Amine-functionalized cellulose polymers for CO
Provided herein are amine-functionalized cellulose polymers useful for carbon dioxide capture and methods of preparation and use thereof.
1 . A method of preparing an amine-functionalized polymer comprises: contacting a cellulose polymer comprising a repeating unit of Formula 2:
with an oxidant comprising (i) 0.1-10% wt laccase and 0.1-10% wt (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), wherein the cellulose polymer is present at a concentration of 0.5-2.0% wt, or (ii) 0.1-1% wt NaBr, 0.01-0.1% wt TEMPO, and 0.1-10% wt NaClO, wherein the cellulose polymer is present at a concentration of 5-10% wt, thereby forming an oxidized cellulose polymer comprising a repeating moiety of Formula 3:
or a conjugate salt thereof, wherein
R 3 is —CO 2 H or —CHO;
contacting the oxidized cellulose polymer with a polyalkylenimine or an alkylsilane, with the proviso that when R 3 is —CO 2 H, a coupling agent is also present during the step of contacting the oxidized cellulose polymer with the polyalkylenimine or the alkylsilane; and thereby forming an amine-functionalized polymer comprising a repeating unit of Formula 1:
or a conjugate salt thereof, wherein R 1 is —(C═O)NHR 2 or —H(C═N—R 2 ); and R 2 is a polyalkylenimine or an alkylsilane.
2 . The method of claim 1 , wherein the cellulose polymer is in the form of a cellulose powder or a textile.
3 . The method of claim 1 , wherein the cellulose polymer is present at a concentration of 0.5-10% wt.
4 . The method of claim 1 , wherein the polyalkylenimine is selected from the group consisting of PEI, TEPA, DETA, and PEHA.
5 . The method of claim 1 , wherein the polyalkylenimine is present at a concentration of 2-10% wt.
6 . The method of claim 5 , wherein —R 3 is CO 2 H and the coupling agent comprises N-(3-(dimethylamino) propyl)-N′-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS).
7 . The method of claim 6 , wherein EDC is present at a concentration of 2-8% by wt; and NHS is present at a concentration of 2-8% by wt.
8 . The method of claim 1 , wherein R 3 is —CHO; the step of contacting the cellulose polymer with the oxidant is conducted at 35-45° C., wherein the cellulose polymer is present at a concentration of 0.5-2.0% wt; the oxidant comprises laccase and TEMPO, wherein the laccase is present at a concentration of 0.1-10% wt; and TEMPO is present at a concentration of 0.1-10% wt; and the step of contacting the oxidized cellulose polymer with the polyalkylenimine is conducted at 20-40° C., wherein the polyalkylenimine is PEI and the PEI is present at a concentration of 2-10% wt.
9 . The method of claim 1 , wherein R 3 is —CO 2 H; the step of contacting the cellulose polymer with the oxidant is conducted at 24-40° C., wherein the cellulose polymer is present at a concentration of 5-10% wt; the oxidant comprises NaClO, TEMPO, and NaBr, wherein NaBr is present at a concentration of 0.1-1% wt; TEMPO is present at a concentration of 0.01-0.1%; and NaClO is present at a concentration of 0.1-10% wt; and the step of contacting the oxidized cellulose polymer with the polyalkylenimine is conducted at 20-27° C., wherein the polyalkylenimine is PEI and the coupling agent comprises EDC and NHS, wherein PEI is present at a concentration of 2-10% wt; EDC is present at a concentration of 2-8% by wt; and NHS is present at a concentration of 2-8% by wt.
10 . The method of claim 1 , wherein the polyalkylenimine or the alkylsilane crosslink two or more repeating units of Formula 1.
11 . The method of claim 1 , further comprises contacting the amine-functionalized polymer with CHO(CH 2 ) n CH 2 CHO, wherein n is a whole number selected between 2-6.
12 . The method of claim 1 , wherein the method further comprises the steps of combining the amine-functionalized polymer with a binder thereby forming a surface finishing solution; contacting a textile with the surface finishing solution thereby forming a surface finishing solution treated textile; and optionally curing the surface finishing solution treated textile, wherein the cellulose polymer is in the form of a cellulose powder.
13 . A surface finishing solution treated textile prepared by the method of claim 12 .