked polymer of anhydroglucose.
  • Cellulose is typically a high molecular weight, polydisperse polymer that is insoluble in water and virtually all common organic solvents.
  • Unmodified cellulose is also utilized in a variety of other applications usually as a film, such as cellophane, as a fiber, such as viscose rayon, or as a powder, such as microcrystalline cellulose used in pharmaceutical applications.
  • Modified cellulose such as cellulose esters are also widely utilized in a wide variety of commercial applications. Prop. Polym. Sci. 2001, 26, 1605-1688.
  • Cellulose esters are generally prepared by first converting cellulose to a cellulose triester before hydrolyzing the cellulose triester in acidic aqueous media to the desired degree of substitution. Hydrolysis of cellulose triacetate under these conditions yields a random copolymer that can consist of 8 different monomers depending upon the final degree of substitution. Macromolecules 1991, 24, 3050.
  • This application describes new regioselectively substituted cellulose esters prepared by first treating cellulose with trifluoroacetic anhydride in trifluoroacetic acid, followed by the addition of acyl donors or acyl donor precursors.
  • the present application discloses a regioselectively substituted cellulose ester comprising:
  • the present application also discloses a regioselectively substituted cellulose ester comprising:
  • the present application also discloses films made from the regioselectively substituted cellulose esters disclosed herein.
  • the present application also discloses processes for preparing the regioselectively substituted cellulose esters disclosed herein.
  • Values may be expressed as “about” or “approximately” a given number.
  • ranges may be expressed herein as from “about” one particular value and/or to “about” or another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value.
  • values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect.
  • Optical films are commonly quantified in terms of birefringence which is, in turn, related to the refractive index n.
  • the refractive index can typically be in the range of 1.4 to 1.8 for polymers in general, and can be approximately 1.46 to 1.50 for cellulose esters. The higher the refractive index, the slower a light wave propagates through that given material.
  • the refractive index will be the same regardless of the polarization state of the entering light wave.
  • the refractive index becomes dependent on material direction.
  • MD machine direction
  • TD transverse direction
  • the difference between any two refractive indices will increase.
  • birefringence This difference is referred to as the “birefringence.” Because there are many combinations of material directions to choose from, there are correspondingly different values of birefringence. The two that are the most common, namely the planar birefringence (or “in-plane” birefringence) ⁇ e and the thickness birefringence (or “out-of-plane” birefringence) ⁇ th , are defined as:
  • ⁇ e is a measure of the relative in-plane orientation between the MD and TD directions and is dimensionless.
  • ⁇ th gives a measure of the orientation of the thickness direction, relative to the average planar orientation.
  • optical retardation R is simply the birefringence times the thickness d, of the film in question.
  • Retardation is a direct measure of the relative phase shift between the two orthogonal optical waves and is typically reported in units of nanometers (nm). Note that the definition of R th varies among some authors, particularly with regards to the sign (+/ ⁇ ), depending on how R th is calculated.
  • Materials are also known to vary with regards to 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. This follows because, on a molecular level, the refractive index is typically higher along the polymer chain's axis and lower perpendicular to the chain. These materials are commonly termed “positively birefringent” and represent most standard polymers, including current commercial cellulose esters. Note that, as we will describe later, a positively birefringent material can be used to make either positive or negative birefringent films or waveplates.
  • intrinsic birefringence is a measure of the birefringence that would occur if the material was fully stretched with all chains perfectly aligned in one direction (for most polymers this is a theoretical limit since they can never be fully aligned). For purposes of the present invention, it also provides a measure of the sensitivity of a given polymer to a given amount of chain orientation. For example, a sample with high intrinsic birefringence is going to exhibit more birefringence during film formation than a sample with low intrinsic birefringence, even though the relative stress levels in the film are approximately the same.
  • Polymers can have positive, negative, or zero intrinsic birefringence. Negative intrinsic birefringent polymers exhibit a higher refractive index perpendicular to the stretch direction (relative to the parallel direction). Certain styrenics and acrylics can have negative intrinsic birefringent behavior due to their rather bulky side groups. Depending on composition, some cellulose esters having aromatic ring structures can exhibit negative intrinsic birefringence as well. Zero intrinsic birefringence, in contrast, is a special case and represents materials that show no birefringence with stretching and thus have a zero intrinsic birefringence. Such materials can be ideal for certain optical applications as they can be molded, stretched, or otherwise stressed during processing without showing any optical retardation or distortion.
  • the actual compensation film(s) that is used in an LCD can take on a variety of forms including biaxial films where all three refractive indices differ and two optical axes exist, and uniaxial films having only one optical axis where two of the three refractive indices are the same.
  • There are also other classes of compensation films where the optical axes twist or tilt through the thickness of the film e.g., discotic films
  • the type of compensation film that can be made is limited by the birefringence characteristics of the polymer (i.e., positive, negative or zero intrinsic birefringence).
  • the sign can be placed before or after the type of film (e.g., +A or A+). A few examples are described below.
  • the x-direction (machine direction) of the film has a high refractive index, whereas the y and thickness directions are approximately equal in magnitude (and lower than n x ).
  • This type of film is also referred to as a positive uniaxial crystal structure with the optic axis along the x-direction.
  • Such films can be made by uniaxially stretching a positive intrinsic birefringent material using, for example, a film stretcher.
  • One method for making a ⁇ A optical film is to stretch a negative intrinsic birefringent polymer or, alternately, by coating a negatively (intrinsic) birefringent liquid crystal polymer onto a surface such that the molecules are lined up in a preferred direction (for example, by using an underlying etched orientation layer).
  • C optical film which can also be “+C” or “ ⁇ C”.
  • the difference between a C and an A optical film is that, in C optical films, the unique refractive index (or optical axis) is in the thickness direction as opposed to in the plane of the film.
  • C optical films can be produced by taking advantage of the stresses that form during solvent casting of a film. Tensile stresses are generally created in the plane of the film due to the restraint imposed by the casting belt, which are also equi-biaxial stretched in nature. 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. As many cellulose ester films used in displays are solvent cast, and many are essentially positive birefringent, then it is apparent that solvent cast cellulose esters normally only produce ⁇ C optical films. These films can also be uniaxially stretched to produce +A optical films (assuming the initial as-cast retardation is very low).
  • Biaxial films are quantified in a variety of ways including simply listing the 3 refractive indices n x , n y and n z in the principal directions (along with the direction of these principal axes). Generally, n x ⁇ n y ⁇ n z .
  • One specific biaxial oriented film has unique optical properties to compensate light leakage of a pair of crossed polarizer or in-plane switching (“IPS”) mode liquid crystal displays.
  • the optical film has a parameter Nz in the range of from about 0.4 to about 0.9, or equals about 0.5, where Nz is defined as
  • Nz ( n x ⁇ n z )/( n x ⁇ n y ) (5)
  • Nz can be chosen to be about 0.5 when used as a compensation film for a pair of crossed polarizers.
  • R th the corresponding out-of-plane retardation
  • Degree of substitution means the average number of substituents per anhydroglucose monomer of the cellulose ester.
  • Degree of substitution can refer to a substituent attached to the anhydroglucose monomer, for example an acyl group.
  • Degree of substitution can also refer to the number of free hydroxyl groups on the anhydroglucose monomer.
  • the degree of substitution can specify the position on the anhydroglucose monomer.
  • the degree of substitution can apply to the C2, C3, or C6 position of the anhydroglucose monomer (e.g., C2DS, C3DS, C6DS):
  • the positional degree of substitution can be expressed by indicating the position before the term “degree of substitution” (e.g., C2 degree of substitution or combined C2 and C3 degree of substitution).
  • “Degree of polymerization” means the number of glucose units that make up one polymer molecule.
  • Regioselectively substituted cellulose esters suitable for use in making optical films can comprise a plurality of alkyl-acyl substituents and a plurality of aryl-acyl substituents.
  • acyl substituent shall denote a substituent having the structure:
  • Such acyl groups in cellulose esters are generally bound to the pyranose ring of the cellulose via an ester linkage (i.e., through an oxygen atom).
  • alkyl-acyl shall denote an acyl substituent where “R” is an alkyl group. Often the carbon units of the alkyl groups are included; for example, (C 1-6 )alkyl-acyl. Examples of alkyl-acyl groups include acetyl, propionyl, butyryl, and the like.
  • alkyl shall denote a hydrocarbon substituent.
  • Alkyl groups suitable for use herein can be straight, branched, or cyclic, and can be saturated or unsaturated. The carbon units in the alkyl group is often included; for example (C 1-6 )alkyl.
  • Alkyl groups suitable for use herein include any (C 1-20 ), (C 1-12 ), (C 1-5 ), or (C 1-3 ) alkyl groups.
  • the alkyl can be a C 1-5 straight chain alkyl group.
  • the alkyl can be a C 1-3 straight chain alkyl group.
  • 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.
  • the acylating agents can be any known in the art for acylating cellulose to produce cellulose esters.
  • the acylating reagent is one or more C 1 -C 20 straight- or branched-chain alkyl or aryl carboxylic anhydrides, carboxylic acid halides, diketene, or acetoacetic acid esters.
  • carboxylic anhydrides include, but are not limited to, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, hexanoic anhydride, 2-ethylhexanoic anhydride, nonanoic anhydride, lauric anhydride, palmitic anhydride, stearic anhydride, benzoic anhydride, substituted benzoic anhydrides, phthalic anhydride, and isophthalic anhydride.
  • carboxylic acid halides include, but are not limited to, acetyl, propionyl, butyryl, hexanoyl, 2-ethylhexanoyl, lauroyl, palmitoyl, benzoyl, substituted benzoyl, and stearoyl halides.
  • acetoacetic acid esters include, but are not limited to, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and tert-butyl acetoacetate.
  • the acylating reagent is at least one C 2 -C 9 straight- or branched-chain alkyl carboxylic anhydrides selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, 2-ethylhexanoic anhydride, nonanoic anhydride, and stearic anhydride.
  • the acylating reagents can be added after the cellulose has been dissolved in the tetraalkylammonium alkylphosphate.
  • the acylating reagent can be added to the tetraalkylammonium alkylphosphate prior to dissolving the cellulose in the tetraalkylammonium alkylphosphate.
  • the tetraalkylammonium alkylphosphate and the acylating reagent can be added simultaneously to the cellulose to produce the cellulose solution.
  • Haloalkyl means an alkyl substituent where at least one hydrogen is replaced with a halogen group.
  • the carbon units in the haloalkyl group is often included; for example halo(C 1-6 )alkyl.
  • the haloalkyl group can be straight or branched.
  • Nonlimiting examples of haloalkyl include chloromethyl, trifluoromethyl, dibromoethyl and the like.
  • Alkenyl means an alkyl group of at least two carbon units containing at least one double bond.
  • the carbon units in the alkenyl group is often included; for example (C 2-6 )alkenyl.
  • the alkenyl group can be straight or branched.
  • Nonlimiting examples of alkenyl include ethenyl, allyl, 1-butenyl, and the like.
  • Cycloalkyl means a cyclic alkyl group having at least three carbon units. The carbon units in the cycloalkyl group is often included; for example (C 3-8 )cycloalkyl.
  • Nonlimiting examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, and the like.
  • Aryl means an aromatic carbocyclic group.
  • the aryl group can be monocyclic or polycyclic. If one of the rings in the polycyclic ring system is aryl, then the polycyclic ring system is considered aryl. In other words, all of the carbocyclic rings in a polycyclic aryl group do not have to be aromatic.
  • the carbon units in the aryl group is often included; for example (C 6-20 )aryl.
  • Nonlimiting examples of aryl include phenyl, naphthalenyl, 1,2,3,4-tetrahydronaphthalenyl, and the like.
  • Heteroaryl means an aryl where at least one of the carbon units in the aryl ring is replaced with a heteroatom such as O, N, and S.
  • the heteroaryl is ring can be monocyclic or polycyclic. Often the units making up the heteroaryl ring system is include; for example a 5- to 20-membered ring system.
  • a 5-membered heteroaryl means a ring system having five atoms forming the heteroaryl ring.
  • Nonlimiting examples of heteroaryl include pyridinyl, quinolinyl, pyrimidinyl, thiophenyl and the like.
  • Alkoxy means alkyl-O— or an alkyl group terminally attached to an oxygen group. Often the carbon units are included; for example (C 1-6 )alkoxy. Nonlimiting examples of alkoxy include methoxy, ethoxy, propoxy and the like.
  • Haloalkoxy means alkoxy where at least one of the hydrogens is replace with a halogent. Often the carbon units are included; for example halo(C 1-6 )alkoxy. Nonlimiting examples of haloalkoxy include trifluoromethoxy, bromomethoxy, 1-bromo-ethoxy and the like.
  • Halo means halogen such as fluoro, chloro, bromo, or iodo.
  • a “Reverse A film” is a film that satisfies the following conditions:
  • the in-plane retardation is in the range of from about 100 nm to about 300 nm as measured at 589 nm, R e 450/R e 550 is less than 1, and R e 650/R e 550 is greater than 1, wherein R e 450, R e 550, and R e 650 are the in-plan retardation values of the film as measured at a wavelength of 450 nm, 550 nm and 650 nm, respectively.
  • a “Reverse NRZ film” is a film that satisfies the following conditions:
  • the in-plane retardation (“R e ”) is in the range of from about 100 nm to about 300 nm as measured at 589 nm
  • out-plane retardation (“R th ”) is in the range of from about ⁇ 50 nm to about 0 nm
  • R e 450/R e 550 is less than 1
  • R e 650/R e 550 is greater than 1, wherein R e 450, R e 550, and R e 650 are the in-plan retardation values of the film as measured at a wavelength of 450 nm, 550 nm and 650 nm, respectively.
  • n x , n y , and n z are refractive indexes of the film in the x, y, and z directions, respectively, and d is the film thickness.
  • a variable chosen from A, B and C means that the variable can be A alone, B alone, or C alone.
  • a variable A, B, or C means that the variable can be A alone, B alone, C alone, A and B in combination, B and C in combination, A and C in combination, or A, B, and C in combination.
  • cellulose esters prepared by the methods of this invention are useful in a variety of applications. Those skilled in the art will understand that the specific application will depend upon the specific type of cellulose ester as factors such as the type of acyl substituent, DS, MW, and type of cellulose ester copolymer significantly impact cellulose ester physical properties. Prog. Polym. Sci. 2001, 26, 1605-1688.
  • the cellulose esters are used in coating applications.
  • coating applications include but, are not limited to, automotive, wood, plastic, or metal coatings.
  • preferred cellulose esters for use in coating applications include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, or a mixture thereof.
  • the cellulose esters are used in applications involving solvent casting of film.
  • these applications include photographic film and protective and compensation films for liquid crystalline displays.
  • preferred cellulose ester for use in solvent cast film applications include cellulose triacetate, cellulose acetate, cellulose propionate, and cellulose acetate propionate.
  • the cellulose esters of the present invention can be used in applications involving solvent casting of film.
  • applications include photographic film, protective film, and compensation film for LCDs.
  • cellulose esters suitable for use in solvent cast film applications include, but are not limited to, cellulose triacetate, cellulose acetate, cellulose propionate, and cellulose acetate propionate.
  • films are produced comprising cellulose esters of the present invention and are used as protective and compensation films for LCD.
  • These films can be prepared by solvent casting as described in US 2009/0096962 or by melt extrusion as described in U.S. Pat. No. 8,344,134, both of which are incorporated in their entirety in this invention to the extent they do not contradict the statements herein.
  • the film When used as a protective film, the film is typically laminated to either side of an oriented, iodinated PVOH polarizing film to protect the PVOH layer from scratching and moisture, while also increasing structural rigidity.
  • compensation films When used as compensation films (or plates), they can be laminated with the polarizer stack or otherwise included between the polarizer and liquid crystal layers. These compensation films can improve the contrast ratio, wide viewing angle, and color shift performance of the LCD. The reason for this important function is that for a typical set of crossed polarizers used in an LCD, there is significant light leakage along the diagonals (leading to poor contrast ratio), particularly as the viewing angle is increased. It is known that various combinations of optical films can be used to correct or “compensate” for this light leakage. These compensation films must have certain well-defined retardation (or birefringence) values, which vary depending on the type of liquid crystal cell or mode used because the liquid crystal cell itself will also impart a certain degree of undesirable optical retardation that must be corrected.
  • Compensation films are commonly quantified in terms of birefringence, which is, in turn, related to the refractive index n.
  • the refractive index is approximately 1.46 to 1.50.
  • the refractive index will be the same regardless of the polarization state of the entering light wave.
  • the refractive index becomes dependent on material direction.
  • anisotropic e.g.
  • birefringence of the material for that particular combination of refractive indices.
  • the birefringence ⁇ e is a measure of the relative in-plane orientation between the MD and TD and is dimensionless. In contrast, ⁇ th gives a measure of the orientation of the thickness direction, relative to the average planar orientation.
  • Retardation is a direct measure of the relative phase shift between the two orthogonal optical waves and is typically reported in units of nanometers (nm). Note that the definition of R th varies with some authors, particularly with regards to the sign ( ⁇ ).
  • Materials are also known to vary with regards to 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. This follows because, on a molecular level, the refractive index is typically higher along the polymer chain's axis and lower perpendicular to the chain. These materials are commonly termed “positively birefringent” and represent most standard polymers including all current conventional cellulose esters.
  • intrinsic birefringence is a measure of the birefringence that would occur if the material was fully stretched with all chains perfectly aligned in one direction (for most polymers this is a theoretical limit since they can never be fully aligned). For purposes of the present invention, it also provides a measure of the sensitivity of a given polymer to a given amount of chain orientation. For example, a sample with high intrinsic birefringence is going to exhibit more birefringence during film formation than a sample with low intrinsic birefringence, even though the relative stress levels in the film are approximately the same.
  • Polymers can have positive, negative, or zero intrinsic birefringence.
  • Negative (intrinsic) birefringent polymers exhibit a higher refractive index perpendicular to the stretch direction (relative to the parallel direction), and consequently also have a negative intrinsic birefringence.
  • Certain styrenics and acrylics are known to have negative intrinsic birefringent behavior due to their rather bulky side groups.
  • some cellulose esters with aromatic ring structure exhibit negative intrinsic birefringence as well.
  • Zero intrinsic birefringence in contrast, is a special case and represents materials that show no birefringence with stretching and thus have a zero intrinsic birefringence. Such materials are ideal for optical applications as they can be molded, stretched, or otherwise stressed during processing without showing any optical retardation or distortion.
  • the actual compensation film(s) that is used in an LCD can take on a variety of forms including biaxial films where all three refractive indices differ and two optical axes exist, and uniaxial films having only one optical axis where two of the three refractive indices are the same.
  • There are also other classes of compensation films where the optical axes twist or tilt through the thickness of the film e.g. discotic films, but these are of lesser importance to understanding the present invention.
  • the important point is that the type of compensation film that can be made is limited by the birefringence characteristics of the polymer (i.e. positive, negative or zero intrinsic birefringence).
  • Compensation films or plates can take many forms depending upon the mode in which the LCD display device operates.
  • a C-plate compensation film is isotropic in the x-y plane, and the plate can be positive (+C) or negative ( ⁇ C).
  • n x n y ⁇ n z .
  • n x n y >n z .
  • A-plate compensation film which is isotropic in the y-z direction, and again, the plate can be positive (+A) or negative ( ⁇ A).
  • aliphatic cellulose esters provide values of R th ranging from about 0 to about ⁇ 350 nm at a film thickness of 60 ⁇ m.
  • the most important factors that influence the observed R th is type of substituent and the DS OH .
  • Film produced using cellulose mixed esters with very low DS OH had R th values ranging from about 0 to about ⁇ 50 nm.
  • U.S. Pat. No. 8,344,134 By significantly increasing DS OH of the cellulose mixed ester demonstrated that larger absolute values of R th ranging from about ⁇ 100 to about ⁇ 350 nm could be obtained.
  • Cellulose acetates typically provide R th values ranging from about ⁇ 40 to about ⁇ 90 nm depending upon DS OH .
  • the films must be stretched.
  • stretch conditions such as stretch temperature, stretch type (uniaxial or biaxial), stretch ratio, pre-heat time and temperature, and post-stretch annealing time and temperature the desired R e , and R th .
  • the precise stretching conditions depend upon the specific composition of the cellulose esters, the amount and type of plasticizer, and the glass transition temperature of that specific composition. Hence, the specific stretching conditions can vary widely.
  • the stretching temperature can range from 140° C. to 190° C.
  • the stretch ratio can range from 1.0 to 1.3 in the machine direction (MD) and can range from 1.1 to 1.8 in the TD.
  • the pre-heat time can range from 10 to 300 s, and the pre-heat temperature can be the same as the stretch temperature.
  • the post-annealing time can range from 0 to 300 s, and the post-annealing temperature can range from 10° C. to 40° C. below the stretching temperature.
  • Film thickness is depends upon the film thickness before stretching and upon the stretching conditions. After stretching, the preferred film thickness is from about 10 ⁇ m to about 200 ⁇ m. More preferred is when the film thickness is from about 20 ⁇ m to about 100 ⁇ m. Even more preferred is when the film thickness is from about 25 ⁇ m to about 70 ⁇ m.
  • the present invention discloses a regioselectively substituted cellulose ester comprising: (i) a plurality of R 1 —CO— substituents; and (ii) a plurality of hydroxyl substituents, wherein the degree of substitution of R 1 —CO— at the C2 position (“C2DS R1 ”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R 1 —CO— at the C3 position (“C3DS R1 ”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of hydroxyl is in the range of from about 0 to about 2.6, and wherein R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalky
  • the degree of substitution of hydroxyl is in the range of from about 0.5 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.1 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.2 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.3 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.4 to about 2.6.
  • the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 5,000 Da to about 250,000 Da. In one embodiment of the regioselectively substituted cellulose ester, the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 25,000 Da to about 250,000 Da. In one embodiment of the regioselectively substituted cellulose ester, the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 50,000 Da to about 250,000 Da.
  • the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one embodiment of the regioselectively substituted cellulose ester, the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one embodiment of the regioselectively substituted cellulose ester, the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one class of this embodiment, the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“Mw”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.3.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.1.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.08
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.06.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.04.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is (C 1-20 )alkyl. In one embodiment of the regioselectively substituted cellulose ester, R 1 is halo(C 1-20 )alkyl. In one embodiment of the regioselectively substituted cellulose ester, R 1 is (C 2-20 )alkenyl. In one embodiment of the regioselectively substituted cellulose ester, R 1 is (C 3-7 )cycloalkyl.
  • R 1 is (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, wherein R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 1 is a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups, R 3 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the regioselectively substituted cellulose ester further comprises a plurality of R 4 —CO— substituents, wherein the degree of substitution of R 4 —CO— at the C6 position (“C6DS R4 ”) is in the range of from about 0.1 to about 1.0, wherein R 4 is chosen from (C 1-20 )alkyl; halo(C 1-5 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 5 groups; or monocyclic or bicyclic heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 6 groups, R 5 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, wherein the degree of substitution of R 4 —CO— at the C
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.5.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.4, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.4.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.3, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.3.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.2, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.2.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da.
  • the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • R 4 is (C 1-20 )alkyl. In one class of this embodiment, R 4 is halo(C 1-5 )alkyl.
  • R 4 is (C 2-20 )alkenyl.
  • R 4 is (C 3-7 )cycloalkyl.
  • R 4 is (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 5 groups, wherein R 5 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 4 is a monocyclic or bicyclic heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 6 groups, and R 6 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 4 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • R 4 is methyl.
  • R 4 is ethyl.
  • R 4 is propyl.
  • R 4 is 1-ethyl-pentyl-.
  • R 4 is phenyl.
  • R 4 is 3,4,5-trimethoxylphenyl.
  • R 4 is 2-naphthyl.
  • R 4 is benzothiophenyl.
  • R 4 is heptadecanyl.
  • the C6DS R1-CO- is less than 0.1. In one embodiment, the C6DS R1-CO- is less than 0.08. In one embodiment, the C6DS R1-CO- is less than 0.06. In one embodiment, the C6DS R1-CO- is less than 0.05. In one embodiment, the C6DS R1-CO- is less than 0.04. In one embodiment, the C6DS R1-CO- is less than 0.02.
  • R 1 —CO— is chosen from acetyl, propionyl, butanoyl, benzoyl, naphthoyl, 3,4,5-trimethoxybenzoyl, biphenyl-CO—, benzoyl-benzoyl, or benzothiophenyl-CO—.
  • R 1 —CO— is propionyl.
  • the degree of substitution for the propionyl i.e., R 1 —CO— is propionyl
  • the degree of substitution for the propionyl is from about 1.0 to about 1.4
  • the degree of substitution for propionyl at the C2 position (“C2DS Pr ”) is from 0.6 to 0.9
  • the degree of substitution for propionyl at the C3 position (“C3DS Pr ”) is from about 0.3 to about 0.5.
  • the degree of substitution for propionyl at the C6 position (“C6DS Pr ”) is less than 0.05.
  • R 1 —CO— is a combination comprising benzoyl and naphthoyl.
  • the degree of substitution of benzoyl is from about 0.2 to about 1.2, and the degree of substitution for naphthoyl is from about 0.8 to about 1.8.
  • the degree of substitution of benzoyl is from about 0.4 to about 0.8
  • the degree of substitution of naphthoyl is from about 1.2 to about 1.6
  • the degree of substitution at the C6 position for the combined benzoyl and naphthoyl is less than 0.05.
  • R 1 —CO— is a combination comprising propionyl and a (C 6-20 )aryl.
  • the degree of substitution at the C6 position for combined propionyl and a (C 6-20 )aryl is less than 0.1.
  • R 1 —CO— is a combination comprising propionyl and benzoyl.
  • the degree of substitution of propionyl is from about 0.4 to about 0.7
  • the degree of substitution of benzoyl is from about 0.2 to about 0.5
  • the degree of substitution at the C6 position for combined propionyl and benzoyl is less than 0.05.
  • the degree of substitution of propionyl is from about 1.1 to about 1.8
  • the degree of substitution of benzoyl is from about 0.1 to about 0.5
  • the degree of substitution at the C6 position for combined propionyl and benzoyl is less than 0.05.
  • R 1 —CO— is a combination comprising propionyl and naphthoyl.
  • the degree of substitution for propionyl is in the range of from 0.2 to 0.9
  • the degree of substitution for naphthoyl is in the range of from 0.4 to 1.4.
  • R 1 —CO— is a combination comprising propionyl or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen.
  • the degree of substitution for propionyl is in the range of from 0.2 to 0.4
  • the degree of substitution for naphthoyl is in the range of from 0.9 to 1.1.
  • R 1 —CO— is a combination comprising propionyl and a (C 6-20 )alkyl-CO—.
  • R 1 —CO— is a combination comprising acetyl and a (C 6-20 )aryl-CO—.
  • the degree of substitution of acetyl is from about 0.7 to about 0.9
  • the degree of substitution of (C 6-20 )aryl-CO— is from about 0.1 to about 0.5
  • the degree of substitution at the C6 position for combined acetyl and (C 6-20 )aryl-CO— is less than 0.1.
  • R 1 —CO— is a combination comprising acetyl and a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen.
  • the degree of substitution of acetyl is from about 0.8 to about 1.1
  • the degree of substitution of 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen is from about 0.1 to about 0.3
  • the degree of substitution at the C6 position for combined acetyl and benzoyl is less than 0.1.
  • the present application also discloses a regioselectively substituted cellulose ester comprising: (i) a plurality of R 1 —CO— substituents; (ii) a plurality of R 4 —CO— substituents; (iii) a plurality of hydroxyl substituents, wherein the degree of substitution of R 1 —CO— at the C2 position (“C2DS R1 ”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R 1 —CO— at the C3 position (“C3DS R1 ”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R 4 —CO— at the C6 position (“C6DS R4 ”) is in the range of from about 0.1 to about 1.0, wherein the degree of substitution of hydroxyl is in the range of from
  • the degree of substitution of hydroxyl is in the range of from about 0.5 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.1 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.2 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.3 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.4 to about 2.6.
  • R 1 —CO— is chosen from acetyl, propionyl, butanoyl, benzoyl, naphthoyl, 3,4,5-trimethoxybenzoyl, biphenyl-CO—, benzoyl-benzoyl-, or benzothiphene-CO—; and wherein R 4 —CO— is chosen from acetyl, propionyl, butyryl, benzoyl, acetyl, naphthoyl, 3,4,5-trimethoxybenzoyl, biphenyl-CO—, benzoyl-benzoyl-, or benzothiphene-CO—.
  • the C6DS R1-CO- is less than 0.1. In one embodiment, the C6DS R1-CO- is less than 0.08. In one embodiment, the C6DS R1-CO- is less than 0.06. In one embodiment, the C6DS R1-CO- is less than 0.05. In one embodiment, the C6DS R1-CO- is less than 0.04. In one embodiment, the C6DS R1-CO- is less than 0.02.
  • R 1 —CO— is propionyl
  • R 4 —CO— is a (C 6-20 )aryl-CO—.
  • R 4 —CO— is a combination of pivaloyl and (C 6-20 )aryl-CO—.
  • (C 6-20 )aryl-CO— is chosen from benzoyl and naphthoyl.
  • the degree of substitution for the pivaloyl is from 0.6 to 0.9; and the degree of substitution for the (C 6-20 )aryl-CO— is from 0.2 to 0.5.
  • the degree of substitution for propionyl is from about 1.0 to about 1.4, the degree of substitution at the C2 position for propionyl is from 0.6 to 0.9, the degree of substitution at the C3 for propionyl is from about 0.3 to about 0.5.
  • the degree of substitution at the C6 position for propionyl is less than 0.05. In one sub-subclass of this subclass, the degree of substitution for the pivaloyl is from 0.6 to 0.9; and the degree of substitution for the (C 6-20 )aryl-CO— is from 0.2 to 0.5.
  • R 4 —CO— is a (C 6-20 )aryl-CO—.
  • R 4 —CO— is a combination of pivaloyl and (C 6-20 )aryl-CO—.
  • (C 6-20 )aryl-CO— is chosen from benzoyl and naphthoyl.
  • the degree of substitution for the pivaloyl is from 0.6 to 0.9; and the degree of substitution for the (C 6-20 )aryl-CO— is from 0.2 to 0.5.
  • the degree of substitution at the C6 position for propionyl is less than 0.05.
  • the degree of substitution for the pivaloyl is from 0.6 to 0.9; and the degree of substitution for the (C 6-20 )aryl-CO— is from 0.2 to 0.5.
  • R 1 —CO— is a combination comprising benzoyl and naphthoyl.
  • R 4 —CO— is (C 1-6 )alkyl-CO—.
  • the degree of substitution of benzoyl is from about 0.2 to about 1.2, wherein the degree of substitution for naphthoyl is from about 0.8 to about 1.8, and wherein the degree of substitution for the (C 1-6 )alkyl-CO— is less than 0.5.
  • R 4 —CO— is propionyl
  • R 1 —CO— is a combination of propionyl and benzoyl.
  • R 4 —CO— is a combination of propionyl and benzoyl.
  • the combined degree of substitution at the combined C2 and C3 positions for benzoyl is from 0.1 to 0.6
  • the degree of substitution at the combined C2 and C3 positions for propionyl is from 0.5 to 1.4
  • the degree of substitution at the C6 position for benzoyl is from 0 to 0.8
  • the degree of substitution for propionyl is from 0 to 1.0.
  • the degree of substitution at the C6 for benzoyl is from 0.1 to 0.2, and wherein the C6 degree of substitution at the C6 for propionyl is from 0.4 to 0.8.
  • the combined degree of substitution at the combined C2 and C3 positions for benzoyl is from 0.05 to 2.0
  • the degree of substitution at the combined C2 and C3 positions for propionyl is from 0.5 to 1.4
  • the degree of substitution at the C6 position for benzoyl is from 0 to 0.8
  • the degree of substitution for propionyl is from 0 to 1.0.
  • the degree of substitution at the C6 for benzoyl is from 0.1 to 0.2, and wherein the C6 degree of substitution at the C6 for propionyl is from 0.4 to 0.8.
  • the combined degree of substitution at the combined C2 and C3 positions for benzoyl is from 0.6 to 2.0
  • the degree of substitution at the combined C2 and C3 positions for propionyl is from 0.5 to 1.4
  • the degree of substitution at the C6 position for benzoyl is from 0 to 0.8
  • the degree of substitution for propionyl is from 0 to 1.0.
  • the degree of substitution at the C6 for benzoyl is from 0.1 to 0.2, and wherein the C6 degree of substitution at the C6 for propionyl is from 0.4 to 0.8.
  • the present application also discloses a regioselectively substituted trifluoroacetyl cellulose ester comprising:
  • the C2DS TFA is from about 0 to about 0.05, and the C3DS TFA is from about 0 to about 0.05. In one class of the embodiment, the C2DS TFA is from about 0 to about 0.02, and the C3DS TFA is from about 0 to about 0.02. In one class of the embodiment, the C2DS TFA is from about 0 to about 0.01, and the C3DS TFA is from about 0 to about 0.02.
  • the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 50,000 Da to about 250,000 Da. In one class of this embodiment, the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 50,000 Da to about 150,000 Da.
  • the present application discloses a film comprising a cellulose ester comprising: (i) a plurality of R 1 —CO— substituents; (ii) a plurality of R 4 —CO-substituents; (iii) a plurality of hydroxyl substituents, wherein the degree of substitution of R 1 —CO— at the C2 position (“C2DS R1 ”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R 1 —CO— at the C3 position (“C3DS R1 ”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R 4 —CO— at the C6 position (“C6DS R4 ”) is in the range of from about 0.1 to about 1.0, wherein the degree of substitution of hydroxyl is in the range of from about
  • the degree of substitution of hydroxyl is in the range of from about 0.5 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.1 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.2 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.3 to about 2.6. In one embodiment, wherein the degree of substitution of hydroxyl is in the range of from about 0.4 to about 2.6.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 5,000 Da to about 250,000 Da. In one embodiment of the regioselective cellulose ester, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 25,000 Da to about 250,000 Da. In one embodiment of the regioselective cellulose ester, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 50,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one embodiment of the regioselective cellulose ester, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one embodiment of the regioselective cellulose ester, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one class of this embodiment, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.3.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.1.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.08.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.06.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • the degree of substitution of R 1 —CO— at the C6 position (“C6DS R1 ”) is in the range of from about 0 to about 0.04.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from a (C 1-20 )alkyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • M w weight average molecular weight of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 80,000 Da to about 150,000 Da.
  • the weight average molecular weight (“M w ”) of the regioselectively substituted cellulose ester is in the range of from about 100,000 Da to about 150,000 Da.
  • R 1 is (C 1-20 )alkyl. In one embodiment of the compositions of matter, R 1 is halo(C 1-20 )alkyl. In one embodiment of the composition, R 1 is (C 2-20 )alkenyl. In one embodiment of the compositions of matter, R 1 is (C 3-7 )cycloalkyl.
  • R 1 is (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, wherein R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 1 is a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups, R 3 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups.
  • R 1 is chosen from a (C 1-20 )alkyl, halo(C 1-20 )alkyl, or an (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups, and R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 1 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl.
  • the regioselectively substituted cellulose ester further comprises a plurality of R 4 —CO— substituents, wherein the degree of substitution of R 4 —CO— at the C6 position (“C6DS R4 ”) is in the range of from about 0.1 to about 1.0, wherein R 4 is chosen from (C 1-20 )alkyl; halo(C 1-5 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 5 groups; or monocyclic or bicyclic heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 6 groups, R 5 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy,
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.5.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.4, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.4.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.3, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.3.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the degree of substitution of R 4 —CO— at the C2 position (“C2DS R4 ”) is in the range of from about 0 to about 0.2, wherein the degree of substitution of R 4 —CO— at the C3 position (“C3DS R4 ”) is in the range of from about 0 to about 0.2.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da. In one subclass of this class, the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 250,000 Da.
  • the weight average molecular weight (“M w ”) is in the range of from about 80,000 Da to about 100,000 Da.
  • the weight average molecular weight (“M w ”) is in the range of from about 100,000 Da to about 250,000 Da.
  • R 4 is (C 1-20 )alkyl. In one class of this embodiment, R 4 is halo(C 1-5 )alkyl.
  • R 4 is (C 2-20 )alkenyl.
  • R 4 is (C 3-7 )cycloalkyl.
  • R 4 is (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 5 groups, wherein R 5 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 4 is a monocyclic or bicyclic heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 6 groups, and R 6 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • R 4 is chosen from methyl, ethyl, propyl, 1-ethyl-pentyl-, phenyl, 3,4,5-trimethoxylphenyl, 2-naphthyl, benzothiophenyl, or heptadecanyl. In one subclass of this class, R 4 is methyl.
  • R 4 is ethyl. In one subclass of this class, R 4 is propyl. In one subclass of this class, R 4 is 1-ethyl-pentyl-. In one subclass of this class, R 4 is phenyl. In one subclass of this class, R 4 is 3,4,5-trimethoxylphenyl. In one subclass of this class, R 4 is 2-naphthyl. In one subclass of this class, R 4 is benzothiophenyl. In one subclass of this class, R 4 is heptadecanyl.
  • the film is a uniaxial or biaxial optical film. In one class of this embodiment, the film is a uniaxial optical film. In one class of this embodiment, the film is a biaxial optical film.
  • the film has a birefringence (“An”) between about 0.007 to about 0.010 as measured at a wavelength of 589 nm. In one embodiment, the film has a ⁇ n between about 0.008 to about 0.010 as measured at a wavelength of 589 nm. In one embodiment, the film has a ⁇ n between about 0.009 to about 0.010 as measured at a wavelength of 589 nm.
  • An birefringence
  • the film has a percent haze of less than about 0.9. In one embodiment, the film has a percent haze of less than about 0.8. In one embodiment, the film has a percent haze of less than about 0.7. In one embodiment, the film has a percent haze of less than about 0.6. In one embodiment, the film has a percent haze of less than about 0.5. In one embodiment, the film has a percent haze of less than 0.4. In one embodiment, the film has a percent haze of less than about 0.3. In one embodiment, the film has a percent haze of less than about 0.2.
  • the film is a C+ film, C ⁇ film, an 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 an A+ film. In one class of this embodiment, the film is an A ⁇ film. In one class of this embodiment, the film is an A ⁇ film.
  • the film is a C+ film, a C ⁇ film, a reverse A film, or a NRZ film.
  • the film in one class of this embodiment, is a C+ film.
  • the film has an out-of-plane retardation (“R th ”) as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) is in the range of from 0 to about 20.
  • R th out-of-plane retardation
  • d thickness of the film
  • the film is a C ⁇ film.
  • the film has an of the out-of-plane retardation (“R th ”) as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) is in the range of from 0 to about ⁇ 12.
  • the film is uniaxially, biaxially, or 45 degree stretched.
  • the film has an of the out-of-plane retardation (“R th ”) as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) is in the range of from 0 to about ⁇ 17.
  • the film is uniaxially, biaxially, or 45 degree stretched.
  • the film has an of the out-of-plane retardation (“R th ”) as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) is in the range of from ⁇ 2 to about ⁇ 17.
  • the film is uniaxially, biaxially, or 45 degree stretched.
  • the film has an of the out-of-plane retardation (“R th ”) as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) is in the range of from ⁇ 5 to about ⁇ 17.
  • the film is uniaxially, biaxially, or 45 degree stretched.
  • the film is a reverse A film.
  • the film satisfies the relations of R e 450/R e 550 ⁇ 1 and R e 650/R e 550>1, wherein R e 450, R e 550, and R e 650 are the in-plane retardations as measured at the wavelengths of 450 nm, 550 nm, and 650 nm, respectively.
  • the film the in-plane retardation (“R e ”) of the film as measured at the wavelength of 589 nm is in the range of from about 100 nm to about 300 nm.
  • the film is uniaxially, biaxially, or 45 degree stretched.
  • the film is a NRZ film.
  • the film satisfies the relations of R e 450/R e 550 ⁇ 1 and R e 650/R e 550>1, wherein R e 450, R e 550, and R e 650 are the in-plane retardations as measured at the wavelengths of 450 nm, 550 nm, and 650 nm, respectively.
  • the film the in-plane retardation (“R e ”) of the film as measured at the wavelength of 589 nm is in the range of from about 100 nm to about 300 nm.
  • the out-of-plane retardation (“R e ”) of the film is in the range of from about 0 nm to about ⁇ 50 nm as measured at the wavelength of 589 nm.
  • the film is uniaxially, biaxially, or 45 degree stretched.
  • the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 50 to 50. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 50 to 0. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 50. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 20 to 20.
  • the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 20 to 0. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 20. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 15 to 15. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 15 to 0.
  • the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 15. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 10 to 10. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 10 to 0. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 10.
  • the previously disclosed films have an R th nm in the range of from ⁇ 5 to 0. In one embodiment, the previously disclosed films have an R th nm in the range of from ⁇ 5 to 0. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 5. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 3 to 3. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 3 to 0.
  • the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 3. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 1 to 1. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 1 to 0. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 1.
  • the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 0.5 to 0.5. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from ⁇ 0.5 to 0. In one embodiment, the previously disclosed films have an R th as measured at a wavelength of 589 nm divided by the thickness of the film (“d”) in the range of from 0 to 0.5.
  • any of the above-described films can have a thickness in the range of from about 40 to about 120 ⁇ m, in the range of from about 40 to about 70 ⁇ m, or in the range of from about 5 to about 20 ⁇ m. Thickness and average thickness are used interchangeably in this application. As used herein, “average thickness” shall denote an average of at least three evenly-spaced measurements of the optical film's thickness.
  • additives such as plasticizers, stabilizers, UV absorbers, antiblocks, slip agents, lubricants, dyes, pigments, retardation modifiers, etc. may be mixed with the regioselectively substituted cellulose esters used in preparing the above-described optical films.
  • additives can be found, for example, in U.S. Patent Application Publication Nos. US 2009/0050842, US 2009/0054638, and US 2009/0096962, the contents of which are incorporated herein by reference.
  • any of the above-described optical films can be made by solvent casting, melt extrusion, lamination, or a coating process. These procedures are generally known in the art. Examples of solvent casting, melt extrusion, lamination, and coating methods can be found, for example, in U.S. Patent Application Publication Nos. US 2009/0050842, US 2009/0054638, and US 2009/0096962, the contents of which are incorporated herein by reference. Further examples of solvent casting, melt extrusion, lamination, and coating methods to form films can be found, for example, in U.S. Pat. Nos. 4,592,885 and 7,172,713, and U.S. Patent Application Publication Nos. US 2005/0133953 and US 2010/0055356, the contents of which are incorporated herein by reference.
  • the films can be stretched.
  • stretch conditions such as stretch temperature, stretch type (uniaxial or biaxial), stretch ratio, pre-heat time and temperature, and post-stretch annealing time and temperature, the desired R e , and R th .
  • the precise stretching conditions may depend upon the specific composition of the regioselectively substituted cellulose ester, the amount and type of plasticizer, and the glass transition temperature of that specific composition. Hence, the specific stretching conditions can vary widely. In various embodiments, the stretching temperature can be in the range of from about 160 to about 210° C.
  • the stretch ratio based on 1.0 in the machine direction (“MD”) can range from about 1.3 to about 2.0 in the transverse direction (“TD”).
  • the pre-heat time can be in the range of from about 10 to about 300 seconds, and the pre-heat temperature can be the same as the stretch temperature.
  • the post-annealing time can range from about 0 to about 300 seconds, and the post-annealing temperature can range from about 10 to about 40° C. below the stretching temperature.
  • Film thickness may depend upon the film thickness before stretching and upon the stretching conditions. After stretching, the film thickness can be from about 1 ⁇ m to about 500 ⁇ m, from about 5 ⁇ m to about 200 ⁇ m, or from about 10 ⁇ m to about 120 ⁇ m.
  • the films prepared from the regioselectively substituted cellulose esters described herein have other valuable features. Many conventional cellulose esters used in LCD displays have relatively high moisture uptake which affects dimensional stability and results in changing optical values of the film. Films prepared from the regioselectively substituted cellulose esters described herein have low moisture uptake, and the optical values of the film change very little at high humidity and temperature.
  • the regioselectively substituted cellulose esters can contain less than 2 weight percent moisture, less than 1 weight percent moisture, or less than 0.5 weight percent moisture.
  • the change in R e for the cellulose ester film can be less than 4 percent, less than 1 percent, or less than 0.5 percent when stored at 60° C., 100 percent relative humidity for 240 hours.
  • regioselectively substituted cellulose esters described herein are surprisingly thermally stable which makes them very useful in melt extrusion of film.
  • one aspect of the present invention relates to regioselectively substituted cellulose esters that have less than 10 percent weight loss by thermogravimetric analysis at 330° C., 340° C., or 350° C.
  • the optical films described herein can be employed in LCDs.
  • the above-described optical films can be employed as part or all of a compensation film in the polarizer stack of an LCD.
  • polarizer stacks generally include two crossed polarizers disposed on either side of a liquid crystal layer. Compensation films can be disposed between the liquid crystal layer and one of the polarizers.
  • the above-described single layer optical film can be employed by itself as a compensation film (i.e., a waveplate) in an LCD.
  • the single layer optical film can be disposed between the liquid crystal layer and one of the polarizing filters of the LCD.
  • the above-described ⁇ A optical film can be employed in a compensation film (i.e., a waveplate) in an LCD.
  • the ⁇ A optical film can be disposed adjacent to at least one additional optical film, where such additional optical film can be a ⁇ C optical film.
  • the above-described +C optical film can be employed in a compensation film (i.e., a waveplate) in an LCD.
  • the +C optical film can be disposed adjacent to at least one additional optical film, where such additional optical film can be a +A optical film.
  • LCDs prepared comprising the optical films described herein can operate in in-plane-switching (“IPS”) mode.
  • IPS in-plane-switching
  • the optical compensation film described herein can also be employed in OLED.
  • a QWP combined with a linear polarizer to form a circular polarizer.
  • the circular polarizer When the circular polarizer is put in front of an OLED device, it can reduce the ambient light reflected from OLED metal electrodes to improved viewing quality, such as high contrast ratio and less color shift, especially when the QWP has a reverse dispersion close to ideal.
  • a single quarter waveplate can be prepared comprising one or more of the above-described optical films of the present invention, which can be used to convert linear polarized light to circular polarized light.
  • This aspect may be particularly valuable for use in circular-polarized 3-dimensional (“3-D”) glasses and/or 3-D media displays, such as televisions (“3-D TV”).
  • a single quarter waveplate can be prepared comprising the above-described single layer optical film.
  • a single quarter waveplate can be prepared comprising the above-described ⁇ A optical film.
  • Such quarter waveplates can be applied to the glass of a 3-D TV, such as above the polarizing stack.
  • such quarter waveplates can be applied to the glass of 3-D glasses.
  • the optical film can be applied so that the optical axis in one lens is perpendicular or substantially perpendicular to the optical axis of the other lens.
  • the result in 3-D glasses is that certain observed polarization is blocked in one lens but will pass through the other lens leading to the observed 3-D optical effect.
  • a quarter waveplate comprising one or more of the above-described optical films can be employed in conjunction with at least one additional polarizer, which can be a linear polarizer.
  • any of the disclosed films can be incorporated into a multilayer film.
  • the present application also relates to a multilayer film comprising any of the disclosed films of the present application.
  • the present application discloses a process for the preparation of a regioselectively substituted cellulose ester having a combined C2 and C3 degree of substitution (“(C2+C3)DS”) in the range of from about 0 to about 2.0, and a C6 degree of substitution (“C6DS”) of from about 0 to about 0.6,
  • TFAA trifluoroacetic anhydride
  • a suitable solvent for this process is any solvent that can dissolve or partially dissolve the starting cellulose or the formed cellulose esters in reaction to lead to the desired product.
  • the suitable solvent is trifluoroacetic acid.
  • the acyl substituent contributing to the (C2+C3)DS and the C6DS is an acyl substituent derived from the first carboxylic acid or any acylating compound.
  • the C6DS is less than 0.4. In one embodiment of this process, the C6DS is less than 0.2. In one embodiment of this process, the C6DS is less than 0.1. In one embodiment of this process, the C6DS is less than 0.08. In one embodiment of this process, the C6DS is less than 0.06. In one embodiment of this process, the C6DS is less than 0.04. In one embodiment of this process, the C6DS is less than 0.02.
  • acyl donor further comprising (2) adding 0.1 to 2.0 eq of one or more of an acyl donor, wherein the equivalents of the acyl donor is based on the sum total of anhydroglucosyl units of the cellulose.
  • the acyl donor is chosen from a second carboxylic acid or an anhydride. In one subclass of this class, the acyl donor is a second carboxylic acid. In one subclass of this class, the acyl donor is an anhydride.
  • the acyl donor is added after at least 50% of the first carboxylic acid is consumed.
  • the acyl donor is chosen from a second carboxylic acid or an anhydride.
  • the acyl donor is a second carboxylic acid.
  • the acyl donor is an anhydride.
  • the acyl donor is added after at least 80% of the first carboxylic acid is consumed.
  • the acyl donor is chosen from a second carboxylic acid or an anhydride.
  • the acyl donor is a second carboxylic acid.
  • the acyl donor is an anhydride.
  • the acyl donor is added after at least 90% of the first carboxylic acid is consumed.
  • the acyl donor is chosen from a second carboxylic acid or an anhydride.
  • the acyl donor is a second carboxylic acid.
  • the acyl donor is an anhydride.
  • the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 5,000 Da to about 250,000 Da. In one embodiment of this process, the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 25,000 Da to about 250,000 Da. In one embodiment of this process, the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 50,000 Da to about 250,000 Da.
  • the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 80,000 Da to about 250,000 Da. In one embodiment of this process, the regioselectively substituted cellulose ester has a weight average molecular weight (“M w ”) in the range of from about 100,000 Da to about 250,000 Da.
  • R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups,
  • R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro, and
  • R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups,
  • R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro, and
  • the cellulose is a softwood cellulose, a hardwood cellulose, cotton linter cellulose or a microcrystalline cellulose. In one embodiment of this process, the cellulose is Placetate F cellulose.
  • the reaction medium is set at a temperature in the range of from about 20° C. to about 80° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 35° C. to about 75° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 00° C. to about 20° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 30° C. to about 50° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 50° C. to about 80° C.
  • the present application discloses a process for the preparation of a regioselectively substituted cellulose ester having a C2 degree of substitution (“C2DS”) of from 0.01 to 1, a C3 degree of substitution (“C3DS”) of from 0.01 to 1, and a C6 degree of substitution (“C6DS”) of from about 0 to about 0.1,
  • C2DS C2 degree of substitution
  • C3DS C3 degree of substitution
  • C6DS C6 degree of substitution
  • TFAA trifluoroacetic anhydride
  • FAA first acylating agent
  • the acyl substituent contributing to the (C2+C3)DS and the C6DS is an acyl substituent derived from the FAA or any other acylating compound added to the reaction medium.
  • a suitable solvent for this process is any solvent that can dissolve or partially dissolve the starting cellulose or the formed cellulose esters in reaction to lead to the desired product.
  • the suitable solvent is trifluoroacetic acid.
  • the C6DS is less than 0.4. In one embodiment of this process, the C6DS is less than 0.2. In one embodiment of this process, the C6DS is less than 0.1. In one embodiment of this process, the C6DS is less than 0.08. In one embodiment of this process, the C6DS is less than 0.06. In one embodiment of this process, the C6DS is less than 0.04. In one embodiment of this process, the C6DS is less than 0.02.
  • the TFAA is present at 0.5 eq to about 5.0 eq. In one embodiment of this process, the TFAA is present at 0.5 eq to about 3.0 eq. In one embodiment of this process, the TFAA is present at 0.5 eq to about 2.0 eq. In one embodiment of this process, the TFAA is present at 1.0 eq to about 2.0 eq.
  • the one or more FAA is introduced after the introduction of the TFAA. In one class of this embodiment, the one or more FAA and the TFAA are added while dissolved in a suitable solvent. In one subclass of this class, the suitable solvent is trifluoroacetic acid. In one embodiment of this process, the one or more FAA is introduced before the introduction of the TFAA. In one class of this embodiment, the one or more FAA and the TFAA are added while dissolved in a suitable solvent. In one subclass of this class, the suitable solvent is trifluoroacetic acid. In one embodiment of this process, the one or more FAA and the TFAA are introduced at the same time. In one class of this embodiment, the one or more FAA and the TFAA are added while dissolved in a suitable solvent. In one subclass of this class, the suitable solvent is trifluoroacetic acid.
  • the FAA is chosen from an anhydride or an acid halide. In one embodiment of this process, the FAA is chosen from a symmetrical anhydride or a mixed anhydride. In a class of this embodiment, the mixed anhydride is generated in the reaction medium by the addition of a carboxylic acid. In one embodiment of this process, the FAA is an acid halide.
  • the FAA is R 1a —C(O)OC(O)—R 1b ,
  • R 1a and R 1b are independently chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups,
  • each R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro, and
  • the FAA is R 1a —C(O)X
  • R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups,
  • each R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro,
  • each R 3 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro, and
  • X is chloro, bromo, or iodo.
  • the cellulose is a hardwood cellulose, a softwood cellulose, cotton linter cellulose or a microcrystalline cellulose. In one embodiment of this process, the cellulose is Placetate F cellulose.
  • the reaction medium is set at a temperature in the range of from about 20° C. to about 80° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 35° C. to about 75° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 00° C. to about 20° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 30° C. to about 50° C. In one class of this embodiment, the reaction medium is set at a temperature in the range of from about 50° C. to about 80° C.
  • the present application discloses a process for the preparation of a regioselectively substituted cellulose ester
  • the acyl substituent contributing to the (C2+C3)DS and the C6DS is an acyl substituent derived from the FAA or any acylating compound added to the first reaction medium.
  • the first suitable solvent for this process is any solvent that can dissolve or partially dissolve the starting cellulose or the formed cellulose esters in reaction to lead to the desired product.
  • the first suitable solvent is trifluoroacetic acid.
  • the second suitable solvent for this process is any solvent that can dissolve or partially dissolve the starting cellulose or the formed cellulose esters in reaction and is inert to the reaction.
  • the second suitable solvent is chosen from methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, 1,3 dimethyl-2-imidazolidinone, dimethylacetamide, dioxane, dimethylformamide, ethyl acetate, butyl acetate, trichloromethane, pryridine, or dichloromethane.
  • the first suitable solvent is trifluoroacetic acid
  • the second suitable solvent is chosen from methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, 1,3 dimethyl-2-imidazolidinone, dimethylacetamide, dioxane, dimethylformamide, ethyl acetate, butyl acetate, trichloromethane, pyridine, or dichloromethane.
  • the C6DS is less than 0.08. In one embodiment of this process, the C6DS is less than 0.06. In one embodiment of this process, the C6DS is less than 0.04. In one embodiment of this process, the C6DS is less than 0.02.
  • the TFAA is present at 0.5 eq to about 8.0 eq. In one embodiment of this process, the TFAA is present at 0.5 eq to about 6.0 eq. In one embodiment of this process, the TFAA is present at 0.5 eq to about 4.0 eq. In one embodiment of this process, the TFAA is present at 0.5 eq to about 3.0 eq. In one embodiment, the TFAA is present at 0.5 eq to about 2.0 eq. In one embodiment of this process, the TFAA is present at 1.0 eq to about 2.0 eq.
  • the one or more FAA is introduced after the introduction of the TFAA in TFA. In one embodiment of this process, the one or more FAA is introduced before the introduction of the TFAA in TFA.
  • the one or more FAA and the TFAA in TFA are introduced at the same time.
  • the FAA is chosen from a symmetrical anhydride or a mixed anhydride. In one embodiment of this process, the FAA is an acid halide.
  • the cellulose is a hardwood cellulose, a softwood cellulose, cotton linter cellulose or a microcrystalline cellulose. In one embodiment of this process, the cellulose is Placetate F cellulose.
  • the first reaction medium is set at a temperature in the range of from about 20° C. to about 80° C. In one class of this embodiment, the first reaction medium is set at a temperature in the range of from about 35° C. to about 75° C. In one class of this embodiment, the first reaction medium is set at a temperature in the range of from about 00° C. to about 20° C. In one class of this embodiment, the first reaction medium is set at a temperature in the range of from about 30° C. to about 50° C. In one class of this embodiment, the first reaction medium is set at a temperature in the range of from about 50° C. to about 80° C.
  • the second reaction medium is set at a temperature in the range of from about 20° C. to about 80° C. In one class of this embodiment, the second reaction medium is set at a temperature in the range of from about 35° C. to about 75° C. In one class of this embodiment, the second reaction medium is set at a temperature in the range of from about 0° C. to about 20° C. In one class of this embodiment, the second reaction medium is set at a temperature in the range of from about 30° C. to about 50° C. In one class of this embodiment, the second reaction medium is set at a temperature in the range of from about 50° C. to about 80° C.
  • TFAA trifluoroacetic anhydride
  • R 1 is chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups,
  • R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro, and
  • R 3 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro.
  • TFAA trifluoroacetic anhydride
  • FAA first acylating agent
  • Embodiment 5 wherein the FAA is chosen from an anhydride or an acid halide.
  • R 1a and R 1b are independently chosen from (C 1-20 )alkyl; halo(C 1-20 )alkyl; (C 2-20 )alkenyl, (C 3-7 )cycloalkyl, (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R 2 groups; or a 5- to 20 membered heteroaryl containing 1 to 3 heteroatoms independently selected from oxygen, sulfur, and nitrogen, wherein the heteroaryl is unsubstituted or substituted by 1 to 6 R 3 groups,
  • each R 2 is chosen from (C 1-6 )alkyl, halo(C 1-6 )alkyl, (C 1-6 )alkoxy, halo(C 1-6 )alkoxy, halo, (C 3-7 )cycloalkyl, (C 6-10 )aryl, or nitro, and
  • a process for the preparation of a regioselectively substituted cellulose ester comprising:
  • the first suitable solvent is trifluoroacetic acid
  • the second suitable solvent is chosen from methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, 1,3 dimethyl-2-imidazolidinone, dimethylacetamide, dioxane, dimethylformamide, ethyl acetate, butyl acetate, trichloromethane, pyridine, or dichloromethane.
  • cellulose is a hardwood cellulose, softwood cellulose, cotton linter cellulose or microcrystalline cellulose.
  • C2DS is degree of substitution of the 2 position of the anydroglucose residue
  • C3DS is degree of substitution of the 3 position of the anhydroglucose residue
  • C6DS is the degree of substitution of the 6 position of the anydroglucose residue
  • CIC is combustion ion chromatography
  • d is deuterated or deuterium
  • Da is dalton
  • DCE is dichloroethane
  • DCM dichloromethane
  • DEP is diethyl phthalate
  • DMAc is N,N-dimethylacetamide
  • DMAP is 4-dimethylaminopyridine
  • DMSO-d6 is hexadeuterated dimethyl sulfoxide
  • min is minute; equiv or eq.
  • Et 2 O is ethyl ether
  • Ex is example; g is gram; GPC is gel permeation chromatography; h is hour; Int is intermediate; KOAc is potassium acetate; min is minute; M w is weight average molecular weight; M is molar; MEK is methyl ethyl ketone; MeOH is methanol; mg is milligram; MHz is megahertz; MIPK is methyl isopropyl ketone; mL or ml is milliliter; ⁇ L is microliter; mm is millimeter; mmHg is millimeters mercury; N 2 is nitrogen; NMR is nuclear magnetic resonance; Np is naphthyl; NpOH is 2-naphthoic acid; NpOH is 2-naphthoic acid; Np 2 O is 2-naphthoic anhydride; ppm is parts per million; Pr is propionyl; i PrOH is is isopropyl alcohol; Pr
  • NMR Characterization Proton NMR data were obtained on a JEOL Model Eclipse-600 NMR spectrometer operating at 600 MHz. The sample tube size was 5 mm, and the sample concentrations were ca. 20 mg/mL DMSO-d6. Each spectrum was recorded at 80° C. using 64 scans and a 15 second pulse delay. One to two drops of trifluoroacetic acid-d were added to each sample to shift residual water from the spectral region of interest. Chemical shifts are reported in ppm from tetramethylsilane with the center peak of DMSO-d 6 as an internal reference (2.49 ppm).
  • Quantitative 13 C NMR data were obtained on a JEOL Model GX-400 NMR spectrometer operating at 100 MHz.
  • the sample tube size was 10 mm, and the sample concentrations were ca. 100 mg/mL DMSO-d 6 .
  • Chromium(III) acetylacetonate was added to each sample at 5 mg/100 mg cellulose ester as a relaxation agent.
  • Each spectrum was typically recorded at 80° C. using 10000 scans and a 1 second pulse delay. Chemical shifts are reported in ppm from tetramethylsilane with the center peak of DMSO-d 6 as an internal reference (39.5 ppm).
  • the proton and carbon NMR assignments, the degree of substitution and the RDS of the various acyl groups of the cellulose esters were determined by adapting the procedures disclosed in US 2012/0262650.
  • the C2, C3, and C6 DS were determined by 13 C NMR.
  • the total DS for any substituent is determined by 1 H NMR.
  • Samples were prepared prepared by weighing 25 mg into a 2 dram screw cap vial and dissolving in 10 ml of the solvent. 10 microliters of toluene were added as a flow rate marker. The instrument was calibrated with a series of 14 narrow molecular weight polystyrene standards ranging from 580 to 3,750,000 in molecular weight. Instrument control and data collection/processing were carried out using Agilent GPC software version 1.2 build 3182.29519. For cellulose samples described in this report, Gel permeation chromatography analysis was performed in 70:30 N-methylpyrrolidinone/tributylmethylammonium dimethylphosphate by weight. The instrumentation consisted of an Agilent series 1100 liquid chromatography system.
  • the system components comprised a degasser, an isocratic pump with a flow rate set at 0.5 ml/min, an auto-sampler with an injection volume of 50 microliters, and a column oven set at 60° C. and a refractive index detector set at 40° C.
  • the column set consisted of an Agilent PLgel 10 micron guard (7.5 ⁇ 50 mm) and a Mixed-B (7.5 ⁇ 300 mm) column in series. Samples were prepared prepared by weighing 12.5 mg into a 2 dram screw cap vial and dissolving in 10 ml of the solvent. 10 ⁇ L of toluene were added as a flow rate marker.
  • the instrument was calibrated with a series of 14 narrow molecular weight polystyrene standards ranging from 580 to 3,750,000 in molecular weight. Instrument control and data collection/processing were carried out using Agilent GPC software version 1.2 build 3182.29519.
  • a solvent (DCM, 10% MeOH in DCM, 10% Acetone in DCM, 10% DCE in DCM, MEK, or MIPK) and the regioselective cellulose ester (8 to 12 wt %) and optionally a plasticizer (10 wt %, DEP or TPP) were mixed to make a dope.
  • films were cast onto glass using a knife applicator and dried either at room temperature, in the case of a DCM based dope or at 85° C. in a forced air oven for 10 min. for dopes made from MEK and MIPK based dopes.
  • the cast films were annealed at 100° C. and 120° C. in a forced air oven for 10 min each to remove the residual solvents.
  • the thickness of the films was measured using a Metricon Prism Coupler 2010 (Metricon Corp.) or PosiTector 6000.
  • the birefringence, optical dispersion and retardations were measured using a M-2000V Ellipsometer (J. A. Woollam Co.).
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the set-point was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt. %).
  • TFA 337 g
  • TFAA 41.9 g
  • the resulting solution was then slowly poured into the reactor.
  • the temperature controller was set to 60° C., and the material was mixed via overhead stirring for ⁇ 75 min.
  • the temperature controller was set to 50° C., and the reaction mixture was stirred for 35 min.
  • the reaction mixture was poured into a beaker containing 2000 mL anhydrous diethyl ether to precipitate the crude product.
  • the precipitate was dispersed to a uniform particle size using a homogenizer, and the resulting solids were collected by vacuum filtration.
  • the solids were rinsed on the filter with diethyl ether (2 ⁇ 200 mL) and subsequently dried under vacuum at room temperature to afford the title product.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C.
  • the reactor was charged with Alfa Aesar A17730 microcrystalline cellulose (10 g, 2.2 wt. %). To a separate 500 mL graduated cylinder was added TFA (297 g) followed by TFAA (149 g). The resulting solution was then slowly poured into the reactor. The material was mixed via overhead stirring at rt. After ⁇ 2-3 hours, the cellulose had fully dissolved, forming a clear, viscous solution.
  • Comparative Ex 1 shows that the Liebert procedure produces a cellulose ester with less selectivity at the C2 position, but more selectivity for the C3 position. Additionally, the M w of the final product is less than half that for Ex 1.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C.
  • the reactor was charged with Placetate F Cellulose Pulp (10 g, 2.2 wt. %). To a separate 500 mL graduated cylinder was added TFA (297 g) followed by TFAA (149 g). The resulting solution was then slowly poured into the reactor. The material was mixed via overhead stirring at rt. After 3 h, the cellulose was not fully dissolved, instead giving viscous, heterogeneous clumps.
  • Comparative Ex 2 illustrates that the Liebert procedure is ineffective in producing cellulose 6-trifluoroacetate from unmodified softwood pulps. Additionally, significant molecular weight degradation is not observed under these conditions.
  • the general procedure for determining the TFAA concentration is as follows. To a reaction vessel containing cellulose was added TFA and TFAA at rt, and the reaction was allowed to warm to 60° C. The mixture was stirred until complete dissolution of the cellulose occurred, and the temperature was lowered to 50° C. whereupon 2.00 equiv Ac 2 O (per anhydroglucose unit of cellulose) was added, and the mixture was allowed to stir overnight. Precipitation and polymer isolation gave the resulting cellulose acetates.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt. %).
  • TFA 337 g
  • TFAA 41.9 g
  • the resulting solution was then slowly poured into the reactor.
  • the temperature controller was set to 60° C., and the material was mixed via overhead stirring for ⁇ 75 min.
  • the temperature controller was set to 50° C., and the reaction mixture was stirred for 35 min.
  • Ac 2 O was (25.1 g, 2.00 equiv) added to the reaction mixture via an overhead addition funnel over 10 min.
  • the resulting mixture was stirred for 12 h.
  • the dope was then precipitated by pouring into 3000 mL deionized water to afford the crude product.
  • the crude product was broken down to a uniform particle size via homogenization.
  • the crude product were collected by filtration on a frit.
  • the crude product was then suspended in 2000 mL of 5 M KOAC (aq.) and slurried for 36 h.
  • the crude product was collected by filtration on a frit and washed continuously with denionized water for 8 h.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper.
  • the reactor was connected via rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the set-point was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt. %).
  • a TFA/TFAA solution was prepared by adding TFAA (42.7 g) to TFA (337 g). The TFA/TFAA solution was then slowly poured into the reactor. The temperature controller was set to 60° C., and the reaction mixture was mixed via overhead stirring (75 min). The set-point was then set to 50° C.
  • PrOH In a separate flask, PrOH (18.26 g, 2.0 equiv) and TFA (30 mL) were stirred under a N 2 atmosphere. To the PrOH/TFA solution was added TFAA (51.8 g, 2.0 eq), and the solution was stirred (45 min) to prepare a mixed anhydride mixture. The mixed anhydride mixture was added over 10 min via an overhead addition funnel, and the resulting reaction mixture was stirred for 12 h. The dope was then precipitated by pouring into deionized water (3000 mL) to afford the crude product. The crude product was broken down to a uniform particle size via homogenization.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper.
  • the reaction vessel was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the set-point was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt %).
  • a solution of TFA/TFFA was prepared by adding TFAA (41.9 g) to TFA (337 g). The TFA/TFAA solution was then slowly poured into the reactor. The temperature controller was set to 60° C., and the reaction mixture was stirred via overhead stirring for ⁇ 75 min.
  • the temperature controller was set to 50° C., and the reaction mixture was stirred for 35 min.
  • Pr 2 O (8.02 g. 0.5 eq) was slowly added to the reaction mixture via an overhead addition funnel.
  • Bz 2 O (41.9 g, 1.50 eq) was added to the reaction mixture portion-wise via a solids addition funnel. Both additions were complete after 10 min.
  • the reaction mixture was stirred for 12 h.
  • the dope was then precipitated by pouring into deionized water (3000 mL) to afford the crude product.
  • the crude product was broken down to a uniform particle size via homogenization.
  • the crude product was collected by filtration on a frit.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the set-point was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt. %).
  • TFA 337 g
  • TFAA 41.9 g
  • the resulting solution was then slowly poured into the reactor.
  • the temperature controller was set to 60° C., and the material was mixed via overhead stirring.
  • the stopcocks for each funnel were opened, and the liquids were added over a period of ⁇ 10 min.
  • the resulting mixture was stirred for 12 h.
  • the dope was then precipitated by pouring into deionized water (3000 mL) to afford the product as a white solid.
  • the solids were broken down to a uniform particle size via homogenization.
  • the solids were collected by filtration on a frit.
  • the crude product were then transferred to a cellulose thimble and extracted with MeOH for 7 h using a Soxhlet apparatus.
  • the crude product were then collected and suspended in 5 M KOAc (aq.) (2000 mL) and slurried for 36 h.
  • Table 8 provides the degree of substitution and molecular weight information for Ex 18-20.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt. %).
  • TFA 337 g
  • TFAA 42.7 g
  • the resulting solution was then slowly poured into the reactor.
  • the temperature controller was set to 60° C., and the material was mixed via overhead stirring.
  • the funnel was opened, and the anhydride solution was added to the cellulose dope such that the addition was complete within 10 min.
  • the resulting mixture was allowed to stir for 12 h.
  • the dope poured over deionized water (3000 mL) to afford the crude product.
  • the crude product was broken down to a uniform particle size via homogenization.
  • the crude product was collected by filtration on a frit.
  • the crude product was then transferred to a cellulose thimble and washed with MeOH for 7 h using a Soxhlet apparatus.
  • the crude product was then collected and suspended in 5 M KOAc (aq.) (2000 mL) and slurried for 36 h.
  • Table 10 provides the degree of substitution and molecular weight information for Ex 22-29, 62-65 and 76-81.
  • Acyl 1, Acyl 2, and Acyl 3 are the acyl substituents from acid 1, acid 2, and acid 3, respectively.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the set-point was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (20 g, 5 wt %).
  • TFA 337 g
  • TFAA 41.9 g
  • the resulting solution was then slowly poured into the reactor.
  • the temperature controller was set to 60° C., and the material was mixed via overhead stirring.
  • the solids were then transferred to a cellulose thimble and extracted with MeOH for 24 h using a Soxhlet apparatus. The solids were then collected and suspended in 5 M KOAc (aq.) (2000 mL) and stirred for 36 h. The solids were collected by filtration on a frit and washed continuously with denionized water for 8 h. The solids were then dried in vacuo (60° C.) for 12 h. Analysis: DS Np :1.4; DS Bz : 0.6; C2DS: 0.9; C3DS is 0.9; C6DS is 0.01; M w is 157,907 Da.
  • Table 13 provides the degree of substitution and molecular weight information for Ex 33-41.
  • a 1000 mL jacketed reaction kettle was fitted with a 4-neck removable top. To the top was affixed an overhead stirring shaft, a temperature probe, a reflux condenser, and a ground glass stopper. The reaction was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C.
  • the reactor was charged with Placetate F cellulose pulp (50 g, 5 wt. %).
  • TFA 843 g
  • TFAA (112 g
  • Table 15 provides the degree of substitution information, molecular weight and glass transition temperature information for Ex 44-57.
  • 2-naphthyl chloride (6.55 g, 0.4 equiv) was taken up into 15-20 mL DMAc with magnetic stirring. Once the 2-naphthyl chloride was completely dissolved, the solution was added to the dissolved cellulose over a period of ⁇ 2 minutes with vigorous stirring. The reaction mixture was allowed to stir at 20° C. for 3-4 hours. After this time period had passed, the reaction mixture was charged with pivaloyl chloride (9.31 g, 0.9 equiv) over a period of 2 minutes with vigorous stirring. Once the addition was complete, the temperature controller was set to 35° C., and the resulting solution was allowed to stir for at least 12 hours.
  • the reaction was then diluted with acetone (150 mL).
  • the resulting mixture was poured over deionized water (3000 mL), and the precipitated crude product was broken down to a uniform size via homogenization.
  • the resultant solids were collected via vacuum filtration on a coarse frit.
  • the crude product was washed on the filter with two portions of i PrOH (2 ⁇ 200 mL)
  • the crude product was then washed continuously with rt deionized water for 8 h.
  • the title compound was obtained after drying in vacuo (60° C.) for 12 h.
  • Table 17 provides degree of substitution, and molecular weight information for Ex 66-73, and 82-88.
  • the reaction temperature was adjusted to 25° C., and 2-benzothiophene carbony chloride (10.3 g, 0.6 equiv) was added over the course of about 2 minutes.
  • the reaction mixture was then allowed to hold for 3 hours, whereupon pivaloyl chloride (8.1 g, 0.77 equiv) was added dropwise over the course of 2 minutes.
  • the reaction mixture was then warmed to 40° C. and allowed to stir for at least 12 hours.
  • the resulting mixture was then diluted with 100 mL acetone and poured into a beaker containing 2000 mL deionized water, causing a white solid to precipitate.
  • the solids were broken down to a uniform size via homogenization, and the solids were collected via vacuum filtration on a coarse frit.
  • Table 19 provides the degrees of substitution for cellulose esters provided in Table 18.
  • Table 20 provides additional degree of substation information for Ex 98-103.
  • Table 21 provides degree of substitution information for Ex 104-109.
  • Table 22 provides the films prepared using the general procedure for the preparation of the films.
  • the following films shown in Table 23 were prepared by adapting the previously disclosed procedures.
  • the films were prepared from the solvent, MEK.
  • Table 24 provides additional properties for the films in Table 23.

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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10640577B2 (en) * 2016-04-22 2020-05-05 Eastman Chemical Company Regioselectively substituted cellulose esters and films made therefrom
WO2018183467A1 (fr) 2017-03-29 2018-10-04 Eastman Chemical Company Esters de cellulose substitués de manière régiosélective
EP3395942A1 (fr) * 2017-04-25 2018-10-31 IMBA-Institut für Molekulare Biotechnologie GmbH Organoïde bi ou multi-différencié
JP2019218468A (ja) * 2018-06-20 2019-12-26 株式会社ダイセル セルロースベンゾエート
JP2020094131A (ja) * 2018-12-13 2020-06-18 株式会社ダイセル セルロース誘導体とその成形体
JP2021008565A (ja) * 2019-07-01 2021-01-28 株式会社ダイセル 酢酸セルロース及び酢酸セルロースの製造方法
TWI879887B (zh) * 2020-02-13 2025-04-11 美商伊士曼化學公司 以經位向選擇取代的纖維素酯為主之具有改良波長色散之負雙折射補償膜
JP7566274B2 (ja) * 2020-06-02 2024-10-15 株式会社Lixil β－１，３－グルカンエステル誘導体及びβ－１，４－グルカンエステル誘導体
JP7655938B2 (ja) * 2020-10-21 2025-04-02 株式会社ダイセル セルロースアセテート及びセルロースアセテート組成物
WO2022168221A1 (fr) * 2021-02-04 2022-08-11 株式会社ダイセル Acylate de cellulose
CN113083039A (zh) * 2021-04-15 2021-07-09 中国农业大学 一种绿色高效制备玉米秸秆基三醋酸纤维素多孔膜的方法
JP2023147936A (ja) * 2022-03-30 2023-10-13 シャープディスプレイテクノロジー株式会社 液晶表示装置
CN116813804B (zh) * 2023-07-12 2025-04-11 四川大学 一种纤维素酯光学材料制备方法

Family Cites Families (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56162617A (en) 1980-05-20 1981-12-14 Fuji Photo Film Co Ltd Preparation of film
CA2070390C (fr) * 1990-03-19 1999-03-30 Charles M. Buchanan Procede pour la preparation d'esters cellulosiques
US5142034A (en) * 1990-04-16 1992-08-25 Eastman Kodak Company Cellulose ester compositions and process for the preparation thereof
WO1991016357A1 (fr) 1990-04-23 1991-10-31 Commonwealth Scientific And Industrial Research Organisation Derives de cellulose
ATE199383T1 (de) * 1990-11-30 2001-03-15 Eastman Chem Co Aliphatisch-aromatische copolyester
WO1993006153A1 (fr) * 1991-09-19 1993-04-01 Nauchno-Proizvodstvennoe Obiedinenie 'novye Tekhnologii Sibiri' Matiere lignocellulosique modifiee, son procede d'obtention et composition d'obtention d'un materiau composite
JPH0632801A (ja) * 1992-05-26 1994-02-08 Eastman Kodak Co セルロースエステルの製造方法
JPH0770201A (ja) * 1993-09-01 1995-03-14 Asahi Chem Ind Co Ltd 耐溶剤性の優れたセルロースエステルおよびその製造法
JPH0770202A (ja) * 1993-09-02 1995-03-14 Asahi Chem Ind Co Ltd セルロースエステルおよびその製造方法
JP3895801B2 (ja) * 1996-04-19 2007-03-22 ダイセル化学工業株式会社 溶解性の優れたセルロースエステル
JP3727755B2 (ja) * 1997-06-17 2005-12-14 富士写真フイルム株式会社 セルロースアセテートフイルム、その製造方法および偏光板保護膜
JPH1135601A (ja) * 1997-07-18 1999-02-09 Nippon Paper Ind Co Ltd エステルエーテル混合セルロース誘導体及びその製造法
JP2002179701A (ja) * 2000-12-15 2002-06-26 Fuji Photo Film Co Ltd セルロースアシレート
JP2002241512A (ja) * 2000-12-15 2002-08-28 Fuji Photo Film Co Ltd セルロースアシレートフイルム、写真材料および光学材料
US7595392B2 (en) * 2000-12-29 2009-09-29 University Of Iowa Research Foundation Biodegradable oxidized cellulose esters
JP4094819B2 (ja) * 2001-01-17 2008-06-04 富士フイルム株式会社 セルロースアシレートフイルムおよびその製造方法
JP4065696B2 (ja) * 2001-01-24 2008-03-26 富士フイルム株式会社 光学フイルム
JP2002265501A (ja) * 2001-03-14 2002-09-18 Fuji Photo Film Co Ltd セルロースアシレート溶液およびセルロースアシレートフイルムの製造方法
JP2002338601A (ja) * 2001-03-14 2002-11-27 Daicel Chem Ind Ltd セルロースアセテート
US7470384B2 (en) 2001-06-15 2008-12-30 Fujifilm Corporation Method of producing of cellulose ester film
JP4189160B2 (ja) * 2001-11-05 2008-12-03 ダイセル化学工業株式会社 セルロースアセテートのアセチル置換度の調整方法
JP4280486B2 (ja) 2002-11-25 2009-06-17 富士フイルム株式会社 溶液製膜方法
CN102276732B (zh) 2003-11-28 2016-01-20 伊士曼化工公司 纤维素共聚体和氧化方法
JP4108077B2 (ja) * 2004-09-22 2008-06-25 ダイセル化学工業株式会社 セルロースエステル及びその製造方法
JP4189372B2 (ja) * 2004-10-26 2008-12-03 富士フイルム株式会社 セルロースアセテート、セルロースアセテート溶液およびその調製方法
JP2007332292A (ja) * 2006-06-15 2007-12-27 Fujifilm Corp セルロース体、セルロース体フィルム、光学補償シート、偏光板、液晶表示装置
JP5073248B2 (ja) * 2006-08-30 2012-11-14 株式会社ダイセル セルロースアセテート及びその製造方法
JP4892313B2 (ja) * 2006-10-13 2012-03-07 富士フイルム株式会社 セルロース化合物、セルロースフィルム、光学補償シート、偏光板および液晶表示装置
US7919631B2 (en) 2007-02-14 2011-04-05 Eastman Chemical Company Production of ionic liquids
US9834516B2 (en) * 2007-02-14 2017-12-05 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom
US20090096962A1 (en) 2007-05-14 2009-04-16 Eastman Chemical Company Cellulose Esters with High Hyrdoxyl Content and Their Use in Liquid Crystal Displays
KR101545032B1 (ko) 2007-08-24 2015-08-17 이스트만 케미칼 컴파니 저복굴절을 갖는 혼합 셀룰로스 에스터 및 이로부터 제조된 필름
JP2009091542A (ja) * 2007-09-21 2009-04-30 Daicel Chem Ind Ltd セルロース混合アシレートの製造方法、及び新規なセルロース混合アシレート
JP2009091543A (ja) * 2007-09-21 2009-04-30 Daicel Chem Ind Ltd セルロースアセテート誘導体の製造方法、及び新規なセルロースアセテート誘導体
US8354525B2 (en) * 2008-02-13 2013-01-15 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
US9777074B2 (en) * 2008-02-13 2017-10-03 Eastman Chemical Company Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom
JP5507819B2 (ja) * 2008-06-19 2014-05-28 富士フイルム株式会社 セルロースエステルフィルム、偏光板および液晶表示装置
JP5222064B2 (ja) 2008-09-02 2013-06-26 富士フイルム株式会社 セルロースアシレート積層フィルム、その製造方法、偏光板および液晶表示装置
US8067488B2 (en) * 2009-04-15 2011-11-29 Eastman Chemical Company Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom
JP2011074113A (ja) * 2009-09-29 2011-04-14 Toray Ind Inc セルロース混合エステルおよびその製造方法
CN102387664B (zh) 2010-09-06 2013-10-09 富葵精密组件(深圳)有限公司 电路板印刷方法
US9975967B2 (en) * 2011-04-13 2018-05-22 Eastman Chemical Company Cellulose ester optical films
US20130063336A1 (en) * 2011-09-08 2013-03-14 Honda Motor Co., Ltd. Vehicle user interface system
WO2013063336A1 (fr) * 2011-10-25 2013-05-02 Virginia Tech Intellectual Properties, Inc. Esters de cellulose substitués de manière régiosélective et leurs procédés efficaces de préparation
US9939554B2 (en) * 2013-01-24 2018-04-10 Akron Polymer Systems, Inc. Wide-view optical film having reversed wavelength dispersion
CN104277122B (zh) * 2013-07-11 2016-08-10 南通醋酸纤维有限公司 溶于丙酮的纤维素酯的直接合成方法及其产品
WO2015019701A1 (fr) * 2013-08-09 2015-02-12 コニカミノルタ株式会社 Dérivé de cellulose, procédé pour le produire, film optique, plaque polarisante circulaire et dispositif d'affichage électroluminescent organique
KR20150050267A (ko) * 2013-10-31 2015-05-08 제일모직주식회사 셀룰로오스계 수지 및 그 제조방법
CN104788575B (zh) * 2014-01-16 2017-09-26 中国科学院化学研究所 一种含dopo结构的纤维素衍生物及其制备方法
EP3099682A1 (fr) * 2014-01-29 2016-12-07 Bayer Pharma Aktiengesellschaft Isothiazoles amino-substitués
JP2015224256A (ja) * 2014-05-26 2015-12-14 コニカミノルタ株式会社 セルロース誘導体の製造方法、置換セルロース誘導体の製造方法、光学フィルム、円偏光板及び有機エレクトロルミネッセンス表示装置
WO2015182445A1 (fr) * 2014-05-26 2015-12-03 コニカミノルタ株式会社 Procédé de production d'un dérivé de saccharide, dérivé de saccharide modifié et composition de dérivé de saccharide modifié
US10640577B2 (en) * 2016-04-22 2020-05-05 Eastman Chemical Company Regioselectively substituted cellulose esters and films made therefrom
WO2018183467A1 (fr) * 2017-03-29 2018-10-04 Eastman Chemical Company Esters de cellulose substitués de manière régiosélective

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