Cellulose interpolymers and method of oxidation

• US 20050192434A1
• Filed: 11/23/2004
• Published: 09/01/2005
• Est. Priority Date: 11/28/2003
• Status: Active Grant

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Watterson, Thelma Lee, Lambert, Juanelle Little, Carty, Susan Northrop, Lindblad, Margaretha Soderqvist, Malcolm, Michael Orlando, Kuo, Chung-Ming, Posey-Dowty, Jessica Dee, Buchanan, Charles Michael, Wood, Matthew Davie, Buchanan, Norma Lindsey
• Granted Patent: US 7,879,994 B2
• Time in Patent Office: Days
• US Class Current: 536/32
• CPC Class Codes: A61K 47/38 Cellulose; Derivatives thereof
• CPC Class Codes: A61K 9/19 lyophilised , i.e. freeze-dried, solutions or dispersions lyophilised products with subsequent particle size reduction A61K9/14; granules or pellets made by lyphilisation A61K9/1682; solid oral dosage forms made by lyophilisation A61K9/2095; lyophilisation additives A61K47/00
• CPC Class Codes: A61K 9/2054 Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
• CPC Class Codes: A61K 9/2866 Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
• CPC Class Codes: A61K 9/4891 Coated capsules; Multilayered drug free capsule shells with drug coating for immediate release A61K9/4808; osmotic devices A61K9/0004
• CPC Class Codes: C08B 15/02 Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
• CPC Class Codes: C08B 15/04 Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
• CPC Class Codes: C08B 3/04 Cellulose formate
• CPC Class Codes: C08B 3/06 Cellulose acetate , e.g. mono-acetate, di-acetate or tri-acetate
• CPC Class Codes: C08B 3/08 of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
• CPC Class Codes: C08B 3/16 Preparation of mixed organic cellulose esters , e.g. cellulose aceto-formate or cellulose aceto-propionate
• CPC Class Codes: C08B 3/22 Post-esterification treatments, including purification
• CPC Class Codes: C08B 3/24 Hydrolysis or ripening
• CPC Class Codes: C08L 1/10 Esters of organic acids , i.e. acylates
• CPC Class Codes: C08L 1/12 Cellulose acetate
• CPC Class Codes: C08L 1/14 Mixed esters, e.g. cellulose acetate-butyrate
• CPC Class Codes: C09D 17/00 Pigment pastes, e.g. for mixing in paints artists' paints C09D5/06

Abstract

This invention provides cellulose ester interpolymers, and methods of oxidizing cellulose interpolymers and cellulose ester interpolymers. The invention also provides routes to access carboxylated cellulose ester derivatives with high acid numbers wherein the carboxyl group is attached directly to the cellulose backbone by a carbon-carbon bond. Through functionalization of an intermediate aldehyde, the corresponding cationic or zwitterionic cellulose ester derivatives can also be accessed. The interpolymers of the present invention have a number of end-use applications, for example, as binder resins in various types of coating compositions and as drug delivery agents.

Claims

1. A cellulose ester interpolymer wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units

2. The cellulose ester interpolymer of claim 1, having an apparent degree of substitution per anhydroglucose unit of X of 0.05 to 1.0, and an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of at least about 0.6.

3. The cellulose ester interpolymer of claim 1, having an apparent degree of substitution per anhydroglucose unit of X of 0.2 to 1.0, and an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8.

4. The cellulose ester interpolymer of claim 1, having an acid number greater than 10.

5. The cellulose ester interpolymer of claim 1, having an acid number greater than 30.

6. The cellulose ester interpolymer of claim 1, having an acid number greater than 30 and less than 150.

7. The cellulose ester interpolymer of claim 1, having an acid number greater than 30 and less than 130.

8. The cellulose ester interpolymer of claim 1, having an acid number greater than 30 and less than 90.

9. The cellulose ester interpolymer of claim 1, wherein X is formyl, carboxy, or a mixture thereof.

10. The cellulose ester interpolymer of claim 1, wherein X is carboxy.

11. The cellulose ester interpolymer of claim 1, wherein X is formyl.

12. The cellulose ester interpolymer of claim 1, wherein X is aminomethyl, R₆—

NH—

CH₂—

, or a mixture thereof.

13. The cellulose ester interpolymer of claim 1, wherein R₁, R₂, R₃, R₄, and R₅ are independently selected from the group consisting of hydrogen, acetyl, propionyl, butyryl, or a mixture thereof.

14. The cellulose ester interpolymer of claim 1, having a weight average molecular weight of at least 5,000 g/mol.

15. The cellulose ester interpolymer of claim 1, having a range of molecular weight of between 10,000 g/mol and 900,000 g/mol.

16. The cellulose ester interpolymer of claim 1, having a degree of polymerization of at least 10.

17. The cellulose ester interpolymer of claim 1, having a degree of polymerization of at least 25.

18. The cellulose ester interpolymer of claim 1, having a degree of polymerization of between 25 and 50.

19. The cellulose ester interpolymer of claim 1, having a degree of polymerization of at least 250.

20. The cellulose ester interpolymer of claim 9, wherein the ratio of carboxy to formyl is greater than or equal to 5:

1, respectively.

21. The cellulose ester interpolymer of claim 9, wherein the ratio of carboxy to formyl is less than or equal to 1:

5, respectively.

22. The cellulose ester interpolymer of claim 9, wherein the ratio of carboxy to formyl is between 5:

1 and 1;

5, respectively.

23. A cellulose ester interpolymer comprising a plurality of anhydroglucose units having a C6 carboxy group and wherein the cellulose ester interpolymer has an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of at least about 0.6 and an acid number of greater than 10.

24. The cellulose ester interpolymer of claim 23 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8.

25. The cellulose ester interpolymer of claim 23 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8, and an acid number of greater than 30 and less than 150.

26. The cellulose ester interpolymer of claim 23 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8, and an acid number of greater than 30 and less than 130.

27. The cellulose ester interpolymer of claim 23 having an apparent degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.7 to 2.8, and an acid number of greater than 30 and less than 90.

28. The cellulose ester interpolymer of claim 23, wherein said C₂-C₁₂ acyl is acetyl, proprionyl, butyryl, or a mixture thereof.

29. The cellulose ester interpolymer of claim 23 having a random distribution throughout the cellulose ester interpolymer of anhydroglucose units having C6 carboxy groups.

30. The cellulose ester interpolymer of claim 23, having a weight average molecular weight of at least 5,000 g/mol.

31. The cellulose ester interpolymer of claim 23, having a range of molecular weight of between 10,000 g/mol and 900,000 g/mol.

32. The cellulose ester interpolymer of claim 23, having a degree of polymerization of at least 10.

33. The cellulose ester interpolymer of claim 23, having a degree of polymerization of at least 25.

34. The cellulose ester interpolymer of claim 23, having a degree of polymerization of between 25 and 50.

35. The cellulose ester interpolymer of claim 23, having a degree of polymerization of about 250.

36. The cellulose ester interpolymer of claim 23, further comprising a plurality of anhydroglucose units having a C6 formyl group.

37. The cellulose ester interpolymer of claim 23, further comprising a plurality of anhydroglucose units having a C6 aminomethyl group.

38. The cellulose ester interpolymer of claim 23, further comprising a plurality of anhydroglucose units having a C6 subsituted aminomethyl group, wherein the aminomethyl group is substuted with substitutent selected from the group consisting of alkyl, aryl, and alkylene aryl.

39. The cellulose ester interpolymer of claim 36, wherein the ratio of C6 carboxy groups to C6 formyl groups is greater than or equal to 5:

1, respectively.

40. The cellulose ester interpolymer of claim 36, wherein the ratio of C6 carboxy groups to C6 formyl groups is less than or equal to 1:

5, respectively.

41. The cellulose ester interpolymer of claim 36, wherein the ratio of C6 carboxy groups to C6 formyl groups is between 5:

1 and 1;

5, respectively.

42. A cellulose interpolymer having a degree of polymerization of at least 10, an acid number of greater than 10, and a random distribution throughout the cellulose interpolymer of anhydroglucose units having a C6 carboxy group.

43. The cellulose interpolymer of claim 42, having an acid number of greater than 30.

44. The cellulose interpolymer of claim 42, having an acid number of greater than 30 and less than 150.

45. The cellulose interpolymer of claim 42, having a weight average molecular weight of at least 5,000 g/mol.

46. The cellulose interpolymer of claim 42, further comprising a plurality of anhydroglucose units having C6 formyl groups.

47. The cellulose interpolymer of claim 46, wherein the ratio of C6 carboxy groups to C6 formyl groups is greater than or equal to 5:

1, respectively.

48. The cellulose interpolymer of claim 46, wherein the ratio of C6 carboxy groups to C6 formyl groups is less than or equal to 1:

5, respectively.

49. The cellulose interpolymer of claim 46, wherein the ratio of C6 carboxy groups to C6 formyl groups is between 5:

1 and 1;

5, respectively.

50. The reaction product of the cellulose interpolymer of claim 46 with a C₂-C₁₂ acyl anhydride or a mixture thereof.

51. A cellulose ester interpolymer comprising anhydroglucose units

52. The cellulose ester interpolymer of claim 51, wherein anhydroglucose units A and B comprise greater than 70% of total anhydroglucose units of the cellulose ester interpolymer.

53. The cellulose ester interpolymer of claim 51, wherein anhydroglucose units A and B comprise greater than 80% of total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer.

54. The cellulose ester interpolymer of claim 51, wherein anhydroglucose units A and B comprise greater than 90% of total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer.

55. The cellulose ester interpolymer of claim 51, wherein the degree of substitution of C₂-C₁₂ acyl groups is from about 1.7 to about 2.3, and having a weight average molecular weight of at least 5,000 g/mol.

56. The cellulose ester interpolymer of claim 51, having a degree of polymerization of at least 10.

57. The cellulose ester interpolymer of claim 51, having a degree of polymerization of at least 25.

58. A cellulose ester interpolymer having a degree of substitution per anhydroglucose unit of formate of 0.5 to 1.3, and a degree of substitution of C₂-C₁₂ acyl of 1.5 to 2.5.

59. The cellulose ester interpolymer of claim 58 having a degree of substitution per anhydroglucose unit of formate of 0.7 to 1.2, and a degree of substitution of C₂-C₁₂ acyl of 1.8 to 2.3.

60. The cellulose ester interpolymer of claim 58 having a degree of substitution per anhydroglucose unit of formate of 0.9 to 1.1, and a degree of substitution of C₂-C₁₂ acyl of 1.9 to 2.1.

61. The cellulose ester interpolymer of claim 58, wherein at least 70% of the total anhydroglucose units of the cellulose ester interpolymer are selected from the group consisting of a 6-O-formate-2,3-O—

C₂-C₁₂ acyl substituted anhydroglucose unit and a 2,3,6-O—

C₂-C₁₂ acyl substituted anhydroglucose unit.

62. The cellulose ester interpolymer of claim 58, wherein at least 80% of the total anhydroglucose units of the cellulose ester interpolymer are selected from the group consisting of a 6-O-formate-2,3-O—

C₂-C₁₂ acyl substituted anhydroglucose unit and a 2,3,6-O—

C₂-C₁₂ acyl substituted anhydroglucose unit.

63. The cellulose ester interpolymer of claim 58, wherein at least 90% of the total anhydroglucose units of the cellulose ester interpolymer are selected from the group consisting of a 6-O-formate-2,3-O—

C₂-C₁₂ acyl substituted anhydroglucose unit and a 2,3,6-O—

C₂-C₁₂ acyl substituted anhydroglucose unit.

64. The cellulose ester interpolymer of claim 58, having a weight average molecular weight of at least 5,000 g/mol.

65. A method for converting a C6 hydroxyl of an anhydroglucose unit of a cellulose polymer to a formyl group or a carboxyl group comprising:

adding an amino substituted cyclic nitroxyl derivative, a primary oxidant, and a terminal oxidant to a cellulose mixture having a pH of less than 4 to form a reaction mixture, wherein

the cellulose mixture comprises a C₂-C₁₂ alkyl acid, water, and a cellulose interpolymer comprising anhydroglucose units having C6 hydroxyl groups; and

passing of a reaction period sufficient to effect conversion of a C6 hydroxyl to a formyl group or a carboxy group and thus produce an oxidized cellulose interpolymer.

66. The method of claim 65, wherein said C₂-C₁₂ alkyl acid comprises acetic acid, propionic, butyric acid, or a mixture thereof.

67. The method of claim 65, wherein the pH of the cellulose mixture is from about 1.5 to about 3.

68. The method of claim 65, wherein the amino substituted cyclic nitroxyl derivative is a 4-amino substituted 2,2,6,6-tetramethyl piperidin-1-oxyl derivative.

69. The method of claim 68, wherein the amino substituted cyclic nitroxyl derivative is 4-amino 2,2,6,6-tetramethyl piperidin-1-oxyl.

70. The method of claim 68, wherein the amino substituted cyclic nitroxyl derivative is a 4-(C₁-C₄ acylamido)-2,2,6,6-tetramethylpiperidin-1-oxyl.

71. The method of claim 68, wherein the amino substituted cyclic nitroxyl derivative is 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl.

72. The method of claim 65, wherein the amount of amino substituted cyclic nitroxyl derivative ranges from about 0.0025 to about 0.1 molar equivalents per mole of anhydroglucose unit monomer in the cellulose interpolymer.

73. The method of claim 65, wherein the primary oxidant comprises salts of Na, K, Mn, Mg, Fe, or Cu, or mixtures thereof.

74. The method of claim 65, wherein the primary oxidant comprises KCl, KBr, NaCl, NaBr, NaI, NaOCl, NaOBr, Oxone, Mn(NO₃)₂, Mn(OAc)₃, KMnO₄, Mn₂O₃, MnO₂, Mg(NO₃)₂, FeCl₃, Cu(NO₃)₂, or mixtures thereof.

75. The method of claim 65, wherein the primary oxidant is Mn(OAc)₃.

76. The method of claim 65, wherein the primary oxidant is Mn(OAc)₃ and the terminal oxidant is peracetic acid.

77. The method of claim 65, wherein the primary oxidant is KMnO₄.

78. The method of claim 65, wherein the amount of primary oxidant ranges from about 0.0001 to about 0.1 molar equivalents per mole of anhydroglucose unit monomer in the cellulose interpolymer.

79. The method of claim 65, wherein the terminal oxidant comprises O₂, ozone, NaOCl, NaOBr, H₂O₂, or CH₃CO₃H.

80. The method of claim 65, wherein the terminal oxidant is CH₃CO₃H.

81. The method of claim 65, wherein the temperature of the reaction mixture is greater than 40°

C. and less than 60°

C.

82. The method of claim 65, wherein water is present in an amount ranging from 1 to 60 weight percent based on total weight of the reaction mixture.

83. The method of claim 65, wherein the oxidized cellulose intepolymer has an acid number greater than 10.

84. The method of claim 65, wherein the oxidized cellulose intepolymer has an acid number greater than 30.

85. The method of claim 65, wherein the oxidized cellulose intepolymer has an acid number between about 30 and 130.

86. The method of claim 65, further comprising the step of isolating an oxidized cellulose interpolymer.

87. The method of claim 65, further comprising reacting the oxidized cellulose interpolymer with a C₂-C₁₂ acyl anhydride or a mixture thereof.

88. A method for converting a C6 hydroxyl of an anhydroglucose unit of a cellulose ester interpolymer to a formyl group or a carboxyl group comprising:

adding an amino substituted cyclic nitroxyl derivative, a primary oxidant, and a terminal oxidant to a cellulose ester mixture having a pH of less than 4 to form a reaction mixture, wherein

the cellulose ester mixture comprises a C₂-C₁₂ alkyl acid, water, and a cellulose ester interpolymer comprising anhydroglucose units having C6 hydroxyl groups; and

passing of a reaction period sufficient to effect conversion of a C6 hydroxyl to a formyl group or a carboxy group and produce an oxidized cellulose ester interpolymer.

89. The method of claim 88, wherein the cellulose ester interpoylmer has a degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of at least 0.5.

90. The method of claim 88, wherein the pH of the cellulose ester mixture is from about 1.5 to about 3.

91. The method of claim 88, wherein the amino substituted cyclic nitroxyl derivative is a 4-amino substituted 2,2,6,6-tetramethyl piperidin-1-oxyl derivative.

92. The method of claim 88, wherein the amino substituted cyclic nitroxyl derivative is 4-amino 2,2,6,6-tetramethyl piperidin-1-oxyl.

93. The method of claim 88, wherein the amino substituted cyclic nitroxyl derivative is a 4-(C₁-C₄ acylamido)-2,2,6,6-tetramethylpiperidin-1-oxyl.

94. The method of claim 88, wherein the amino substituted cyclic nitroxyl derivative is 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl.

95. The method of claim 88, wherein the amount of amino substituted cyclic nitroxyl derivative ranges from about 0.0025 to about 0.1 molar equivalents per mole of anhydroglucose unit monomer in the cellulose ester interpolymer.

96. The method of claim 88, wherein the primary oxidant comprises a salt of Na, K, Mn, Mg, Fe, or Cu, or mixtures thereof.

97. The method of claim 88, wherein the primary oxidant comprises KCl, KBr, NaCl, NaBr, NaI, NaOCl, NaOBr, Oxone, Mn(NO₃)₂, Mn(OAc)₃, KMnO₄, Mn₂O₃, MnO₂, Mg(NO₃)₂, FeCl₃, Cu(NO₃)₂, or mixtures thereof.

98. The method of claim 88, wherein the primary oxidant is manganese triacetate.

99. The method of claim 98, wherein the terminal oxidant is peracetic acid.

100. The method of claim 88, wherein the primary oxidant is KMnO₄.

101. The method of claim 88, wherein the amount of primary oxidant ranges from about 0.0001 to about 0.1 molar equivalents per mole of anhydroglucose unit monomer in the cellulose ester interpolymer.

102. The method of claim 88, wherein the terminal oxidant comprises O₂, ozone, NaOCl, NaOBr, H₂O₂, or CH₃CO₃H.

103. The method of claim 88, wherein the terminal oxidant is CH₃CO₃H.

104. The method of claim 88, wherein the amount of terminal oxidant ranges from about 0.1 to about 10 molar equivalents per mole of anhydroglucose unit monomer in the cellulose ester interpolymer.

105. The method of claim 88, wherein the temperature of the reaction mixture is greater than 40°

C. and less than 60°

C.

106. The method of claim 88, wherein the contact time is of a duration operable to provide an oxidized cellulose ester interpolymer having a degree of polymerization of greater than 10.

107. The method of claim 88, wherein the contact time is of a duration operable to provide an oxidized cellulose ester interpolymer having a degree of polymerization of greater than 10.

108. The method of claim 88, wherein water is present in an amount ranging from 1 to 60 weight percent based on total weight of the reaction mixture.

109. The method of claim 88, wherein the oxidized cellulose ester intepolymer has an acid number greater than 10.

110. The method of claim 88, wherein the oxidized cellulose ester intepolymer has an acid number greater than 30.

111. The method of claim 88, further comprising the step of isolating an oxidized cellulose ester interpolymer.

112. A method for preparing a stable form of a cellulose formate ester interpolymer comprising:

(1) mixing formic acid, water, and an C₂-C₁₂ acyl anhydride to form a mixed anhydride mixture at a first contact temperature;

(2) contacting the mixed anhydride mixture and a cellulose compound to form a reaction mixture at a second contact temperature;

(3) adding an acid catalyst to the reaction mixture;

(4) passing of a formylation period;

wherein

a resulting cellulose formate ester interpolymer has a degree of substitution per anhydroglucose unit of formate of about 0.5 to about 1.5.

113. The method of claim 112, wherein the resulting cellulose formate ester interpolymer has a degree of substitution per anhydroglucose unit of formate of about 0.7 to about 1.2.

114. The method of claim 112, wherein the resulting cellulose formate ester interpolymer has a degree of substitution per anhydroglucose unit of formate of about 0.9 to about 1.1.

115. The method of claim 112, wherein the acid catalyst is sulfuric acid.

116. The method of claim 112, wherein the acid catalyst is added in an amount ranging from about 0.25 to about 15 weight percent based on weight of cellulose compound.

117. The method of claim 112, wherein the amount of formic acid added in step (1) is from about 4 to about 15 molar equivalents based on moles of cellulose compound.

118. The method of claim 112, wherein the first contact temperature ranges from about −

10 to about 15°

C.

119. The method of claim 112, wherein the second contact temperature ranges from about 10 to about 70°

C.

120. The method of claim 112, further comprising the step of isolating the resulting cellulose formate ester interpolymer.

121. A method for preparing a stable form of a cellulose ester interpolymer comprising:

(1) mixing formic acid, water, and an C₂-C₁₂ acyl anhydride to form a mixed anhydride mixture at a first contact temperature;

(2) contacting the mixed anhydride mixture and a cellulose compound to form a reaction mixture at a second contact temperature;

(3) adding an acid catalyst to the reaction mixture;

(4) passing of a formylation period;

(5) adding a C₂-C₁₂ acyl anhydride to the reaction mixture;

(6) heating the reaction mixture to a third contact temperature;

(7) passing of an acylation period;

wherein

a resulting cellulose ester interpolymer has a degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of about 1.5 to about 2.5, and a degree of substitution per anhydroglucose unit of formate of about 0.5 to about 1.5.

122. The method of claim 121, wherein the resulting cellulose ester interpolymer has a degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.8 to 2.3, and a degree of substitution per anhydroglucose unit of formate of 0.7 to 1.2.

123. The method of claim 121, wherein the resulting cellulose ester interpolymer has a degree of substitution per anhydroglucose unit of C₂-C₁₂ acyl of 1.9 to 2.1, and a degree of substitution per anhydroglucose unit of formate of 0.9 to 1.1.

124. The method of claim 121, wherein the acid catalyst is sulfuric acid.

125. The method of claim 121, wherein the acid catalyst is added in an amount ranging from about 0.25 to about 15 weight percent based on weight of cellulose compound.

126. The method of claim 121, wherein the the amount of formic acid added in step (1) is from about 4 to about 13 molar equivalents based on moles of cellulose compound.

127. The method of claim 121, wherein the first contact temperature ranges from about −

10 to about 15°

C.

128. The method of claim 121, wherein the second contact temperature ranges from about 10 to about 70°

C.

129. The method of claim 121, wherein the third contact temperature ranges from about 40 to about 60°

C.

130. The method of claim 121, wherein the C₂-C₁₂ acyl anhydride comprises acetic, propionic, butyric anydride, or mixture thereof.

131. The method of claim 121, further comprising the step of removing by hydrolysis or alcoholysis the formate ester groups substituted on the cellulose ester.

132. The method of claim 121, further comprising the step of isolating the cellulose ester interpolymer.

133. The method of claim 121, further comprising the step of:

adding an amino substituted cyclic nitroxyl derivative, a primary oxidant, and a terminal oxidant to the reaction mixture, wherein the reaction mixture has a pH of less than 4, and

passing of a reaction period sufficient to effect conversion of a C6 hydroxyl group of an anhydroglucose unit of the cellulose ester interpolymer.

134. A method for converting a primary alcohol to a formyl, carboxylate, or mixture thereof, comprising:

adding a 4-substituted piperdine nitroxyl derivative wherein the substitutent is capable of hydrogen bonding, a primary oxidant, and a terminal oxidant to a mixture to form a reaction mixture, wherein

the mixture has a pH of less than about 4 and comprises a compound comprising a primary alcohol functional group;

passing of a reaction period sufficient to effect conversion of the primary alcohol functional group.

135. The method of claim 134, wherein the primary alcohol is a group on a polysaccharide selected from starch esters and other polysaccharides esters having α

-1,4 glycosidic linkages, pullulan esters and other polysaccharides esters having α

-1,3 glycosidic linkages, cellulose esters and other polysaccharides esters having β

-1,4 glycosidic linkages, and other β

-glucan esters selected from chitin, chitosan, fructans, glactomannans, glucomannas, xyloglucans, and arabinoxylans.

136. The method of claim 134, wherein the primary oxidant is a Mn(III) salt.

137. The method of claim 136, wherein the Mn salt is or manganese triacetate.

138. The method of claim 134, wherein the primary oxidant further comprises a salt of Cu, Mg, Fe, Na, K, or mixtures thereof.

139. The method of claim 134, wherein the reaction mixture further comprises water.

140. The method of claim 134, wherein the reaction mixture further comprises water and a C₂-C₁₂ alkyl acid.

141. The method of claim 134, wherein the amino substituted cyclic nitroxyl derivative is a 4-amino substituted 2,2,6,6-tetramethyl piperidin-1-oxyl derivative.

142. The method of claim 134, wherein the amino substituted cyclic nitroxyl derivative is 4-amino 2,2,6,6-tetramethyl piperidin-1-oxyl.

143. The method of claim 134, wherein the amino substituted cyclic nitroxyl derivative is a 4-(C₁-C₄ acylamido)-2,2,6,6-tetramethylpiperidin-1-oxyl.

144. The method of claim 134, wherein the amino substituted cyclic nitroxyl derivative is 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl.

145. The method of claim 134, wherein the amino substituted cyclic nitroxyl derivative is immobilized on an inert resin.

146. A coating composition comprising

(i) about 0.1 to about 50 weight percent, based on the total weight percent of (i) and (ii), in said composition, of cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolymer are in the alcohol oxidation state, and comprising anhydroglucose units

wherein R₁, R₂, R₃, R₄, and R₅ are independently selected from the group consisting of hydrogen and C₂-C₁₂ acyl groups, wherein at least one of R₁, R₂, R₃, R₄, and R₅ is a C₂-C₁₂ acyl group;

and X is formyl, hydroxymethylene, aminomethyl, R₆—

NH—

CH₂—

or carboxy or a mixture thereof, wherein R₆ is selected from the group consisting of alkyl, aryl, or alkylene-aryl, provided when at least some of X is carboxy, the acid number is greater than 10;

wherein the anhydroglucose units A and B comprise greater than 65% of the total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer; and

(ii) about 0.1 to 50 weight percent, based on the total weight of (i) and (ii) in said composition, of a resin which is other than (i); and

(iii) an organic solvent or solvent mixture;

wherein the total weight of (i) and (ii) is about 5 to 70 weight percent of the total weight of (i), (ii), and (iii).

147. The composition of claim 146, wherein the resin which is other than (i) is selected from the group consisting of polyesters, polyester-amides, cellulose esters, alkyds, polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers, polyisocyanates, melamines, silicone resins, and nitrocellulose.

148. The composition of claim 146, further comprising about 0.1 to about 15 weight percent, based on the weight of the composition, of one or more coatings additives selected from the group consisting of leveling, rheology, and flow control agents;

flatting agents;

pigment wetting and dispersing agents;

surfactants;

ultraviolet light absorbers;

ultraviolet light stabilizers;

pigments;

defoaming and anti-foaming agents;

anti-settling, anti-sag and bodying agents;

anti-skimming agents;

anti-flooding and anti-floating agents;

fungicides and mildewcides;

corrosion inhibitors;

thickening agents; and

coalescing agents.

157. An article coated with the composition of claim 146.

149. A waterborne coating composition comprising

(i) about 0.1 to about 50 weight percent, based on the total weight percent of (i) and (ii), in said composition, of cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units

wherein R₁, R₂, R₃, R₄, and R₅ are independently selected from the group consisting of hydrogen and C₂-C₁₂ acyl groups, wherein at least one of R₁, R₂, R₃, R₄, and R₅ is a C₂-C₁₂ acyl group;

and X is formyl, hydroxymethylene, aminomethyl, R₆—

NH—

CH₂—

or carboxy or a mixture thereof, wherein R₆ is selected from the group consisting of alkyl, aryl, or alkylene-aryl, provided when at least some of X is carboxy, the acid number is greater than 10;

wherein the anhydroglucose units A and B comprise greater than 65% of the total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer,

wherein at least about 25 percent of all free carboxyl groups on said interpolymer have been neutralized with a base; and

(ii) at least one compatible water-soluble or water dispersible resin;

(iii) water; and

(iv) at least one organic solvent;

wherein the total weight of (i) and (ii) is between 5 and 50 weight percent of the total composition and the organic solvent comprises less than 20 weight percent of the total weight of the composition.

158. An article coated with the composition of claim 149.

150. A pigment dispersion comprising about 40 to 90 weight percent by weight of at least one pigment and correspondingly about 10 to 60 weight percent of cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units

151. An oral pharmaceutical composition comprising a therapeutic agent having coated thereon or admixed therewith a composition comprising a cellulose ester interpolymer wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units

152. The pharmaceutical composition of claim 151, wherein the composition further comprises a water soluble polymer selected from the group consisting of hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, cellulose acetate phthalate, cellulose acetate succinate, cellulose acetate trimellitate, hydroxypropyl methyl cellulose phthalate, cellulose acetate, cellulose acetate propionate, or cellulose acetate butyrate.

153. The pharmaceutical composition of claim 151, further comprising at least one solubility enhancer.

154. A method for treating a mammal in need thereof, with at least one therapeutic agent, which comprises administering to said mammal an oral pharmaceutical composition comprising a therapeutic agent having coated thereon or admixed therewith a composition comprising a cellulose ester interpolymer wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units

155. The method of claim 154, wherein the cellulose ester interpolymer modifies ordinary release rate profile of the therapeutic agent.

156. The method of claim 154, wherein the cellulose ester interpolymer increases the solubility of the the at least one therapeutic agent, thereby increasing the oral bioavailability.