Multi-stage catalytic carboxylation of mercerized cellulose fibers
View Patent ↗Carboxylated, mercerized cellulose fiber having at least 12 meq/100 g of carboxyl substitution at the C-6 position of the anhydroglucose units, which includes at least 20% cellulose II, may be produced by catalytically carboxylating mercerized cellulose fiber in at least two catalytic carboxylation stages in a continuous series in which the pH is adjusted, and a primary oxoammonium salt catalyst (or precursor thereof) and secondary oxidant is added, at the beginning of each stage. Optionally, the carboxylated, mercerized cellulose may be made substantially free of aldehyde groups by means of a stabilizing step following the final carboxylation stage, in which aldehyde groups present in the fibers are converted to carboxyl groups.
1. A method of producing fibrous carboxylated cellulose, the method comprising:
obtaining mercerized cellulose fibers;
carboxylating the mercerized cellulose fibers by catalytically carboxylating said fibers in an aqueous alkaline suspension in at least two catalytic carboxylation stages, with each of said stages carried out in one of at least two corresponding catalytic carboxylation reactors, in which said stages and reactors are in series and each later stage and reactor further carboxylates the fibers from the previous stage and reactor;
wherein the first stage of the at least two catalytic carboxylation stages is carried out in a first reactor and includes adjusting the pH of the fibers to 8-11, followed by providing amounts of a precursor of an active oxoammonium salt catalyst and a secondary oxidant adapted to generate the active catalyst sufficient to effect carboxylation;
wherein each subsequent stage of the at least two catalytic carboxylation stages is carried out in a subsequent reactor and a includes adjusting the pH of the fibers to 8-11, followed by providing additional amounts of the precursor and the secondary oxidant sufficient to effect further carboxylation;
wherein the time in each of the at least two catalytic carboxylation stages is about 10 seconds to 5 minutes; and
wherein the precursor is selected from the group consisting of heterocyclic nitroxides in which the carbon atoms adjacent the nitroxide nitrogen lack hydrogen substitution, their corresponding amines and hydroxylamines, and mixtures thereof, and is stable under aqueous alkaline conditions.
2. The method of claim 1 , wherein the obtaining further includes mercerizing native cellulose fibers to obtain mercerized cellulose that includes at least 20% cellulose II.
3. The method of claim 2 , wherein the mercerizing includes treating one or more of native northern bleached softwood kraft and native southern bleached softwood kraft cellulose fibers in aqueous sodium hydroxide concentrations of about 14-18%.
4. The method of claim 3 , wherein the mercerizing is performed at a temperature of at least 50° C. over a period of about 5-30 minutes.
5. The method of claim 3 , wherein the native cellulose fibers are below about 4% consistency.
6. The method of claim 1 , wherein the precursor is one or more of 2,2,6,6-tetramethylpiperidinyl-1-oxy free radical (TEMPO) and triacetoamine ethylene glycol ketal nitroxide (TAA-EGK-NO).
7. The method of claim 1 , wherein the secondary oxidant is one or more of chlorine dioxide, chlorine, sodium hypochlorite and sodium bromide.
8. The method of claim 1 , further including:
subsequent to the last stage of the at least two catalytic carboxylation stages, stabilizing the carboxylated fibers by treating the fibers with a stabilizing agent under conditions adapted to convert aldehyde groups present in the fibers to carboxyl groups.
9. The method of claim 8 , wherein the stabilizing agent includes one or more tertiary oxidizers selected from a group consisting of a peroxide, a chlorite, and an acid.
10. The method of claim 8 , wherein the stabilizing agent includes one or more of sodium chlorite, hydrogen peroxide, and sulfuric acid.
11. The method of claim 8 , wherein the stabilizing is performed at a pH of about 1.0-3.5.
12. The method of claim 11 , wherein the stabilizing is performed at about 40-70° C.
13. The method of claim 11 , wherein the stabilizing is performed over a period of about 30 minutes to 2 hours.