Methods for Biodegradable Derivatization of Cellulosic Surfaces

Abstract

The present invention describes methods of treating cellulosic materials with a composition that provides increased hydrophobicity to such materials without sacrificing the biodegradability thereof. The methods as disclosed provide for esterification of available hydroxyl groups on cellulosic materials, where such hydroxyl groups are “masked” by bulky organic chains, including that the disclosure provides products made by such methods. The materials thus treated display higher hydrophobicity, barrier function, and mechanical properties, and may be used in any application where such features are desired.

1 . A method for treating a surface of a solid cellulose-containing material comprising:
 applying to said surface a composition comprising:
 an alkanoic acid derivative having the formula (I) or formula (II):
   R—CO—X  Formula (I)
 
   X—CO—R—CO—X 1   (II) Formula (II),
 
 
   
       wherein R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 6 to 50 carbon atoms, and wherein X and X 1  are independently Cl, Br, or O(CO)OR,
 a base, and 
 a first solvent; 
 heating the applied composition on said surface; 
 rinsing said surface with a second solvent; and 
 drying said rinsed surface, 
 
       wherein said composition esterifies at least a portion of the hydroxyl groups available on the surface of the cellulose-containing material. 
     
     
         2 . The method of  claim 1 , wherein the surface of the solid cellulose-containing material exhibits greater hydrophobicity relative to the surface of the solid cellulose-containing material without said treating. 
     
     
         3 . The method of  claim 1 , wherein the base is non-nucleophilic. 
     
     
         4 . The method of  claim 3 , wherein the base is organic. 
     
     
         5 . The method of  claim 4 , wherein the organic base is selected from the group consisting of aziridines, azetidines, piperazines, piperidines, pyridines, bipyridines, terpyridines, dihydropyridines, morpholines: N-alkylmorpholines, 1,4-diazabicyclo[2.2.2]octanes, 1,8-diazabicycloundecanes, 1,8-diazabicycloundecenes, dimethylated pentylamines, trimethylated pentylamines, pyrimidines, pyrroles, pyrrolidines, pyrrolidinones, indoles, indolines indanones, benzindazones, imidazoles, benzimidazoles, imidazolones, imidazolines, oxazoles, isoxazoles, oxazolines, oxadiazoles, thiadiazoles, carbazoles, quinolines, isoquinolines, naphthyridines, triazines, triazoles, tetrazoles, triethylamines, pyrazoles, pyrazolines and combinations thereof. 
     
     
         6 . The method of  claim 1 , wherein the first and second solvents are selected from the group consisting of pentane, hexane, heptane, octane, petroleum ether, naphtha, kerosene, petroleum, paraffin oil, benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, methylene chloride, chloroform, 1,2-dichloro-ethane, chlorobenzene, carbon tetrachloride, tetrabromoethylene, cyclopentane, cyclohexane, methylcyclohexane, anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzyl ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether, tetrahydrofuran, triisopropyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether (diglyme), diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycol monobutyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol monomethyl ether, acetone, diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methyl isobutyl ketone, methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate and combinations thereof. 
     
     
         7 . The method of  claim 1 , wherein the solid cellulose-containing material comprises a cellulose selected from the group consisting of nanocellulose, cellulose nanofibres, whiskers or microfibril, microfibrillated or nanofibril cellulose, sugarcane cellulose, cotton or cotton blends, and combinations thereof. 
     
     
         8 . The method of  claim 1 , wherein the solid cellulose-containing material is selected from the group consisting of a carton for food storage, a bag for food storage, a shopping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle, for non-carbonated liquid storage, film for wrapping food, a garbage disposal container, a food handling implement, a fabric fibre, a water storage, and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic, goods, an internal or external piece of furniture, a curtain, upholstery, film, box, sheet, tray, pipe, water conduit, clothing, medical device, contraceptive, camping equipment, molded material and combinations thereof. 
     
     
         9 . The method of  claim 1 , wherein the alkanoic acid derivative is selected from the group consisting of acid chlorides, acid bromides, acid iodides, anhydrides, ketenes, diketenes, chlorocarbolic acid esters, carbonic acid diesters, 2,5-diketooxazolidines, isatinic anhydride, isocyanates, carbamoyl chlorides, thiocyanates, thiocarbamoyl chlorides, sulfonyl chlorides, sulfonic acid anhydrides, N-chlorosulfonamides, sulfinic acid chlorides, N-chlorosulfinamides, and combinations thereof, 
       wherein the resulting surface of the solid cellulose-containing material exhibits a water contact angle of between about 60° to about 120°. 
     
     
         10 . The method of  claim 1 , wherein said esterified hydroxyl groups are stable from about −100° C. to about 300° C. 
     
     
         11 . The method of  claim 1 , wherein the portion of the available hydroxyl groups esterified on the surface of the cellulose of the material is greater than about 40%. 
     
     
         12 . The method of  claim 1 , the portion of the available hydroxyl groups esterified on the surface of the cellulose of the material greater than about 50%. 
     
     
         13 . The method of  claim 1 , wherein the portion of the available hydroxyl groups esterified on the surface of the cellulose of the material is between about 60-90%. 
     
     
         14 . The method of  claim 1 , wherein the resulting solid cellulose-containing material is contained in a product selected from the group consisting of a carton for food storage, a bag for food storage, a shipping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposal container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internal or external piece of furniture, a curtain, upholstery, fabric, film, box, sheet, tray, pipe, water conduit, clothing, medical device, contraceptive, camping equipment, molded material and combinations thereof. 
     
     
         15 . The solid cellulose-containing material of  claim 27 , wherein the esterified solid cellulose-containing material has a water vapour permeability of less than about 20 Barrer units. 
     
     
         16 . The solid cellulose-containing material of  claim 27 , wherein the esterified solid cellulase-containing material has an oxygen permeability of less than about 10 Barrer units. 
     
     
         17 . A product resulting from the process of  claim 1 , wherein the solid surface of the cellulose-containing material exhibits a water contact angle of between about 60° to about 120°. 
     
     
         18 . The product of  claim 17 , wherein said esterified hydroxyl groups are stable from about −100° C. to about 300° C. 
     
     
         19 . The product of  claim 17 , wherein the water vapour permeability of the treated surface is less than about 20 Barrer units. 
     
     
         20 . The product of  claim 17 , wherein the oxygen permeability of the treated surface is less than about 10 Barter units. 
     
     
         21 . The product of  claim 17 , wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is greater than 40%. 
     
     
         22 . The product of  claim 17 , wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is greater than 50%. 
     
     
         23 . The product of  claim 17 , wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is between about 60-90%. 
     
     
         24 . The product of  claim 17 , wherein the product is biodegradable. 
     
     
         25 . The product of  claim 17 , wherein the product is selected from the group consisting of a carton for food storage, a bag for food storage, a shopping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposal container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internal or external piece of furniture, a curtain, upholstery, fabric, film, box, sheet, tray, pipe, water conduit, clothing, medical device, contraceptive, camping equipment and combinations thereof. 
     
     
         26 . A method for treating a surface of a solid cellulose-containing material comprising:
 applying to said surface a composition comprising:
 an alkanoic acid derivative having the formula (I) or formula (II):
   R—CO—X  Formula (I)
 
   X—CO—R—CO—X 1   Formula (II),
 
 
 wherein R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 10 to 40 carbon atoms, and wherein X and X1 are independently Cl, Br, or O(CO)OR; 
 a base, and 
 a first solvent, 
   heating the applied composition on said surface;   rinsing said surface with a second solvent; and   drying said rinsed surface,   wherein the resulting treated cellulose-containing material exhibits properties selected from the group consisting of a water contact angle of about 100°, is stable up to at least about 200° C., an oxygen permeability of less than about 10 Barrer units, a water vapour permeability of less than about 20 Barrer units, contains hydroxyl groups esterified on the surface of the cellulose-containing material is greater than about 40%, and combinations thereof.   
     
     
         27 . A solid cellulose-containing material, wherein at least a portion of the oxygen atoms contained in the hydroxyl groups available on the surface of the solid cellulose-containing material are attached directly via an ester bond to the carbon atom of the acyl group of an alkanoic acid derivative having the formula (I):
   R—CO—
   
       wherein R is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 10 to 40 carbon atoms, and wherein the surface of the esterified solid cellulose-containing material exhibits a water contact angle of between 60° to about 120°. 
     
     
         28 . The solid cellulose-containing material of  claim 27 , wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is greater than 40%. 
     
     
         29 . The solid cellulose-containing material of  claim 27 , wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is greater than 50%. 
     
     
         30 . The solid cellulose-containing material of  claim 27 , wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is between about 60-90%. 
     
     
         31 . The solid cellulose-containing material of  claim 27 , wherein the number of carbon atoms in the alkanoic acid derivative is 12 or 14. 
     
     
         32 . The solid cellulose-containing material of  claim 27 , wherein the solid cellulose-containing material is selected from the group consisting of a carton for food storage, a bag for food storage, a shipping bag, eating utensil, container for holding hot or cold beverages, cup, plate, a bottle for carbonated liquid storage, a bottle for non-carbonated liquid storage, film for wrapping food, a garbage disposal container, a food handling implement, a fabric fibre, a water storage and conveying implement, a storage and conveying implement for alcoholic or non alcoholic drinks, an outer casing or screen for electronic goods, an internal or external piece of furniture, a curtain, upholstery, fabric, film, box, sheet, tray, pipe, water conduit, clothing, medical device, contraceptive, camping equipment and combinations thereof. 
     
     
         33 . The solid cellulose-containing material of  claim 27 , wherein the product is biodegradable. 
     
     
         34 . The solid cellulose-containing material of  claim 27 , wherein the esterified solid cellulose-containing material comprises a cellulose selected from the group consisting of nanocellulose, cellulose nanofibres whiskers or microfibril, microfibrillated or nanofibril cellulose, sugarcane cellulose, cotton or cotton blends and combinations thereof. 
     
     
         35 . A solid cellulose-containing material, wherein at least a portion of the oxygen atoms contained in the hydroxyl groups available on the surface of the solid cellulose-containing material are attached directly via an ester bond to the carbon atom of the acyl group of an alkanoic acid derivative having the formula (I):
   R—CO—
   
       wherein K is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon radical having from 10 to 40 carbon atoms, wherein the surface of the esterified solid cellulose-containing material exhibits a water contact angle of between 60° to about 120°, wherein the portion of the hydroxyl groups esterified on the surface of the cellulose-containing material is greater than 40%, wherein the esterified solid cellulose-containing material has a an oxygen permeability of less than about 10 Barrer units, a water vapour permeability of less than about 20 Barrer units and wherein said esterified hydroxyl groups are stable from about −100° C. to about 300° C.