REGIOSELECTIVELY SUBSTITUTED CELLULOSE ESTERS

Abstract

The present application discloses regioselectively substituted cellulose esters, films made from the regioselectively substituted cellulose esters and methods for making the same. The regioselectively substituted cellulose esters are synthesized using trifluoroacetic anhydride and cellulose with various acyl donors or acyl donor precursors.

Claims

1. A regioselectively substituted cellulose ester comprising: (i) a plurality of R.sup.1—CO— substituents; (ii) a plurality of R.sup.4—CO— substituents; (iii) a plurality of hydroxyl substituents, wherein the degree of substitution of R.sup.1—CO— at the C2 position (“C2DS.sub.R1-CO”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R.sup.1—CO— at the C3 position (“C3DS.sub.R1-CO”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R.sup.1—CO— at the C6 position (“C6DS.sub.R1-CO”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R.sup.4—CO— at the C6 position (“C6DS.sub.R4-CO”) 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 0 to about 2.6, wherein R.sup.1 is (C.sub.6-20)aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.2 groups, and wherein R.sup.2 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro, wherein R.sup.4 is (C.sub.1-20)alkyl.

2. The regioselectively substituted cellulose ester of claim 1, wherein C6DS.sub.R1-CO— is less than 0.1.

3. The regioselectively substituted cellulose ester of claim 1, wherein the degree of substitution of R.sup.4—CO— at the C2 position (“C2DS.sub.R4-CO”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R.sup.4—CO— at the C3 position (“C3DS.sub.R4-CO”) is in the range of from about 0 to about 0.5.

4. The regioselectively substituted cellulose ester of claim 1, wherein R.sup.1—CO— is a combination comprising benzoyl and naphthoyl.

5. The regioselectively substituted cellulose ester of claim 4, wherein 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.

6. The regioselectively substituted cellulose ester of claim 1, wherein R.sup.4—CO— is propionyl.

7. The regioselectively substituted cellulose ester of claim 1, wherein the weight average molecular weight (“M.sub.w”) is in the range from about 50,000 Da to about 500,000 Da.

8. A regioselectively substituted cellulose ester comprising: (i) a plurality of R.sup.1—CO— substituents; (ii) a plurality of R.sup.4—CO— substituents; (iii) a plurality of hydroxyl substituents, wherein the degree of substitution of R.sup.1—CO— at the C2 position (“C2DS.sub.R1”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R.sup.1—CO— at the C3 position (“C3DS.sub.R1”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R.sup.1—CO— at the C6 position (“C6DS.sub.R1”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R.sup.4—CO— at the C6 position (“C6DS.sub.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 0 to about 2.6, wherein R.sup.1 is chosen from (C.sub.1-20)alkyl; halo(C.sub.1-20)alkyl; (C.sub.2-20)alkenyl, (C.sub.3-7)cycloalkyl, (C.sub.6-20)aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.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.sup.3 groups, wherein R.sup.2 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro, wherein R.sup.3 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro; wherein R.sup.4 is a combination of an (C.sub.1-20)alkyl and an (C.sub.6-20)aryl, and wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.5 groups, R.sup.5 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro.

9. The regioselectively substituted cellulose ester of claim 1, wherein C6DS.sub.R1-CO— is less than 0.1.

10. The regioselectively substituted cellulose ester of claim 1, wherein the degree of substitution of R.sup.4—CO— at the C2 position (“C2DS.sub.R4-CO”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R.sup.4—CO— at the C3 position (“C3DS.sub.R4-CO”) is in the range of from about 0 to about 0.5.

11. The regioselectively substituted cellulose ester of claim 1, wherein the weight average molecular weight (“M.sub.w”) is in the range from about 50,000 Da to about 500,000 Da.

12. A regioselectively substituted cellulose ester comprising: (i) a plurality of R.sup.1—CO— substituents; (ii) a plurality of R.sup.4—CO— substituents; (iii) a plurality of hydroxyl substituents, wherein the degree of substitution of R.sup.1—CO— at the C2 position (“C2DS.sub.R1”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R.sup.1—CO— at the C3 position (“C3DS.sub.R1”) is in the range of from about 0.2 to about 1.0, wherein the degree of substitution of R.sup.1—CO— at the C6 position (“C6DS.sub.R1”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R.sup.4—CO— at the C6 position (“C6DS.sub.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 0 to about 2.6, wherein R.sup.1 is a combination of propionyl and an (C.sub.6-20)aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.2 groups, wherein R.sup.2 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro, wherein R.sup.4 is chosen from (C.sub.1-20)alkyl; halo(C.sub.1-5)alkyl; (C.sub.2-20)alkenyl, (C.sub.3-7)cycloalkyl, (C.sub.6-20)aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.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.sup.6 groups, R.sup.5 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro, and R.sup.6 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro.

13. The regioselectively substituted cellulose ester of claim 12, wherein C6DS.sub.R1-CO— is less than 0.1.

14. The regioselectively substituted cellulose ester of claim 12, wherein the degree of substitution of R.sup.4—CO— at the C2 position (“C2DS.sub.R4-CO”) is in the range of from about 0 to about 0.5, wherein the degree of substitution of R.sup.4—CO— at the C3 position (“C3DS.sub.R4-CO”) is in the range of from about 0 to about 0.5.

15. The regioselectively substituted cellulose ester of claim 12, wherein the R.sup.1—CO— is a combination comprising propionyl and benzoyl.

16. The regioselectively substituted cellulose ester of claim 15, wherein 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, and the degree of substitution at the C6 position for combined propionyl and benzoyl is less than 0.05.

17. The regioselectively substituted cellulose ester of claim 15, wherein 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, and the degree of substitution at the C6 position for combined propionyl and benzoyl is less than 0.05.

18. The regioselectively substituted cellulose ester of claim 12, wherein R.sup.1—CO— is a combination comprising propionyl and naphthoyl.

19. The regioselectively substituted cellulose ester of claim 18, wherein the degree of substitution for propionyl is in the range of from 0.2 to 0.9, and the degree of substitution for naphthoyl is in the range of from 0.4 to 1.4.

20. The regioselectively substituted cellulose ester of claim 12, wherein the weight average molecular weight (“M.sub.w”) is in the range from about 50,000 Da to about 500,000 Da.

Description

EMBODIMENTS

[0315] Embodiment 1. A regioselectively substituted cellulose ester comprising:

[0316] (i) a plurality of R.sup.1—CO— substituents;

[0317] (ii) a plurality of R.sup.4—CO— substituents;

[0318] (iii) a plurality of hydroxyl substituents, [0319] wherein the degree of substitution of R.sup.1—CO— at the C2 position (“C2DS.sub.R1”) is in the range of from about 0.2 to about 1.0, [0320] wherein the degree of substitution of R.sup.1—CO— at the C3 position (“C3DS.sub.R1”) is in the range of from about 0.2 to about 1.0, [0321] wherein the degree of substitution of R.sup.1—CO— at the C6 position (“C6DS.sub.R1”) is in the range of from about 0 to about 0.5, [0322] wherein the degree of substitution of R.sup.4—CO— at the C6 position (“C6DS.sub.R4”) is in the range of from about 0.1 to about 1.0, [0323] wherein the degree of substitution of hydroxyl is in the range of from about 0 to about 2.6, [0324] wherein R.sup.1 is chosen from (C.sub.1-20)alkyl; halo(C.sub.1-20)alkyl; (C.sub.2-20)alkenyl, (C.sub.3-7)cycloalkyl, (C.sub.6-20)aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.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.sup.3 groups, [0325] wherein R.sup.2 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro, [0326] wherein R.sup.3 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro; [0327] wherein R.sup.4 is chosen from (C.sub.1-20)alkyl; halo(C.sub.1-5)alkyl; (C.sub.2-20)alkenyl, (C.sub.3-7)cycloalkyl, (C.sub.6-20)aryl, wherein the aryl is unsubstituted or substituted by 1 to 6 R.sup.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.sup.6 groups, [0328] R.sup.5 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro, and [0329] R.sup.6 is chosen from (C.sub.1-6)alkyl, halo(C.sub.1-6)alkyl, (C.sub.1-6)alkoxy, halo(C.sub.1-6)alkoxy, halo, (C.sub.3-7)cycloalkyl, (C.sub.6-10)aryl, or nitro.
Embodiment 2. The regioselectively substituted cellulose ester of Embodiment 1, wherein R.sup.1—CO— is chosen from acetyl, propionyl, butanoyl, benzoyl, naphthoyl, 3,4,5-trimethoxybenzoyl, biphenyl-CO—, benzoyl-benzoyl-, or benzothiphene-CO—; and wherein R.sup.4—CO— is chosen from acetyl, propionyl, butyryl, benzoyl, acetyl, naphthoyl, 3,4,5-trimethoxybenzoyl, biphenyl-CO—, benzoyl-benzoyl-, or benzothiphene-CO—.
Embodiment 3. The regioselectively substituted cellulose ester of any one of Embodiments 1 or 2, wherein C6DS.sub.R1-CO— is less than 0.1.
Embodiment 4. The regioselectively substituted cellulose ester of any one of Embodiments 1-3, wherein R.sup.1—CO— is propionyl.
Embodiment 5. The regioselectively substituted cellulose ester of Embodiment 4, wherein the degree of substitution for propionyl is from about 1.0 to about 1.4, the C2 degree of substitution for propionyl is from 0.6 to 0.9, the C3 degree of substitution for propionyl is from about 0.3 to about 0.5.
Embodiment 6. The regioselectively substituted cellulose ester of Embodiment 5, wherein the degree of substitution at the C6 position for propionyl is less than 0.05.
Embodiment 7. The regioselectively substituted cellulose ester of any one of Embodiments 4-6, wherein R.sup.4—CO— is a (C.sub.6-20)aryl-CO—.
Embodiment 8. The regioselectively substituted cellulose ester of any one of Embodiments 4-6, wherein R.sup.4—CO— is a combination of pivaloyl and (C.sub.6-20)aryl-CO—.
Embodiment 9. The regioselectively substituted cellulose ester of Embodiment 8, wherein (C.sub.6-20)aryl-CO— is chosen from benzoyl and naphthoyl.
Embodiment 10. The regioselectively substituted cellulose ester of any one of Embodiments 8-9, wherein the degree of substitution for the pivaloyl is from 0.6 to 0.9; and the degree of substitution for the (C.sub.6-20)aryl-CO— is from 0.2 to 0.5.
Embodiment 11. The regioselectively substituted cellulose ester of Embodiments 1-3, wherein R.sup.1—CO— is a combination comprising benzoyl and naphthoyl.
Embodiment 12. The regioselectively substituted cellulose ester of Embodiment 11, wherein R.sup.4—CO— is (C.sub.1-6)alkyl-CO—.
Embodiment 13. The regioselectively substituted cellulose ester of Embodiment 12, wherein 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.sub.1-6)alkyl-CO— is less than 0.5.
Embodiment 14. The regioselectively substituted cellulose ester of Embodiment 13, wherein R.sup.4—CO— is propionyl.
Embodiment 15. The regioselectively substituted cellulose ester of any one of Embodiments 1-3, wherein R.sup.1—CO— is a combination of propionyl and benzoyl.
Embodiment 16. The regioselectively substituted cellulose ester of Embodiment 15, wherein R.sup.4—CO— is a combination of propionyl and benzoyl.
Embodiment 17. The regioselectively substituted cellulose ester of Embodiment 16, wherein the combined C2 and C3 degree of substitution for benzoyl is from 0.1 to 0.6, wherein the combined C2 and C3 degree of substitution for propionyl is from 0.5 to 1.4, wherein the C6 degree of substitution for benzoyl is from 0 to 0.8, and wherein the C6 degree of substitution for propionyl is from 0 to 1.0.
Embodiment 18. The regioselectively substituted cellulose ester of Embodiment 17, wherein the C6 degree of substitution for benzoyl is from 0.1 to 0.15, and wherein the C6 degree of substitution for propionyl is from 0.4 to 0.8.
Embodiment 19. The regioselectively substituted cellulose ester of any one of Embodiments 1-18, wherein the weight average molecular weight (“M.sub.w”) is in the range from about 50,000 Da to about 500,000 Da.

EXPERIMENTAL

Abbreviations

[0330] AcOH is acetic acid; Ac.sub.2O is acetic anhydride; AcCl is acetyl chloride; aq. is aqueous; Bu.sub.2O is butanoic anhydride; BzOH is benzoic acid; Bz.sub.2O is benzoic anhydride; Bzt is benzothiephenylC-CO—; BztOH is benzothiephenyl-COOH; BztCl is benzothiephenylCO-Cl; ° C. is degree Celsius; 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 is 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. is equivalent; Et.sub.2O 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.sub.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; μL is microliter; mm is millimeter; mmHg is millimeters mercury; N.sub.2 is nitrogen; NMR is nuclear magnetic resonance; Np is naphthyl; NpOH is 2-naphthoic acid; NpOH is 2-naphthoic acid; Np.sub.2O is 2-naphthoic anhydride; ppm is parts per million; Pr is propionyl; .sup.iPrOH is isopropyl alcohol; PrOH is propionic acid; Pr.sub.2O is propionic anhydride; RDS is relative degree of substitution; rt is room temperature; SM is starting material; TFA is trifluoroacetic acid; TFAA is trifluoroacetic anhydride; T.sub.g is glass transition temperature; TMBz is 2,3,4-trimethoxybenzoyl; TMBzOH is 2,3,4-trimethoxybenzoic acid; TMBzCl is 2,3,5-trimethoxybenzoyl chloride; TPP is triphenyl phosphate; wt % is weight percent;

Materials and Methods

NMR Characterization

[0331] 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-d.sub.6. 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.sub.6 as an internal reference (2.49 ppm).

[0332] Quantitative .sup.13C 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.sub.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.sub.6 as an internal reference (39.5 ppm).

[0333] 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 .sup.13C NMR. The total DS for any substituent is determined by .sup.1H NMR.

Molecular Weight Determination

[0334] For cellulose esters described in this report, Gel permeation chromatography analysis was performed in N-Methylpyrrolidinone containing 1% glacial acetic acid 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 0.8 ml/min, an auto-sampler with an injection volume of 50 microliters, and a column oven set at 40° 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 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 by weighing 12.5 mg into a 2 dram screw cap vial and dissolving in 10 ml of the solvent. 10 μL 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.

Dope Preparations

[0335] The solutions of the cellulose esters for preparation of the films and the film preparation were made by adapting the procedures disclosed in US 2012/0262650.

General Procedure for Film Casting and Optical Film Analysis

[0336] 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. Then, 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.).

EXAMPLES

Example 1: 6-Trifluoroacetyl Substituted Cellulose

[0337] 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. %). To a separate 500 mL graduated cylinder was added TFA (337 g) followed by 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. Analysis: Total DS: 1.1, C2DS: 0.03, C3DS: 0.1, C6DS: 1.0, and M.sub.w: 497,487.

Comparative Example 1. Cellulose-6-Trifluoroacetate Made According to Liebert Using Microcrystalline Cellulose

[0338] 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. The solution was allowed to mix for 1 hour whereupon the solution was poured into a beaker containing 1500 mL anhydrous Et.sub.2O. The precipitate was dispersed to a uniform particle size using a homogenizer, and the solids were collected using vacuum filtration. The solids were rinsed on the filter with diethyl ether (2×200 mL) and subsequently dried in vacuo at rt to afford the title compound. Analysis: Total DS: 1.2; C2DS 0.08; C3DS: 0.09; C6DS: 1.0; M.sub.w: 220,902.

[0339] 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.sub.w of the final product is less than half that for Ex 1.

Comparative Example 2. Cellulose-6-Trifluoroacetate Made According to Liebert Using Placetate F Cellulose Pulp

[0340] 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. This mixture was allowed to mix further for 1 h before being transferred to a beaker containing anhydrous Et.sub.2O (1.5 L). The material was dispersed to a uniform particle size using a homogenizer, and the solids were collected using vacuum filtration. The solids were rinsed on the filter with diethyl ether (2×200 mL) and subsequently dried in vacuo at rt to afford the title compound. Analysis: Total DS 1.4; C2DS: 0.1; C3DS: 0.7; C6DS: 0.7; M.sub.w: 1,322,504.

[0341] Comparative Ex 2 illustrates that the Liebert procedure is inefective in producing cellulose 6-trifluoroacetate from unmodified softwood pulps. Additionally, significant molecular weight degradation is not observed under these conditions.

Determination of Optimal TFAA Concentration for Acylation of Cellulose

[0342] 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.sub.2O (per anhydroglucose unit of cellulose) was added, and the mixture was allowed to stir overnight. Precipitation and polymer isolation gave the resulting cellulose acetates.

[0343] These preliminary studies are outlined in Table 1. When 0.6 equiv of TFAA were added, we saw a total DS.sub.Ac of 1.36 with a small amount of esterification at C.sub.6. This result indicated selective trifluoroacetylation at C.sub.6, although the acylation was not complete. We were pleased to find, however, that when 1.6 equiv TFAA were used, we saw good acetylation at C.sub.2 and C.sub.3 with virtually no substitution at C.sub.6. We then examined the effect of additional charges of TFAA to determine if trifluoroacetylation was also selective for C.sub.2 or C.sub.3, although the addition of 2.6 and 3.6 equiv TFAA gave no promise for this added selectivity. We finally determined that 1.65 equiv TFAA was the ideal stoichiometry for selective trifluoroacetylation at C.sub.6 while also leaving C.sub.2 and C.sub.3 open for further functionalization.

TABLE-US-00001 TABLE 1 Stoichiometry Trial # of TFAA Total DS.sub.Ac DS C.sub.2 DS C.sub.3 DS C.sub.6 1 0.6 1.4 0.7 0.4 0.1 2 1.6 1.7 0.8 0.8 0.05 3 2.6 1.6 0.6 0.7 0.03 4 3.6 1.6 0.7 0.7 0.04 5 1.6 1.7 0.8 0.8 0.00

[0344] The results compare favorably with known methods for acetylation of cellulose pulps (Table 2). The heterogeneous preparation of a cellulose acetate such as Eastman™ CA-320s affords a randomly-substituted copolymer with the acetyl groups distributed amongst C.sub.2, C.sub.3, and C.sub.6. Cellulose acetate prepared via the formate protocol developed by Buchanan (Example 13 of U.S. Pat. No. 9,243,072) affords a CA bearing siginificantly less substitution at C.sub.6 (DS C.sub.6=0.3). By contrast, polymers isolated via the TFA/TFAA protocol contain virtually no substitution at C.sub.6. For example, cellulose acetate of Ex 2 contains DS=0.05 while the remaining functionality is exclusively populated on C2 and C3. Notably, Ex 2 may be prepared in a significantly higher molecular weight than Eastman™ CA 320S or Ex 13 of Buchanan. These data illustrate the improved qualities for cellulose esterification using the TFA/TFAA process.

TABLE-US-00002 TABLE 2 Ex # Total DS.sub.Ac C2DS C3DS C6DS GPC M.sub.w EASTMAN ™ 1.8 0.6 0.6 0.6 50,450 CA 320S EX 13 OF 1.8 0.7 0.8 0.3 43,719 BUCHANAN 2 1.9 0.9 0.9 0.05 118,627

Example 2: Cellulose 2,3-Acetate

[0345] 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. %). To a separate 500 mL graduated cylinder was added TFA (337 g) followed by 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. Then the temperature controller was set to 50° C., and the reaction mixture was stirred for 35 min. Following, Ac.sub.2O 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.sub.(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. The title compound was then dried in a ceramic dish in vacuo at 60° C. for 12 h. Analysis: Total DS.sub.Ac: 1.9, C2DS.sub.Ac: 0.9, C3DS.sub.Ac: 0.9, C6DS.sub.Ac: 0.05, Mw: 118,627 Da

[0346] By adapting the synthetic procedure for the synthesis of Ex 2, Ex 3-5 were synthesized.

TABLE-US-00003 TABLE 3 Anhydride Total M.sub.w Ex # (eq) DS C2DS C3DS C6DS (Da) 3 Pr.sub.2O (2.0) 2.00 0.9 0.9 0.01 154,987 4 Bu.sub.2O (2.0) 2.00 0.9 0.9 0.02 140,588 5 Bz.sub.2O (2.0) 1.9 0.9 0.9 0.02 161,381

Example 6: Cellulose-2,3-Propionate

[0347] 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. In a separate flask, PrOH (18.26 g, 2.0 equiv) and TFA (30 mL) were stirred under a N.sub.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. The crude product was collected by filtration on a frit, and the crude product was then suspended in 5 M KOAc.sub.(aq.) (2000 mL) and slurried for 36 h. The crude product were collected by filtration on a frit and washed continuously with denionized water for 8 h. The title compound was obtained after drying the material in vacuo (60° C.) for 12. Analysis: DS.sub.Pr: 2.0, C2DS.sub.Pr: 0.8, C3DS.sub.Pr: 0.9, C6DS.sub.Pr: 0.03, Mw: 163,340 Da.

[0348] By adapting the procedure for the synthesis of Ex 6, Ex 7-12, and Ex 58-61 were synthesized.

TABLE-US-00004 TABLE 4 Acid Total M.sub.w Ex # (Eq.) DS C2DS C3DS C6DS (Da) 7 AcOH (2.0) 1.7 0.8 0.8 0.06 182,827 8 PrOH (2.0) 2.0 0.8 0.9 0.03 163,340 9 BuOH (2.0) 2.1 0.8 0.9 0.05 223,652 10 BzOH (2.0) 1.6 0.9 0.9 0.00 227,721 11 NpOH (2.0) 2.1 1.0 1.0 0.00 N/A 12 TMBzOH (1.4) 1.4 0.8 0.4 0.05 150,756 58 BzOH (1.5) 1.7 0.8 0.7 0.04 124,496 59 PrOH (1.3) 1.2 0.8 0.4 0.01 103,946 60 PrOH (1.2) 1.1 0.7 0.4 0.01  98,185 61 PrOH (1.2) 1.2 0.8 0.4 0.03 — 89 PrOH (1.2) 1.15 0.66 0.36 0.03 — 90 PrOH (1.44) 1.51 0.80 0.56 0.03 — 91 PrOH (1.3) 1.37 0.77 0.46 0.02 — 92 PrOH (1.2) 1.20 0.77 0.34 0.06 — 93 PrOH (1.3) 1.17 0.78 0.35 0.03 — 94 BuOH (1.3) 1.4 0.85 0.4 0.07 — 95 PrOH (1.7) 1.8 0.9 0.8 0.06 — 96 PrOH (1.5) 1.6 0.85 0.6 0.06 — 97 PrOH (1.7) 1.7 0.9 0.8 0.03 —

Example 13: Cellulose 2,3 Benzoate Propionate

[0349] 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.sub.2O (8.02 g. 0.5 eq) was slowly added to the reaction mixture via an overhead addition funnel. During the addition of the Pr.sub.2O, Bz.sub.2O (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. The solids were then re-suspended in .sup.iPrOH and slurried for 30 min. The crude product was collected by filtration on a frit. The crude product was then suspended in 5 M KOAc.sub.(aq.) (2000 mL) and stirred (36 h). The crude product was collected by filtration on a frit and washed continuously with denionized water for 8 h. The title compound was obtained after drying in vacuo (60° C.) for 12 h. Analysis: DS.sub.Bz: 0.9, DS.sub.Pr: 1.0, C2DS: 0.9, C3DS: 1.0: C6DS: 0.0, M.sub.w: 132,072 Da.

[0350] By adapting the procedure for the synthesis of Ex 13, Ex 14-16 were synthesized.

TABLE-US-00005 TABLE 5 Ex # Eq Bz.sub.2O Eq Pr.sub.2O 14 1.0 1.0 15 0.5 1.5 16 1.2 0.8

[0351] Table 6 provides the degree of substitution for Ex 14-16.

TABLE-US-00006 TABLE 6 M.sub.w Ex # DS.sub.Bz DS.sub.Pr C2DS C3DS C6DS (Da) 14 1.9 0.2 1.0 1.0 0.0 174,466 15 1.9 0.05 0.9 0.9 0.0 ND 16 0.5 1.5 0.9 1.0 0.0 146,421

Example 17: Cellulose 2,3-(2-Naphthoate) Propionate

[0352] 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. %). To a separate 500 mL graduated cylinder was added TFA (337 g) followed by 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. After ˜75 min, the mixture had formed a dark orange solution, at which point the temperature controller was set to 50° C. While this process was taking place, a separate oven-dried 250 mL round bottomed flask was charged with 2-NpOH (21.2 g, 1.0 eq) and TFA (60 mL) with magnetic stirring under an atmosphere of nitrogen. To this solution was slowly added TFAA (25.9 g, 1.0 eq), and the solution was allowed to stir for 45 min whereupon the slurry became homogeneous. The reaction kettle was then fitted with two separate liquids addition funnels. One funnel was charged with the freshly-prepared solution of the NpOH/TFAA, while the second funnel was charged with Pr.sub.2O (4.8 g, 0.3 eq). 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.sub.(aq.) (2000 mL) and slurried for 36 h. The crude product were collected by filtration on a frit and washed continuously with denionized water for 8 h. The title compound was obtained after drying in vacuo (60° C.) for 12 h. Analysis: DS.sub.Np: 0.7, DS.sub.Pr: 0.6, C2DS: 0.7, C3DS: 0.4, C6DS: 0.07, Mw: 90,003 Da.

[0353] By adapting the procedure for the synthesis of Ex 17, Ex 18-20 were prepared.

TABLE-US-00007 TABLE 7 Ex # Eq NpOH/TFAA Eq Pr.sub.2O 18 1.0 0.3 19 1.2 0.1 20 0.8 0.5

[0354] Table 8 provides the degree of substitution and molecular weight information for Ex 18-20.

TABLE-US-00008 TABLE 8 M.sub.w Ex # DS.sub.Np DS.sub.Pr C2DS C3DS C6DS (Da) 18 0.7 0.6 0.7 0.4 0.07 90,003 19 1.4 0.2 0.8 0.6 0.02 140,686 20 0.4 0.9 0.8 0.5 0.01 124,096

Example 21: Cellulose 2,3-(2-Naphthoate) Propionate

[0355] 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. %). To a separate 500 mL graduated cylinder was added TFA (337 g) followed by 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. After −75 min, the mixture had formed a dark orange solution, at which point the temperature controller was set to 50° C. While this process was taking place, a separate oven-dried 250 mL round bottomed flask was charged with 2-NpOH (25.5 g, 1.2 eq), PrOH (2.74 g, 0.3 eq), and TFA (60 mL) with magnetic stirring under a N.sub.2 atmosphere. To this solution was slowly added TFAA (38.87 g, 1.5 eq), and the solution was allowed to stir for 45 min whereupon the slurry became homogeneous. The reaction kettle was then fitted with a liquids addition funnel. The funnel was then charged with the previously prepared mixture of anhydrides. 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.sub.(aq.) (2000 mL) and slurried for 36 h. The solids were collected by filtration on a frit and washed continuously with denionized water for 8 h. The title compound was obtained after drying in vacuo (60° C.) for 12 h. Analysis: DS.sub.Np: 1.3, DS.sub.Pr: 0.3, C2DS: 0.9, C3DS: 0.6, Mw: 124,916 Da

[0356] By adapting the procedure for the synthesis of Ex 21, the examples in Table 9 were prepared.

TABLE-US-00009 TABLE 9 Acid 1 Acid 2 Acid 3 Ex # (eq) (eq) (eq) 22 PrOH (0.3) BztOH (1.1) — 23 PrOH (1.0) BuOH (1.0) — 24 PrOH (1.0) BzOH (1.0) — 25 PrOH (0.6) BuOH (0.6) Benzoate (0.6) 26 PrOH (0.6) NpOH (0.6) Benzoate (0.6) 27 PrOH (1.0) 2-ethylhexanoic — Acid (1.0) 28 PrOH (1.0) Stearatic Acid (1.0) — 29 PrOH (1.0) Crotonic Acid (1.0) — 62 PrOH (1.2) BzOH (0.45) — 63 PrOH (1.2) BzOH (0.32) — 64 PrOH (1.4) BzOH (0.32) — 65 PrOH (1.2) BzOH (0.25) — 76 AcOH (0.8) BzOH (0.2) N/A 77 AcOH (0.8) BzOH (0.2) N/A 78 AcOH (1.3) N/A N/A 79 AcOH (0.8) BzOH (0.2) N/A 80 AcOH (0.5) BzOH (0.2) N/A 81 AcOH (1.0) BztOH (0.2) N/A 110 PrOH (0.6) BzOH (0.35) N/A 111 PrOH (0.5) BzOH (0.35) N/A

[0357] 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.

TABLE-US-00010 TABLE 10 DS DS DS Ex Acyl Acyl Acyl M.sub.w # 1 2 3 C2DS C3DS C6DS (Da) 22 0.3 1.0 — 0.7 0.5 0.02 168,587 23 1.0 1.1 — 0.8 0.9 0.03 193,570 24 1.2 0.8 — 0.9 0.9 0.03 164,411 25 0.7 0.7 0.6 0.9 0.8 0.03 166,560 26 0.7 0.7 0.6 0.9 0.8 0.03 109,183 27 1.0 1.0 — 0.9 0.9 0.03 186,928 28 0.9 1.1 — — — — 102,968 29 1.0 0.9 — 0.9 0.8 0.04 129,012 62 1.3 0.2 — 0.8 0.4 0 105,134 63 1.3 0.4 — 0.8 0.7 0 94,974 64 1.6 0.3 — 0.8 0.8 0 109,951 65 1.2 0.2 — 0.8 0.5 0 111281 76 0.86 0.23 N/A 0.64 0.27 0.01 105464 77 0.81 0.23 N/A 0.59 0.33 0.04 113371 78 1.3 N/A N/A 0.51 0.51 0.15 104824 79 0.83 0.19 N/A 0.54 0.38 0.04 128046 80 0.5 0.33 N/A 0.35 0.24 0.1 117467 81 1.08 0.18 N/A 0.71 0.43 0.04 93378 110 0.61 0.38 N/A 0.56 0.33 0.04 109739 111 0.51 0.39 N/A 0.48 0.34 0.01 105400

Example 30: Procedure for Regioselective C.SUB.6 .Propionylation of 2,3-Substituted Cellulose Esters

[0358] An oven-dried 500 mL jacketed round bottomed flask was charged with a freshly dried (22 mmHg, 50° C., 12 h) Ex 58 (50 g, 8.9 wt % solids) under an atmosphere of nitrogen with mechanical stirring. The reaction vessel was connected via a rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C. To the flask was added DMAc (448 g), pyridine (61.6 g, 5.00 eq), and DMAP (1.90 g, 0.1 eq). The temperature controller was set to 50° C. and the mixture was stirred until the solids dissolved (˜1-2 h), and the reaction mixture was cooled to rt. Then Pr.sub.2O (27.3 g, 1.35 eq) was added via liquids addition funnel (2 min). The mixture was allowed to stir 12 h at rt, and the mixture was diluted with acetone (150 mL). The resulting mixture was poured over deionized water (3000 mL). The precipitated crude product was broken down to a uniform size via homogenization, and the crude product was collected via vacuum filtration on a coarse frit. The crude product was washed on the filter with MeOH (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. Analysis: DS.sub.Pr:1.4; DS.sub.Bz:1.5; C2DS: 0.9; C3DS: 0.9; C6DS: 1.0; M.sub.w: 120,125 Da.

Example 31: Regioselectively 2,3-Substituted Benzoate/2-Naphthoate Propionate Cellulose

[0359] 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 %). To a separate 500 mL graduated cylinder was added TFA (337 g) followed by 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. After −75 min, the mixture had formed a dark orange solution, at which point the temperature controller was set to 50° C. The glass stopper on the reaction kettle was replaced with a plastic funnel, and a mixture of Bz.sub.2O (27.8 g, 1.00 eq) and 2-Np.sub.2O (40.1 g, 1.00 eq) was added portion-wise. The reaction was allowed to stir for 12 h whereupon the dope was then precipitated by pouring into 3000 mL deionized water 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 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.sub.(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.sub.Np:1.4; DS.sub.Bz: 0.6; C2DS: 0.9; C3DS is 0.9; C6DS is 0.01; Mw is 157,907 Da.

[0360] By adapting the procedure for the synthesis of Ex 31, the examples in Table 11 were prepared.

TABLE-US-00011 TABLE 11 Ex Bz.sub.2O Np.sub.2O GPC # (eq) (eq) DS.sub.Bz DS.sub.Np C2DS C3DS C6DS Mw 74 1.5 0.5 1.1 0.8 0.9 0.9 0.05 156,992 75 0.5 1.5 0.2 1.8 0.9 0.9 0.01 136,457

Example 32

[0361] An oven-dried 500 mL jacketed round bottomed flask was charged with a freshly dried (50° C., 22.5 mmHg, 12 h) Ex 31 (10 g, 8.9 wt % solids) under an N.sub.2 atmosphere with mechanical stirring. 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. To the flask was added DMAc (93 g), pyridine (9.4 g, 5.00 eq), and DMAP (0.29 g, 0.1 eq), and the temperature controller was set to 50° C. to facilitate dissolution of the starting material. Once complete dissolution of the cellulose ester was observed, the reaction was allowed to cool to room temperature, whereupon Pr.sub.2O (0.93 g, 0.3 eq) was added via dropwise syringe addition over a duration of approximately 2 min. The mixture was allowed to stir 12 h at rt whereupon the reaction mixture was diluted with 100 mL acetone. The resulting mixture was poured into water (2000 mL) to precipitate the crude product. The solids were broken down to a uniform size via homogenization, and the solids were collected via vacuum filtration on a coarse frit. The solids were washed on the filter with 200 mL MeOH (200 mL) and washed continuously with water for 8 h. The solids were then dried in vacuo (60° C.) for 12 h. Analysis: DS.sub.Np: 1.4; DS.sub.Bz: 0.6; DS.sub.Pr: 0.3; C2DS: 0.9; C3DS: 0.9; C6DS: 0.3; Mw is 166,868 Da.

[0362] By adapting the procedure for the preparation of Ex 32, the examples in Table 12 were prepared.

TABLE-US-00012 TABLE 12 Starting CE Ex # (Ex #) Acylating Agent/Eq 33 31 Pr.sub.2O (0.5) 34 31 Pr.sub.2O (0.7) 36 74 Pr.sub.2O (0.3) 37 74 Pr.sub.2O (0.5) 38 74 Pr.sub.2O (0.7) 39 75 Pr.sub.2O (0.3) 40 75 Pr.sub.2O (0.5) 41 75 Pr.sub.2O (0.7)

[0363] Table 13 provides the degree of substitution and molecular weight information for Ex 33-41.

TABLE-US-00013 TABLE 13 M.sub.w Ex # DS.sub.Pr DS.sub.Np DS.sub.Bz C2DS C3DS C6DS (Da) 33 0.6 1.4 0.5 1.0 0.9 0.5 161,816 34 0.7 1.4 0.5 1.0 1.0 0.6 152,283 36 0.4 0.8 1.1 0.9 0.9 0.3 156,943 37 0.5 0.8 1.1 0.9 1.0 0.4 N/A 38 0.7 0.8 1.1 1.0 0.9 0.6 156,091 39 0.3 1.8 0.2 0.9 1.0 0.3 164,366 40 0.6 1.8 0.2 1.0 1.0 0.5 159,715 41 0.7 1.8 0.2 1.0 1.0 0.6 153,615

Example 42. Cellulose 2,3-Benzoate

[0364] 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. %). To a separate 500 mL graduated cylinder was added TFA (843 g) followed by TFAA (112 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. After −75 min, the mixture had formed a dark orange solution, at which point the temperature controller was set to 50° C. The glass stopper on the reaction kettle was replaced with a plastic funnel, and Bz.sub.2O (125 g, 1.00 eq) was added portion-wise. The reaction was allowed to stir for 12 h whereupon 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 solids were then transferred to a beaker containing .sup.iPrOH (3000 mL) and slurried for 30 min. The solids were then collected by filtration on a coarse frit. The solids were then collected and suspended in 5 M KOAc.sub.(aq.) (2000 mL) and the mixture was stirred for 36 h. The solids were collected by filtration on a frit and washed continuously with water for 8 h. The solids were then dried in vacuo (60° C.) for 12 h. Analysis: DS.sub.Pr: 0.0; DS.sub.Bz: 1.3 (appears lower due to poor resolution in the NMR solvent); C2DS: 0.8; C3DS: 0.9; C6DS: 0.02; M.sub.w: 129,434 Da.

Example 43. Cellulose 2,3-Benzoate-6-Propionate

[0365] A 1000 mL jacketed round bottomed flask was charged with a freshly vacuum dried (22.5 mmHg, 50° C., 12 h) Ex 42 (50 g, 8.9 wt % solids) under a N.sub.2 atmosphere with mechanical stirring. 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. To the flask was added DMAc (443 g), pyridine (55.9 g, 5.00 eq), and DMAP (1.73 g, 0.1 eq), and the temperature controller was set to 50° C. The mixture was stirred until dissolution of the solids (˜1-2 h). The reaction mixture was allowed to cool to rt and Pr.sub.2O (18.38 g, 1.0 eq) was added drop-wise (2 min). The mixture was allowed to stir 12 h at rt, and the reaction mixture was diluted with acetone (200 mL). The resulting mixture was poured into deionized water (3000 mL). The precipitated crude product was broken down to a uniform size via homogenization, and the crude product was collected via vacuum filtration on a coarse frit. The crude product was washed on the filter with MeOH (200 mL) and then a continuous stream of water at rt for 8 h. The title compound was obtained after drying (22.5 mmHg, 60° C., 12 h). Analysis: DS.sub.Pr: 1.1; DS.sub.Bz: 2.1; C2DS: 1.0; C3DS: 1.0; C6DS: 0.8; M.sub.w: 139,604 Da; T.sub.g: 171.2° C.

[0366] Using the procedure for the preparation of Ex 43, the examples in Table 14 were prepared.

TABLE-US-00014 TABLE 14 Acylating Agent Ex # SM (eq) 44 13 Pr.sub.2O (5.0) 45 13 Pr.sub.2O (5.0) 46 13 Pr.sub.2O (1.3) 47 58 Pr.sub.2O (1.35) 48 42 Pr.sub.2O (1) 49 13 Pr.sub.2O (1.3) 50 13 Pr.sub.2O (1.4) 51 13 Pr.sub.2O (5.0) 52 13 Pr.sub.2O (1) 53 13 Pr.sub.2O (2) 54 13 Pr.sub.2O (1.33) 55 5 Pr.sub.2O (0.3) 56 5 Pr.sub.2O (0.5) 57 13 Pr.sub.2O (0.7)
Table 15 provides the degree of substitution information, molecular weight and glass transition temperature information for Ex 44-57.

TABLE-US-00015 TABLE 15 T.sub.g Ex # DS.sub.Pr DS.sub.Bz C2DS C3DS C6DS M.sub.w (° C.) 44 2.2 0.9 1.0 1.0 1.0 138,053 134.8 45 1.2 2.0 1.0 1.0 1.0 146,246 146.2 46 1.3 1.3 0.9 0.8 0.9 116,036 167.7 47 1.4 1.5 0.9 0.9 1.0 120,125 146.6 48 1.1 2.1 1.0 1.0 0.8 139,604 171.2 49 1.8 1.1 1.0 0.9 1.0 131,067 143.8 50 1.4 1.4 1.0 0.9 1.0 126,285 150.7 51 1.2 1.9 1 1 1 129,911 151.2 52 1.0 1.7 0.9 0.9 0.8 123,319 180.8 53 1.6 1.5 1.0 1.0 1 137,023 144.3 54 1.1 1.8 1.0 0.8 1.0 141,888 148.7 55 0.3 2.2 0.9 0.9 0.3 159,457 150.0 56 0.5 2.1 0.9 0.9 0.4 148,598 180.8 57 0.7 2.0 0.9 0.9 0.6 152,743 181.4

Example 67: Synthesis of Cellulose 2,3-propionate-6-naphthoate pivalate

[0367] An oven-dried 500 mL jacketed round bottomed flask was charged with freshly dried (22 mmHg, 50° C., 12 h) Ex 60 (20 g, 8.3 wt % solids) under an atmosphere of nitrogen with mechanical stirring. The reaction vessel was connected via rubber tubing to a Thermo Neslab RTE-7 temperature controller, and the setpoint was set to 25° C. To the flask was added DMAc (97 g) and pyridine (122 g). The temperature controller was set to 50° C. and the mixture was stirred until the solids dissolved completely (˜1-2 h). The reaction mixture was then cooled to 20° C. In a separate vessel, 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 .sup.iPrOH (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.

[0368] The examples in Table 16 were prepared by adapting the procedure for the preparation of Ex 67.

TABLE-US-00016 TABLE 16 Acyl1 Donor Acyl2 Donor Ex # SM (eq) (eq) 66 59 Bz.sub.2O (0.4) PivCl (0.9) 67 60 Np.sub.2O (0.4) PivCl (0.9) 68 61 Bz.sub.2O (0.6) — 69 62 Bz.sub.2O (0.4) PivCl (0.9) 70 63 TMBzCl (0.6) PivCl (0.75) 71 64 TMBzCl (0.6) PivCl (0.75) 72 63 Np.sub.2O (0.6) PivCl (0.75) 73 65 Bz.sub.2O (0.4) PivCl (0.9) 82 76 BzCl (0.4) PivCl (0.9) 83 76 PivCl (1.3) N/A 84 77 PivCl (0.9) N/A 85 78 Ac.sub.2O (0.7) BzCl (0.7) 86 79 BzCl (0.4) PivCl (0.9) 87 80 BzCl (0.6) Ac.sub.2O (0.9) 88 81 Ac.sub.2O (0.9) N/A 112 110 BzCl (0.25) Pr.sub.2O (0.9) 113 110 BzCl (0.35) Pr.sub.2O (0.8) 114 111 BzCl (0.45) Pr2O (0.7) 115 111 BzCl (0.45) Pr2O (0.9)

[0369] Table 17 provides degree of substitution, and molecular weight information for Ex 66-73, and 82-88.

TABLE-US-00017 TABLE 17 Ex # DS.sub.Pr DS.sub.Pv DS.sub.Acyl1 DS.sub.Acyl2 C2DS C3DS C6DS GPC M.sub.w 66 1.3 0.8 Acyl1 = N/A 0.8 0.5 1.0 103,666 Bz, 0.3 67 1.2 0.7 Acyl1 = N/A 0.8 0.5 1.0 107,643 Np, 0.4 68 1.3 0 Acyl1 = N/A 0.8 0.5 0.5 102,971 Bz, 0.6 69 1.3 0.6 Acyl1 = N/A 0.9 0.5 1.0 98,052 Bz, 0.6 70 1.3 0.6 Acyl1 = Acyl2 = 0.9 0.7 1.0 115,286 TMBz, 0.5 Bz, 0.4 71 1.5 0.5 Acyl1 = Acyl2 = 0.9 0.9 1.0 131,278 TMBz, 0.5 Bz, 0.3 72 1.3 0.5 Acyl1 = Acyl2 = 0.9 0.8 1.0 106,659 Bz, 0.4 Np, 0.6 73 1.2 0.7 Acyl1 = Acyl2 = 0.9 0.6 1.0 118,396 Bz, 0.6 Pv, 0.7 82 0.83 0.70 Acyl1 = N/A 0.78 0.38 0.97 112095 Bz, 0.62 83 0.83 1.07 N/A N/A 0.72 0.37 0.97 109607 84 0.77 0.34 N/A N/A 0.60 0.37 0.73 159187 85 2.58 0 N/A 0.1 0.92 0.67 0.98 93970 86 0.80 0.76 Acyl1 = N/A 0.67 0.48 0.97 134357 Bz, 0.64 87 1.44 0 Acyl1 = N/A 0.77 0.43 0.93 138436 Bz, 0.8 88 1.94 N/A N/A N/A 0.83 0.54 0.63 99169 112 1.48 N/A Acyl1 = N/A 0.61 0.74 0.45 123212 Bz, 0.61 113 1.38 N/A Acyl1 = N/A 0.73 0.48 0.82 119919 Bz, 0.70 114 1.19 N/A Acyl1 = N/A 0.69 0.43 0.82 112167 Bz, 0.81 115 1.36 N/A Acyl1 = N/A 0.75 0.44 0.91 107455 Bz, 0.80
Preparation of Example 98: An oven-dried 500-mL jacketed 3-neck round-bottomed flask was transferred to the fume hood and affixed to the hood scaffolding. The flask was then allowed to purge under an atmosphere of nitrogen while cooling. The flask was then fitted with a mechanical stirrer and adapter along with a positive pressure of nitrogen. The flask was then charged with Ex 89 (20 grams) using a solids addition funnel. DMAc (50 mL) was added to the flask followed by pyridine (150 mL). The reaction temperature was adjusted to 50° C., and the mixture was allowed to stir until complete dissolution of the cellulose ester was observed. 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. The solids were washed on the filter twice with 200 mL PrOH. The solids were then washed continuously with room temperature deionized water for 8 hours. The solids were then dried in vacuo in a ceramic dish (22.5 mm Hg, 60° C.) for 12 hours. The product was analyzed by 1H NMR, .sup.13C NMR, GPC, and CIC. DSBz=0.29, DSC2=0.83, DSC3=0.52, DSC6=0.96.

[0370] By adapting general procedure B, the following cellulose esters were prepared

TABLE-US-00018 TABLE 18 SM Aryl Acylating Piv Ex # (Ex #) Agent, eq (Piv eq) 99 59 BzCl, 0.4 0.8 100 59 NpCl, 0.4 0.9 101 90 BzCl, 0.6 0 102 89 TMBzCl, 0.6 0.75 103 91 BzCl, 0.8 0 104 92 NpCl, 0.6 0.75 105 93 NpCl, 0.6 0.4.sup.1 106 93 BztCl, 0.6 0.75 107 61 NpCl, 0.6 0.5 108 61 BzBzCl, 0.6 0.4 109 4 BiphCl, 0.8 0 .sup.1Propionic anhydride is used instead of pivaloyl chloride.

[0371] Table 19 provides the degrees of substitution for cellulose esters provided in Table 18.

TABLE-US-00019 TABLE 19 Ex # DS.sub.Ar Ds.sub.Pv DS C.sub.2 DS C.sub.3 DS C.sub.6 DS.sub.OH 99 Ar = 0.79 0.83 0.52 0.96 0.69 Bz, 0.29 100 Ar = 0.71 0.84 0.52 0.95 0.69 Np, 0.40 101 Ar = 0 0.83 0.61 0.52 1.04 Bz, 0.61 102 Ar = 0.85.sup.3 0.72 0.49 0.91 0.88 TMBz, 0.24 103 Ar = 0 0.81 0.50 0.47 1.12 Bz, 0.57 104 Ar = 0.45 0.83 0.39 0.89 0.89 Np, 0.53 105 Ar = 1.57.sup.2 0.79 0.41 0.44 1.36 Np, 0.11 106 Ar = 0.44 0.81 0.42 0.85 0.92 Bzt, 0.52 107 Ar = 0.27.sup.3 0.87 0.44 0.92 0.77 Np, 0.76 108 Ar = 0.10 0.95 0.48 0.95 0.62 BzBz, 0.59 109 Ar = 0 0.95 0.75 0.72 0.58 Biph, 0.80 .sup.2This value is DS.sub.Pr not DS.sub.Pv. .sup.3This value is higher than the theoretical due to overlap of NMR peaks.

[0372] Table 20 provides additional degree of substation information for Ex 98-103.

TABLE-US-00020 TABLE 20 C.sub.2/C.sub.3 Aliphatic C.sub.6 Aromatic Group acyl Group C.sub.6 Residual EX # (C.sub.2/C.sub.3DS.sub.Ak) (C.sub.6DS.sub.Ar) Hydroxyl 98 Pr (1.18) Bzt (0.59) 0 99 Pr (1.33) Bz (0.29) 0 100 Pr (1.33) Np (0.40) 0 101 Pr (1.50) Bz (0.61) 0.39 102 Pr (1.15) TMBz (0.24) 0 103 Pr (1.37) Bz (0.57) 0.43

[0373] Table 21 provides degree of substitution information for Ex 104-109.

TABLE-US-00021 TABLE 21 C.sub.2/C.sub.3 Aliphatic C.sub.6 Aromatic Group Group C.sub.2/C.sub.3 Residual C.sub.6 Residual EX # (C.sub.2/C.sub.3DS.sub.Ak) (C.sub.6DS.sub.Ar) Hydroxyl Hydroxyl 104 Pr (1.21) Np (0.53) 0.79 0.11 105 Pr (1.57) Np (0.11) 0.43 0.89 106 Pr (1.17) Bzt (0.52) 0.83 0.04 107 Pr (1.27) Np (0.76) 0.73 0 108 Pr (1.80) BzBz (0.59) 0.20 0.31 109 Pr (1.79) Biph (0.80) 0.2 0.2

Films

[0374] Table 22 provides the films prepared using the general procedure for the preparation of the films.

TABLE-US-00022 TABLE 22 Unstretched Films Re R.sub.th Film CE d (589 (589 Film Film # Ex # Solvent (μm) nm) nm) R.sub.th/d Color Haze 33.1 33 MEK 9.3 0.1 83.2 9.0 — — 34.1 34 MEK 10.2 0.2 67.7 6.7 — — 35.1 35 DCM 8.9 0.5 166.8 18.8 — — 36.1 36 Cyclopen- 18.9 1.3 230.6 12.2 — — tanone 37.1 37 Cyclopen- 16.2 3.9 181.0 11.2 — — tanone 38.1 38 MEK 6.4 1.0 75.5 11.7 — — 39.1 39 DCM 8.6 3.4 6.4 0.7 — — 40.1 40 DCM 9.0 3.1 −12.5 −1.4 — — 41.1 41 DCM 10.4 4.6 −12.0 −1.2 — — 44.1 44 MEK 34.0 2.8 282.5 8.3 0.8 2.4 45.1 45 MEK 36.7 9.1 28.8 0.7 1.6 33.6 46.1 46 MEK 14.7 0.8 77.7 5.3 0.3 2.1 47.1 47 MEK 58.0 13.2 289.7 5.0 1.3 7.5 48.1 48 MEK 10.9 2.0 114.5 10.5 0.5 1.2 49.1 49 MEK 14.2 1.4 91.1 6.4 0.4 2.6 50.1 50 MEK 13.9 2.0 119.5 8.4 0.3 1.8 51.1 51 MEK 13.19 0.7 92.7 7.0 1.0 18.3 52.1 52 MEK 6.5 0.7 49.7 7.7 0.3 0.6 53.1 53 MEK 18.7 2.7 109.1 6.8 0.4 0.5 54.1 54 MEK 13.3 0.6 57.6 4.3 0.3 1.3 55.1 55 Insoluble — — — — — — 56.1 56 Cyclopen- 12.5 −0.1 89.0 7.1 0.4 1.58 tanone 57.1 57 MEK 6.5 0.2 54.7 8.6 0.3 0.19

[0375] The following films shown in Table 23 were prepare by adapting the previously disclosed procedures. The films were prepared from the solvent, MEK.

TABLE-US-00023 TABLE 23 CE Stretch d Film # Ex # Ratio Temp (μm) 30.1 30 None NA 42.0 30.2 30 1 × 1.4 190 43.0 30.3 30 1 × 1.4 180 39.0 43.1 43 None 10.9 43.2 43 1 × 1.2 185 50.0 43.3 43 1 × 1.2 175 47.0 43.4 43 1 × 1.1 195 52.0 46.2 46 None 92.0 46.3 46 1.12 185 90.0 46.4 46 1.14 185 82.0 46.5 46 1.1  185 90.0 50.2 50 None 87.0 50.3 50 1 × 1.2 175 60.0 54.2 54 None 58.0 54.3 54 1.14 180 36.0 54.4 54 1.4 × 1.4.sup.  200 21.0 54.5 54 1 × 1.4 190 29.0 57.2 57 None 61.0 57.3 57 1 × 1.4 195 56.0 57.4 57 1 × 1.2 195 58.0 57.5 57 1 × 1.1 195 60.0 57.6 57  1 × 1.05 195 66.0 57.7 57  1 × 1.07 195 62.0 57.8 57  1 × 1.02 195 62.0 52.2 52 None NA 41.0 52.3 52 None NA 40.0 52.4 52 1.4 × 1.4.sup.  190 41.0 52.5 52 1 × 1.4 180 48.0 53.2 53 None NA 48.0 53.3 53 1.4 × 1.4.sup.  200 52.0 53.4 53 1 × 1.4 190 49.0 53.5 53 1 × 1.4 180 54.0 69.1 69 1 × 1.4 150 58.0 69.2 69 1 × 1.4 150 52.0 69.3 69 1 × 1.4 160 68.0 69.4 69 1 × 1.2 160 66.0 69.5 69 1 × 1.6 160 64.0 70.1 70 1 × 1.1 135 46.0 70.2 70 1 × 1.2 135 52.0 70.3 70 1 × 1.4 135 42.0 70.4 70 1 × 1.5 135 42.0 70.5 70 1 × 1.6 135 40.0 71.1 71 1 × 1.2 135 52.0 71.2 71 1 × 1.4 135 46.0 71.3 71 1 × 1.5 135 48.0 71.4 71 1 × 1.6 135 41.0 71.5 71 1 × 1.8 135 34.0 71.6 71 1 × 2.sup.  135 41.0 72.1 72 1 × 1.1 135 56.0 72.2 72 1 × 1.2 135 54.0 72.3 72 1 × 1.3 135 52.0 72.4 72 1 × 1.4 135 60.0 72.5 72 1 × 1.6 135 48.0 73.1 73 1 × 1.2 160 46.0 73.2 73 1 × 1.4 160 54.0 73.3 73 1 × 1.6 160 48.0 73.4 73 1 × 1.8 160 43.0 73.5 73 1 × 1.8 165 41.0 73.6 73 1 × 1.2 175 56.0 73.7 73 1 × 1.4 175 52.0 73.8 73 1 × 1.6 175 44.0 73.9 73 1 × 1.8 175 42.0 82.1 82 1 × 1.sup.  N/A 51 82.2 82 1 × 1.2 215 52 82.3 82 1 × 1.4 215 52 82.4 82 1 × 1.6 215 45 83.1 83 1 × 1.sup.  N/A 43 83.2 83 1 × 1.2 205 49 83.3 83 1 × 1.4 205 49 83.4 83 1 × 1.6 205 42 84.1 84 1 × 1.sup.  N/A 37 84.2 84 1 × 1.2 205 47 84.3 84 1 × 1.4 205 42 85.1 85 1 × 1.sup.  N/A 38 85.2 85 1 × 1.2 185 46 85.3 85 1 × 1.4 185 46 86.1 86 1 × 1.sup.  N/A 42 86.2 86 1 × 1.2 200 54 86.3 86 1 × 1.4 200 52 86.4 86 1 × 1.6 200 43 87.1 87 1 × 1.sup.  N/A 37 87.2 87 1 × 1.2 215 49 87.3 87 1 × 1.4 215 43 87.4 87 1 × 1.6 215 43 88.1 88 1 × 1.sup.  N/A 36 88.2 88 1 × 1.2 215 49 88.3 88 1 × 1.4 215 42 88.4 88 1 × 1.6 215 40

[0376] Table 24 provides additional properties for the films in Table 23.

TABLE-US-00024 TABLE 24 R.sub.e R.sub.e R.sub.th R.sub.th Film R.sub.e R.sub.th Rth/d (450 nm/ (650 nm/ (450 nm/ (650 nm/ # (589 nm) (589 nm) (589 nm) 550 nm) 550 nm) 550 nm) 550 nm) 30.1 15.1 306.7 0.7 1.1 0.97 1.10 0.95 30.2 20.6 89.0 0.7 1.1 0.96 1.09 0.95 30.3 38.3 217.0 0.8 1.1 0.96 1.09 0.95 43.1 2.2 112.7 4.0 1.1 0.98 1.09 0.95 43.2 −111.6 110.6 0.9 1.1 0.96 1.05 0.97 43.3 −160.4 −87435.2 0.9 1.1 0.96 2.53 0.41 43.4 −113.5 124.2 0.8 1.1 0.96 1.06 0.96 46.2 26.6 526.6 0.5 1.1 0.96 1.08 0.96 46.3 −652.0 too large 0.5 46.4 too large too large 0.6 46.5 −649.0 too large 0.5 50.2 52.3 571.6 0.6 1.08 0.96 1.08 0.95 50.3 too large too large 0.8 54.2 24.84 279.37 0.9 1.08 0.96 1.03 0.99 54.3 −189.99 296.20 1.5 1.08 0.96 1.07 0.93 54.4 10.80 64.75 2.6 1.08 0.96 1.09 0.95 54.5 −106.93 145.89 1.9 1.08 0.96 1.09 0.95 57.2 5.04 422.51 0.9 1.09 0.97 1.08 0.97 57.3 −596.00 too large 1.0 57.4 −118.00 too large 1.0 57.5 −371.00 too large 1.0 57.6 −257.72 357.51 0.9 1.08 0.96 1.05 0.98 57.7 −303.98 422.16 0.9 1.08 0.96 1.05 0.98 57.8 −175.67 423.38 0.9 1.05 0.96 1.08 0.96 52.2 194.86 −767.84 1.3 1.06 0.96 1.69 0.68 52.3 46.53 680.17 1.3 1.08 0.96 1.06 0.95 52.4 −85.00 470.77 1.3 1.08 0.96 1.03 0.98 52.5 57.86 367.01 1.1 1.08 0.96 0.95 1.00 53.2 24.61 231.50 1.1 1.07 0.96 1.11 0.94 53.3 15.18 111.97 1.0 1.08 0.96 1.09 0.96 53.4 17.45 109.23 1.1 1.07 0.96 1.09 0.95 53.5 13.38 82.13 1.0 1.08 0.96 1.08 0.96 66.1 0.3 −55.8 −5.7 3.6 6.8 1.0 1.0 67.1 0.3 −89.7 −10.6 −3.5 2.1 1.2 1.0 68.1 0.2 −158.0 −11.2 0.2 2.0 1.0 1.0 69.1 51.2 −117.6 −2.0 0.9 1.1 1.0 1.0 69.2 44.0 −151.1 −2.9 0.8 1.1 1.0 1.0 69.3 89.6 −109.3 −1.6 0.9 1.0 1.1 1.0 69.4 60.8 −113.7 −1.7 0.9 1.0 1.0 1.0 69.5 76.6 −87.5 −1.4 0.9 1.0 1.0 1.0 70.1 5.5 −11.4 −0.2 0.7 1.1 0.8 1.1 70.2 6.8 −17.0 −0.3 0.6 1.2 0.9 1.1 70.3 4.6 −11.1 −0.3 −0.3 1.7 0.9 1.1 70.4 5.7 −8.0 −0.2 −0.1 1.5 0.6 1.2 70.5 −1.0 −12.3 −0.3 3.5 −0.2 0.6 1.2 71.1 6.1 −5.4 −0.1 0.7 1.2 0.8 1.1 71.2 7.6 −4.7 −0.1 0.5 1.2 0.6 1.2 71.3 8.4 −4.3 −0.1 0.5 1.2 0.5 1.2 71.4 8.5 −4.3 −0.1 0.5 1.2 0.4 1.3 71.5 5.0 −3.6 −0.1 0.0 1.5 0.2 1.6 71.6 4.3 −4.8 −0.1 −0.4 1.8 −0.2 2.0 72.1 6.3 −8.1 −0.1 0.8 1.1 0.9 1.0 72.2 6.1 −8.7 −0.2 0.7 1.2 0.9 1.0 72.3 2.7 −8.0 −0.2 0.1 1.6 0.9 1.1 72.4 −2.6 −13.8 −0.2 2.1 0.4 1.0 1.0 72.5 −14.5 −2.2 −0.05 1.3 0.8 −1.6 2.6 73.1 25.0 −22.7 −0.5 0.8 1.1 0.9 1.0 73.2 34.8 −22.3 −0.5 0.8 1.1 0.8 1.1 73.3 26.4 −17.8 −0.4 0.7 1.2 0.8 1.1 73.4 19.1 −20.6 −0.5 0.7 1.1 0.8 1.2 73.5 18.6 −14.5 −0.4 0.6 1.2 0.7 1.2 73.6 26.8 −14.4 −0.2 0.9 1.0 0.9 1.0 73.7 30.2 −15.8 −0.3 0.8 1.1 0.8 1.1 73.8 26.1 −13.4 −0.3 0.8 1.1 0.8 1.1 73.9 22.9 −11.3 −0.3 0.7 1.1 0.7 1.1 82.1 3.209 −158.097 3.0999 1.103 0.917 0.982 1.015 82.2 61.747 −34.630 0.666 0.997 1.003 0.999 0.991 82.3 73.351 −38.657 0.743 0.992 1.004 0.993 0.994 82.4 78.489 −42.247 0.939 0.991 1.006 1.077 0.975 83.1 2.122 −83.432 −1.940 0.922 1.017 0.972 1.024 83.2 24.891 −15.009 −0.306 0.892 1.053 0.896 1.050 83.3 35.226 −20.047 −0.409 0.877 1.060 0.886 1.054 83.4 38.401 −22.457 −0.535 0.859 1.068 0.872 1.060 84.1 1.919 −99.118 −2.679 0.815 1.066 0.958 1.019 84.2 69.881 −41.347 −0.880 0.907 1.049 0.916 1.041 84.3 74.817 −42.662 −1.016 0.895 1.052 0.903 1.046 85.1 3.002 −132.495 −3.487 0.955 1.011 0.995 1.003 85.2 83.935 −51.382 −1.117 0.916 1.043 0.929 1.035 85.3 104.780 −65.776 −1.430 0.925 1.039 0.936 1.032 86.1 1.078 −91.626 −2.182 0.786 1.128 0.841 0.990 86.2 11.163 −2.170 −0.040 0.585 1.208 3.780 −5.568 86.3 12.626 −1.063 −0.020 0.504 1.278 2.390 −2.516 86.4 13.025 −2.825 −0.066 0.477 1.349 5.068 −6.635 87.1 3.119 −183.472 −4.959 0.953 1.028 1.009 0.995 87.2 55.589 −35.083 −0.716 0.825 1.085 0.861 1.066 87.3 58.971 −35.006 −0.814 0.794 1.103 0.826 1.084 87.4 62.773 −34.244 −0.796 0.770 1.113 0.783 1.106 88.1 1.634 −142.284 −3.952 0.859 1.089 0.960 1.015 88.2 66.429 −39.755 −0.811 0.705 1.134 0.742 1.106 88.3 61.407 −38.319 −0.912 0.624 1.167 0.695 1.129 88.4 55.016 −36.105 −0.903 0.553 1.201 0.627 1.172 98.1 — — −4.39 — — — — 99.1 — — −5.70 — — — — 100.1 — — −8.54 — — — — 101.1 — — −6.58 — — — — 102.1 — — −3.87 — — — — 103.1 — — −9.15 — — — — 104.1 — — −11.09 — — 1.06 0.97 105.1 — — −9.67 — — 1.02 0.99 106.1 — — −11.33 — — 1.07 0.97 107.1 — — −12.08 — — 1.07 0.96 108.1 — — −16.0085 — — 1.06 0.97 109.1 — — −10.5215 — — 1.10 0.95

Claims not Limited to Disclosed Embodiments

[0377] The preferred forms of the invention described above are to be used as illustration only, and should not be used in a limiting sense to interpret the scope of the present invention. Modifications to the exemplary embodiments, set forth above, could be readily made by those skilled in the art without departing from the spirit of the present invention.

[0378] The inventors hereby state their intent to rely on the Doctrine of Equivalents to determine and assess the reasonably fair scope of the present invention as it pertains to any apparatus not materially departing from but outside the literal scope of the invention as set forth in the following claims.