Fast and high-capacity intelligent cellulose-based oil-absorbing material and preparation method and use thereof

Abstract

The present disclosure provides a fast and high-capacity intelligent cellulose-based oil-absorbing material and a preparation method and use thereof. The material includes an intelligent response layer and an adsorption layer. The intelligent response layer is a pH-responsive nanofiber layer with an adjustable pH response performance and is obtained by grafting hyperbranched polycarboxylic acid-modified polyethyleneimine on to carboxylated cellulose nanofibers. The hyperbranched polycarboxylic acid is prepared by melting and polycondensing at a high temperature, using trimethylolpropane as a core, citric acid as a reactive monomer, and p-toluenesulfonic acid as a catalyst. The adsorption layer is prepared by coating ferroferric oxide with the carboxylated cellulose nanofibers to prepare magnetic carboxylated cellulose nanofibers, and then modifying the magnetic carboxylated cellulose nanofibers with hexadecylamine.

Claims

1. An intelligent cellulose-based oil-absorbing material, wherein the material comprises an intelligent response layer and an adsorption layer; the intelligent response layer is a pH-responsive nanofiber layer with an adjustable pH response performance, wherein the material is prepared by a method comprising the following steps: S1, preparation of carboxylated cellulose nanofibers: selectively oxidizing hydroxyl groups on C2 and C3 of a cellulose structural unit of a paper pulp to aldehyde groups using sodium periodate to prepare dialdehyde cellulose; then oxidizing the aldehyde groups on C2 and C3 and hydroxyl groups on C6 of the cellulose structural unit of the dialdehyde cellulose to carboxyl groups using a TEMPO reagent to prepare the carboxylated cellulose nanofibers; S2, preparation of the adsorption layer: 1) preparation of a modified magnetic fluid Fe.sub.3O.sub.4: making FeCl.sub.3.6H2O and FeSO4.7H2O undergo a chemical co-precipitation reaction under alkaline conditions to obtain Fe.sub.3O.sub.4 particles, and then using triethylenetetramine as a complexing agent to modify the Fe.sub.3O.sub.4 particles to obtain the modified magnetic fluid Fe.sub.3O.sub.4; 2) preparation of magnetic carboxylated cellulose nanofibers by coating ferroferric oxide onto the carboxylated cellulose nanofibers: dispersing the carboxylated cellulose nanofibers prepared in the step S1 in water to prepare a carboxylated cellulose nanofiber dispersion, after adding the modified magnetic fluid Fe.sub.3O.sub.4 and mixing, adding 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the mixture in turn, then reacting at room temperature for 12 to 18 hours, washing and drying to obtain the magnetic carboxylated cellulose nanofibers comprising Fe.sub.3O.sub.4 coated carboxylated cellulose nanofibers; a mass fraction of the carboxylated cellulose nanofiber dispersion is 2% to 5%, a volume/mass/mass/mass ratio of the carboxylated cellulose nanofiber dispersion, the modified magnetic fluid Fe.sub.3O.sub.4, 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is 150 mL:(0.5-1.0 g):500 mg:500 mg; 3) preparation of the adsorption layer by modifying the magnetic carboxylated cellulose nanofibers with hexadecylamine: dissolving the hexadecylamine in ethanol, dispersing the magnetic carboxylated cellulose nanofibers in water, mixing the hexadecylamine in ethanol and the magnetic carboxylated cellulose nanofibers in water into a mixture, after ultrasonicating for 25 to 35 minutes, adding 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the mixture in turn, then reacting at room temperature for 6 to 24 hours, washing, and freeze drying to prepare the adsorption layer with magnetic responsiveness and a superhydrophobic-superlipophilic performance; and a mass ratio of hexadecylamine, the magnetic carboxylated cellulose nanofibers, 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is (5-10):(3-6):0.25:0.25; S3, preparation of the intelligent response layer: (1) preparation of a hyperbranched polycarboxylic acid by melting and polycondensing: using trimethylolpropane as a core, citric acid as a reactive monomer, and p-toluenesulfonic acid as a catalyst; mixing the trimethylolpropane, the citric acid and the p-toluenesulfonic acid and reacting at 135° C. to 150° C. under stirring conditions for 1.5 to 2.5 hours to obtain the hyperbranched polycarboxylic acid; (2) dissolving polyethyleneimine and the hyperbranched polycarboxylic acid in a sodium hydroxide aqueous solution at a mass ratio of 1:(0.2-0.6) or 1:(1.6-2.2), then adding sodium hypophosphite into the mixture at a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:(0.8-1.2), then after a reaction with stirring at 100° C. to 105° C. is completed, cooling the mixture to room temperature to obtain a hyperbranched polycarboxylic acid-modified polyethyleneimine; when regulating a mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid to 1:(0.2-0.6), so that a molar ratio of amino groups to carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained is 1:(0.1-0.5); or when regulating the mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid to 1:(1.6-2.2), so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained is 1:(1.5-2.0); (3) after mixing the carboxylated cellulose nanofibers prepared in the step S1 and the hyperbranched polycarboxylic acid-modified polyethyleneimine at a mass ratio of 1:(2-20), adding 1-[3-(dimethylamino)propyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the mixture in turn, then reacting at room temperature for 8 to 24 hours, then rinsing with an HCl solution, centrifuging, and freeze drying to graft the hyperbranched polycarboxylic acid-modified polyethyleneimine on to the carboxylated cellulose nanofibers and obtain the intelligent response layer; and a mass ratio of the carboxylated cellulose nanofibers, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is 1:(0.25-0.5):(0.25-0.5); and S4, preparation of the intelligent cellulose-based oil-absorbing material: suction filtering the adsorption layer, then suction filtering the intelligent response layer to form a double-layer structure, a mass ratio of the adsorption layer to the intelligent response layer being (10-50):1; after forming the double-layer structure, controlling a vacuum degree during suction filtration to 0.01 to 0.04 MPa, spraying the cross-linking agent epichlorohydrin on a surface of the double-layer structure, relying on vacuum to penetrate the cross-linking agent inside the material double-layer structure, soaking in water at room temperature for 0.5 to 2.0 hours, and then freeze-drying to form an aerogel to obtain the intelligent cellulose-based oil-absorbing material; a mass of the added epichlorohydrin is 1% to 10% of a total mass of the adsorption layer and the intelligent response layer.

2. The intelligent cellulose-based oil-absorbing material according to claim 1, wherein a specific operation of the preparation of the modified magnetic fluid Fe.sub.3O.sub.4 in the step 1) is as follows: adding deionized water into a mixture of FeCl.sub.3.6H.sub.2O and FeSO.sub.4.7H.sub.2O, stirring in a 70° C. to 80° C. water bath until dissolved, after bubbling nitrogen for 5 to 15 minutes, quickly adding an ammonia water with a mass fraction of 30% to 35%, continuing stirring under nitrogen protection for 1 to 3 hours to obtain the Fe.sub.3O.sub.4 particles; adding the Fe.sub.3O.sub.4 particles into a triethylenetetramine aqueous solution with a mass fraction of 2% to 5%, stirring for 0.5 to 1.0 hours, heating to 90° C. to 95° C., curing with heat preservation for 20 to 30 minutes to obtain the modified magnetic fluid Fe.sub.3O.sub.4; and a mass/mass/volume/volume/volume ratio of FeCl.sub.3.6H.sub.2O, FeSO.sub.4.7H.sub.2O, deionized water, the ammonia water with the mass fraction of 30% to 35% and the triethylenetetramine aqueous solution with the mass fraction of 2% to 5% is 18 g:(9-10 g):20 mL:30 mL:30 mL.

3. The intelligent cellulose-based oil-absorbing material according to claim 1, wherein the paper pulp is one of or a mixture of two or more of a bleached bagasse pulp fiber, a bleached eucalyptus pulp fiber, a bleached bamboo pulp fiber, a bleached masson pine pulp fiber, and a bleached wheat straw pulp fiber.

4. The intelligent cellulose-based oil-absorbing material according to claim 1, wherein the intelligent response layer has an intelligent response performance of superhydrophilic-superoleophobic or superhydrophobic-superlipophilic to pH; the intelligent response layer has a water contact angle <10° and an oil contact angle >150° when having superhydrophilic-superoleophobic property to pH, and has a water contact angle >150° and an oil contact angle <10° when having superhydrophobic-superlipophilic property to pH; regulating the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine to 1:(0.1-0.5) or 1:(1.5-2.0) to regulate a molar ratio of amino groups to carboxyl groups on a fiber of the intelligent response layer to 1:(0.1-0.5) or 1:(1.5-2.0), when the molar ratio of the amino groups to the carboxyl groups is 1:(0.1-0.5) and pH of the intelligent response layer is acidic, the intelligent response layer has superhydrophilic-superoleophobic property, when the pH of the intelligent response layer changes from acidic to alkaline, the intelligent response layer changes from superhydrophilic-superoleophobic property to superhydrophobic-superlipophilic property; when the molar ratio of the amino groups to the carboxyl groups is 1:(1.5-2.0) and the pH of the intelligent response layer is acidic, the intelligent response layer has superhydrophobic-superlipophilic property, when the pH of the intelligent response layer changes from acidic to alkaline, the intelligent response layer changes from superhydrophobic-superlipophilic property to superhydrophilic-superoleophobic property; the adsorption layer has superhydrophobic-superlipophilic performance, with a water contact angle >150° and an oil contact angle <10°.

5. The intelligent cellulose-based oil-absorbing material according to claim 2, wherein the intelligent response layer has an intelligent response performance of superhydrophilic-superoleophobic or superhydrophobic-superlipophilic to pH; the intelligent response layer has a water contact angle <10° and an oil contact angle >150° when having superhydrophilic-superoleophobic property to pH, and has a water contact angle >150° and an oil contact angle <10° when having superhydrophobic-superlipophilic property to pH; regulating the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine to 1:(0.1-0.5) or 1:(1.5-2.0) to regulate a molar ratio of amino groups to carboxyl groups on a fiber of the intelligent response layer to 1:(0.1-0.5) or 1:(1.5-2.0), when the molar ratio of the amino groups to the carboxyl groups is 1:(0.1-0.5) and pH of the intelligent response layer is acidic, the intelligent response layer has superhydrophilic-superoleophobic property, when the pH of the intelligent response layer changes from acidic to alkaline, the intelligent response layer changes from superhydrophilic-superoleophobic property to superhydrophobic-superlipophilic property; when the molar ratio of the amino groups to the carboxyl groups is 1:(1.5-2.0) and the pH of the intelligent response layer is acidic, the intelligent response layer has superhydrophobic-superlipophilic property, when the pH of the intelligent response layer changes from acidic to alkaline, the intelligent response layer changes from superhydrophobic-superlipophilic property to superhydrophilic-superoleophobic property; the adsorption layer has superhydrophobic-superlipophilic performance, with a water contact angle >150° and an oil contact angle <10°.

6. The intelligent cellulose-based oil-absorbing material according to claim 3, wherein the intelligent response layer has an intelligent response performance of superhydrophilic-superoleophobic or superhydrophobic-superlipophilic to pH; the intelligent response layer has a water contact angle <10° and an oil contact angle >150° when having superhydrophilic-superoleophobic property to pH, and has a water contact angle >150° and an oil contact angle <10° when having superhydrophobic-superlipophilic property to pH; regulating the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine to 1:(0.1-0.5) or 1:(1.5-2.0) to regulate a molar ratio of amino groups to carboxyl groups on a fiber of the intelligent response layer to 1:(0.1-0.5) or 1:(1.5-2.0), when the molar ratio of the amino groups to the carboxyl groups is 1:(0.1-0.5) and pH of the intelligent response layer is acidic, the intelligent response layer has superhydrophilic-superoleophobic property, when the pH of the intelligent response layer changes from acidic to alkaline, the intelligent response layer changes from superhydrophilic-superoleophobic property to superhydrophobic-superlipophilic property; when the molar ratio of the amino groups to the carboxyl groups is 1:(1.5-2.0) and the pH of the intelligent response layer is acidic, the intelligent response layer has superhydrophobic-superlipophilic property, when the pH of the intelligent response layer changes from acidic to alkaline, the intelligent response layer changes from superhydrophobic-superlipophilic property to superhydrophilic-superoleophobic property; the adsorption layer has superhydrophobic-superlipophilic performance, with a water contact angle >150° and an oil contact angle <10°.

Description

DETAILED DESCRIPTION

Embodiment 1

(1) S1. Preparation of carboxylated cellulose nanofibers: 20 g of absolute dry bleached bagasse pulp fiber was taken into a conical flask, 1000 mL of a potassium hydrogen phthalate buffer (0.05 M, pH=3) was added, 10.0 g of sodium periodate was then added, after the conical flask was wrapped with tinfoil, stirring was conducted at 30° C. for 4.5 hours, finally 50 mL of ethylene glycol was added to terminate the reaction, and the product was suction filtered, washed and dried to obtain dialdehyde cellulose. 10 g of the dialdehyde cellulose was added with 900 mL of a sodium phosphate buffer (0.05M, pH=6.8), the suspension was stirred in a sealed flask at 500 rmp and 55° C., and then 0.15 g of TEMPO was added, then 5.915 mL of 1.69 M sodium hypochlorite solution was added, finally 10.6535 g of sodium chlorite was added, oxidation was conducted for 17 hours, and 25 mL of ethanol was added to quench, and washing and drying were conducted to obtain the carboxylated cellulose nanofibers.

(2) S2. Preparation of an adsorption layer:

(3) 1) preparation of a modified magnetic fluid Fe.sub.3O.sub.4: 90 g FeCl.sub.3.6H.sub.2O and 45 g FeSO.sub.4.7H.sub.2O were weighed into a 500 mL 3-neck flask, 100 mL deionized water was added, stirring was conducted in a 70° C. water bath until dissolved, after nitrogen was bubbled for 15 minutes, 150 mL of ammonia water with a mass fraction of 30% was quickly added, stirring was continued for 3 hours under the protection of nitrogen, a magnetic was used for separation, deionized water was used to wash until the supernatant is neutral to obtain the Fe.sub.3O.sub.4 particles; the Fe.sub.3O.sub.4 particles were added to 150 mL of triethylenetetramine aqueous solution with a mass fraction of 2%, stirring was conducted for 0.5 hour, temperature was increased to 95° C., curing was conducted with heat preservation for 20 minutes, the solid was separated with a magnet, deionized water was used to wash until the supernatant is neutral to obtain the modified magnetic fluid Fe.sub.3O.sub.4.

(4) 2) preparation of magnetic carboxylated cellulose nanofibers: the carboxylated cellulose nanofibers prepared in the step S1 were dispersed in water to prepare 150 mL of dispersion with a mass fraction of 2%, 0.5 g of modified magnetic fluid Fe.sub.3O.sub.4 was added, after mixed well, 500 mg of 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and 500 mg of N-hydroxysuccinimide were added in turn into the mixture, then reaction was conducted at room temperature for 12 hours, and washing and drying were conducted to obtain the magnetic carboxylated cellulose nanofibers with the carboxylated cellulose nanofibers coating Fe.sub.3O.sub.4.

(5) 3) preparation of an adsorption layer: 5 g of hexadecylamine was dissolved into 50 mL of ethanol, 3 g of the magnetic carboxylated cellulose nanofibers were dispersed into 50 mL of water, the two were mixed, after 25 minutes of ultrasonication, 250 mg of 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and 250 mg of N-hydroxysuccinimide were added in turn in to the mixture, then reaction was conducted at room temperature for 6 hours, after reaction, washing was conducted with ethanol water with a volume fraction of 70%, and freeze drying was conducted to prepare the adsorption layer with magnetic responsiveness and a superhydrophobic-superlipophilic performance.

(6) S3. Preparation of an intelligent response layer:

(7) (1) preparation of hyperbranched polycarboxylic acid: 0.1 mol of trimethylolpropane (13.4 g), 0.3 mol of citric acid (57.6 g) and p-toluenesulfonic acid (0.71 g) were placed in a 250 mL 3-neck flask first; and then the 3-neck flask was placed in an oil bath and was connected with a the mechanical stirring device. The middle port was inserted with a stirrer with a rotation speed of 250 r/min, the left port was plugged with a rubber plug, the right port was connected to a condensation bend, and the top of the flask was covered with a rag to make it easier for water vapor to flow out of the bend during the reaction. The oil bath was set to 140° C., and reaction time was 2 hours. At the end of the reaction, the product hyperbranched polycarboxylic acid was quickly poured from the side port with less water vapor into a small beaker, and the beaker was sealed with plastic wrap, cooled at room temperature, and finally was stored in a dryer.

(8) (2) Polyethyleneimine and hyperbranched polycarboxylic acid were dissolved in 2 wt % sodium hydroxide aqueous solution at a mass ratio of 1:0.2, then sodium hypophosphite was added to the mixture at a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:0.8, then after the reaction was finished by stirring at 100° C., the mixture was cooled to room temperature to obtain the hyperbranched polycarboxylic acid-modified polyethyleneimine; and a mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid was regulated to 1:0.2, so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained was 1:0.1.

(9) (3) After the carboxylated cellulose nanofibers prepared in the step S1 and the hyperbranched polycarboxylic acid-modified polyethyleneimine were mixed well at a mass ratio of 1:2, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (mass ratio of the carboxylated cellulose nanofibers to N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride was 1:0.25) and N-hydroxysuccinimide (mass ratio of the carboxylated cellulose nanofibers to N-hydroxysuccinimide was 1:0.25) were added into the mixture in turn, then reaction was continued for 8 hours at room temperature, then 0.1 mol/L HCl solution was used to rinse, finally centrifugation was conducted at a speed of 10000 r/min to neutral, and freeze drying was conducted to obtain the intelligent response layer.

(10) S4. Preparation of a fast and high-capacity intelligent cellulose-based oil-absorbing material:

(11) The intelligent response layer and the adsorption layer formed a double-layer structure by layer by layer vacuum filtration: the adsorption layer was suction filtered, then the intelligent response layer was suction filtered to form the double-layer structure, and a mass ratio of the adsorption layer to the intelligent response layer was 10:1; after the double-layer structure was formed, a vacuum degree during suction filtration was controlled to 0.01 MPa, a cross-linking agent epichlorohydrin (a mass of the added epichlorohydrin is 1% of a total mass of the adsorption layer and the intelligent response layer) was sprayed on a surface of the double-layer structure by a spray way, the cross-linking agent was penetrated inside the material relying on low vacuum, soaking was conducted in water at room temperature for 0.5 hour, and then freeze drying was conducted to form an aerogel to obtain the fast and high-capacity intelligent cellulose-based oil-absorbing material.

Embodiment 2

(12) S1. Preparation of carboxylated cellulose nanofibers: 20 g of absolute dry bleached bagasse pulp fiber was taken in to a conical flask, 1000 mL of potassium hydrogen phthalate buffer (0.05M, pH=3) was added, 12 g of sodium periodate was then added, after the conical flask was wrapped with tinfoil, stirring was conducted at 35° C. for 4 hours, finally 50 mL of ethylene glycol was added to terminate the reaction, and the product was suction filtered, washed and dried to obtain dialdehyde cellulose. 10 g of the dialdehyde cellulose was added with 900 mL of sodium phosphate buffer (0.05M, pH=6.8), the suspension was stirred in a sealed flask at 500 rmp and 60° C., and then 0.16 g of TEMPO was added, then 5.915 mL of 1.69 M sodium hypochlorite solution was added, finally 10.6535 g of sodium chlorite was added, oxidation was conducted for 16 hours, and 25 mL of ethanol was added to quench, and washing and drying were conducted to obtain the carboxylated cellulose nanofibers.

(13) S2. Preparation of an adsorption layer:

(14) 1) Preparation of a modified magnetic fluid Fe.sub.3O.sub.4: 90 g FeCl.sub.3.6H.sub.2O and 48 g FeSO.sub.4.7H.sub.2O were weighed into a 500 mL 3-neck flask, 100 mL of deionized water was added, stirring was conducted in a 75° C. water bath until dissolved, after nitrogen was bubbled for 10 minutes, 150 mL of ammonia water with a mass fraction of 30% was quickly added, stirring was continued for 2 hours under the protection of nitrogen, a magnetic was used for separation, deionized water was used to wash until the supernatant is neutral to obtain the Fe.sub.3O.sub.4 particles; the Fe.sub.3O.sub.4 particles were added to 150 mL of triethylenetetramine aqueous solution with a mass fraction of 3%, stirring was conducted for 0.75 hour, temperature was increased to 92° C., curing was conducted with heat preservation for 25 minutes, the solid was separated with a magnet, deionized water was used to wash until the supernatant is neutral to obtain the modified magnetic fluid Fe.sub.3O.sub.4.

(15) 2) Preparation of magnetic carboxylated cellulose nanofibers: the carboxylated cellulose nanofibers prepared in the step S1 were dispersed in water to prepare 150 mL of dispersion with a mass fraction of 4%, 0.8 g of the modified magnetic fluid Fe.sub.3O.sub.4 was added, after mixed well, 500 mg of 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and 500 mg of N-hydroxysuccinimide were added into the mixture in turn, then reaction was conducted at room temperature for 15 hours, and washing and drying were conducted to obtain the magnetic carboxylated cellulose nanofibers with the carboxylated cellulose nanofibers coating Fe.sub.3O.sub.4.

(16) 3) Preparation of an adsorption layer: 7.5 g of hexadecylamine was dissolved in 50 mL of ethanol, 4.5 g of the magnetic carboxylated cellulose nanofibers were dispersed in 50 mL of water, the two were mixed, after 30 minutes of ultrasonication, 250 mg of 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and 250 mg of N-hydroxysuccinimide were added into the mixture in turn, then reaction was conducted at room temperature for 12 hours, after reaction, washing was conducted with ethanol water with a volume fraction of 70%, and freeze drying was conducted to prepare the adsorption layer with magnetic responsiveness and a superhydrophobic-superlipophilic performance.

(17) S3. Preparation of an intelligent response layer:

(18) (1) Preparation of hyperbranched polycarboxylic acid: 0.1 mol of trimethylolpropane (13.4 g), 0.35 mol of citric acid (67.2 g) and p-toluenesulfonic acid (0.64 g) were placed in a 250 mL 3-neck flask first; and then the 3-neck flask was placed in an oil bath and was connected with a the mechanical stirring device. The middle port was inserted with a stirrer with a rotation speed of 250 r/min, the left port was plugged with a rubber plug, the right port was connected to a condensation bend, and the top of the flask was covered with a rag to make it easier for water vapor to flow out of the bend during the reaction. The oil bath was set to 135° C., and reaction time was 1.5 hours. At the end of the reaction, the product hyperbranched polycarboxylic acid was quickly poured from the side port with less water vapor into a small beaker, and the beaker was sealed with plastic wrap, cooled at room temperature, and finally was stored in a dryer.

(19) (2) Polyethyleneimine and hyperbranched polycarboxylic acid were dissolved in 2 wt % sodium hydroxide aqueous solution at a mass ratio of 1:0.4, then sodium hypophosphite was added to the mixture at a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:1, then after the reaction was finished by stirring at 100° C., the mixture was cooled to room temperature to obtain the hyperbranched polycarboxylic acid-modified polyethyleneimine; and a mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid was regulated to 1:0.4, so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained was 1:0.3.

(20) (3) After the carboxylated cellulose nanofibers prepared in the step S1 and the hyperbranched polycarboxylic acid-modified polyethyleneimine were mixed well at a mass ratio of 1:10, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (mass ratio of carboxylated cellulose nanofibers to N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride was 1:0.4) and N-hydroxysuccinimide (mass ratio of carboxylated cellulose nanofibers to N-hydroxysuccinimide was 1:0.4) were added into the mixture in turn, then reaction was continued for 12 hours at room temperature, then 0.1 mol/L HCl solution was used to rinse, finally centrifugation was conducted at a speed of 10000 r/min to neutral, and freeze drying was conducted to obtain the intelligent response layer.

(21) S4. Preparation of a fast and high-capacity intelligent cellulose-based oil-absorbing material:

(22) The intelligent response layer and the adsorption layer formed a double-layer structure by layer by layer vacuum filtration: the adsorption layer was suction filtered, then the intelligent response layer was suction filtered to form the double-layer structure, a mass ratio of the adsorption layer to the intelligent response layer was 30:1; after the double-layer structure was formed, a vacuum degree during suction filtration was controlled to 0.03 MPa, a cross-linking agent epichlorohydrin (a mass of the added epichlorohydrin is 5% of a total mass of the adsorption layer and the intelligent response layer) was sprayed on a surface of the double-layer structure by a spray way, the cross-linking agent was penetrated inside the material relying on low vacuum, soaking was conducted in water at room temperature for 1.0 hour, and then freeze drying was conducted to form an aerogel to obtain the fast and high-capacity intelligent cellulose-based oil-absorbing material.

Embodiment 3

(23) S1. Preparation of carboxylated cellulose nanofibers: 20 g of absolute dry bleached bagasse pulp fiber was taken into a conical flask, 1000 mL of potassium hydrogen phthalate buffer (0.05 M, pH=3) was added, 15 g of sodium periodate was then added, after the conical flask was wrapped with tinfoil, stirring was conducted at 40° C. for 3.5 hours, finally 50 mL of ethylene glycol was added to terminate the reaction, and the product was suction filtered, washed and dried to obtain dialdehyde cellulose. 10 g of the dialdehyde cellulose was added with 900 mL of sodium phosphate buffer (0.05 M, pH=6.8), the suspension was stirred in a sealed flask at 500 rmp and 65° C., and then 0.175 g of TEMPO was added, then 5.915 mL of 1.69M sodium hypochlorite solution was added, finally 10.6535 g of sodium chlorite was added, oxidation was conducted for 15 hours, and 10 mL of ethanol was added to quench, and washing and drying were conducted to obtain the carboxylated cellulose nanofibers.

(24) S2. Preparation of an adsorption layer:

(25) 1) Preparation of a modified magnetic fluid Fe.sub.3O.sub.4: 90 g FeCl.sub.3.6H.sub.2O and 50 g FeSO.sub.4.7H.sub.2O were weighed into a 500 mL 3-neck flask, 100 mL of deionized water was added, stirring was conducted in a 80° C. water bath until dissolved, after nitrogen was bubbled for 5 minutes, 150 mL of ammonia water with a mass fraction of 30% was quickly added, stirring was continued for 1 hour under the protection of nitrogen, a magnetic was used for separation, deionized water was used to wash until the supernatant is neutral to obtain the Fe.sub.3O.sub.4 particles; the Fe.sub.3O.sub.4 particles were added to 150 mL of triethylenetetramine aqueous solution with a mass fraction of 5%, stirring was conducted for 1 hour, temperature was increased to 90° C., curing was conducted with heat preservation for 30 minutes, the solid was separated with a magnet, deionized water was used to wash until the supernatant is neutral to obtain the modified magnetic fluid Fe.sub.3O.sub.4.

(26) 2) Preparation of magnetic carboxylated cellulose nanofibers: the carboxylated cellulose nanofibers prepared in the step S1 were dispersed in water to prepare 150 mL of dispersion with a mass fraction of 4%, 1 g of modified magnetic fluid Fe.sub.3O.sub.4 was added, after mixed well, 500 mg of 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and 500 mg of N-hydroxysuccinimide were added into the mixture in turn, then reaction was conducted at room temperature for 18 hours, and washing and drying were conducted to obtain the magnetic carboxylated cellulose nanofibers with the carboxylated cellulose nanofibers coating Fe.sub.3O.sub.4.

(27) 3) Preparation of an adsorption layer: 10 g of hexadecylamine was dissolved in 50 mL of ethanol, 6 g of magnetic carboxylated cellulose nanofibers were dispersed in 50 mL of water, the two were mixed, after 35 minutes of ultrasonication, 250 mg of 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride and 250 mg of N-hydroxysuccinimide were added into the mixture in turn, then reaction was conducted at room temperature for 24 hours, after reaction, washing was conducted with ethanol water with a volume fraction of 70%, and freeze drying was conducted to prepare the adsorption layer with magnetic responsiveness and a superhydrophobic-superlipophilic performance.

(28) S3. Preparation of an intelligent response layer:

(29) (1) Preparation of hyperbranched polycarboxylic acid: 0.1 mol of trimethylolpropane (13.4 g), 0.4 mol of citric acid (76.8 g) and p-toluenesulfonic acid (1.35 g) were placed in a 250 mL 3-neck flask first; and then the 3-neck flask was placed in an oil bath and was connected with a the mechanical stirring device. The middle port was inserted with a stirrer with a rotation speed of 250 r/min, the left port was plugged with a rubber plug, the right port was connected to a condensation bend, and the top of the flask was covered with a rag to make it easier for water vapor to flow out of the bend during the reaction. The oil bath was set to 150° C., and reaction time was 2.5 hours. At the end of the reaction, the product hyperbranched polycarboxylic acid was quickly poured from the side port with less water vapor into a small beaker, and the beaker was sealed with plastic wrap, cooled at room temperature, and finally was stored in a dryer.

(30) (2) Polyethyleneimine and hyperbranched polycarboxylic acid were dissolved in 2 wt % sodium hydroxide aqueous solution at a mass ratio of 1:0.6, then sodium hypophosphite was added to the mixture at a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:1.2, then after the reaction was finished by stirring at 105° C., the mixture was cooled to room temperature to obtain the hyperbranched polycarboxylic acid-modified polyethyleneimine; and a mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid was regulated to 1:0.6, so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained was 1:0.5.

(31) (3) After the carboxylated cellulose nanofibers prepared in the step S1 and the hyperbranched polycarboxylic acid-modified polyethyleneimine were mixed well at a mass ratio of 1:20, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (mass ratio of carboxylated cellulose nanofibers to N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride was 1:0.5) and N-hydroxysuccinimide (mass ratio of carboxylated cellulose nanofibers to N-hydroxysuccinimide was 1:0.5) were added into the mixture in turn, then reaction was continued for 24 hours at room temperature, then 0.1 mol/L HCl solution was used to rinse, finally centrifugation was conducted at a speed of 10000 r/min to neutral, and freeze drying was conducted to obtain the intelligent response layer.

(32) S4. Preparation of a fast and high-capacity intelligent cellulose-based oil-absorbing material:

(33) The intelligent response layer and the adsorption layer formed a double-layer structure by layer by layer vacuum filtration: the adsorption layer was suction filtered, then the intelligent response layer was suction filtered to form the double-layer structure, a mass ratio of the adsorption layer to the intelligent response layer was 50:1; after the double-layer structure was formed, a vacuum degree during suction filtration was controlled to 0.04 MPa, a cross-linking agent epichlorohydrin (a mass of the added epichlorohydrin is 10% of a total mass of the adsorption layer and the intelligent response layer) was sprayed on a surface of the double-layer structure by a spray way, the cross-linking agent was penetrated inside the material relying on low vacuum, soaking was conducted in water at room temperature for 2.0 hour, and then freeze drying was conducted to form an aerogel to obtain the fast and high-capacity intelligent cellulose-based oil-absorbing material.

Embodiment 4

(34) The differences from Embodiment 1 were that in the step S3 (2), the polyethyleneimine and the hyperbranched polycarboxylic acid were dissolved in 2 wt % sodium hydroxide aqueous solution at a mass ratio of 1:1.6, and then sodium hypophosphite was added into the mixture with a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:0.8, then after a reaction of stirring at 100° C. was completed, the mixture was cooled to room temperature to obtain the hyperbranched polycarboxylic acid-modified polyethyleneimine; the mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid was regulated to 1:1.6, so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained was 1:1.5; and other steps and methods are the same as Embodiment 1.

Embodiment 5

(35) The differences from Embodiment 1 were that in the step S3 (2), the polyethyleneimine and the hyperbranched polycarboxylic acid were dissolved in 2 wt % sodium hydroxide aqueous solution at a mass ratio of 1:1.9, and then sodium hypophosphite was added into the mixture with a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:0.8, then after a reaction of stirring at 100° C. was completed, the mixture was cooled to room temperature to obtain the hyperbranched polycarboxylic acid-modified polyethyleneimine; the mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid was regulated to 1:1.9, so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained was 1:1.75; and other steps and methods are the same as Embodiment 1.

Embodiment 6

(36) The differences from Embodiment 1 were that in the step S3 (2), the polyethyleneimine and the hyperbranched polycarboxylic acid were dissolved in 2 wt % sodium hydroxide aqueous solution at a mass ratio of 1:2.2, and then sodium hypophosphite was added into the mixture with a mass ratio of the polyethyleneimine to sodium hypophosphite of 1:0.8, then after a reaction of stirring at 100° C. was completed, the mixture was cooled to room temperature to obtain the hyperbranched polycarboxylic acid-modified polyethyleneimine; the mass ratio of the polyethyleneimine to the hyperbranched polycarboxylic acid was regulated to 1:2.2, so that the molar ratio of the amino groups to the carboxyl groups on the hyperbranched polycarboxylic acid-modified polyethyleneimine correspondingly obtained was 1:2.0; and other steps and methods are the same as Embodiment 1.

(37) Performance Test of the Fast and High-Capacity Intelligent Cellulose-Based Oil-Absorbing Materials Prepared in Embodiments 1-6:

(38) 1. Test of Oil Absorption Rate and Regeneration Rate of the Materials Prepared in Embodiments 1-6:

(39) Oil product was put into a dry beaker, the sample was put into the beaker containing the oil products, after 2 minutes' standing and adsorption under normal temperature conditions, the material was taken out for standing and draining, and weighed, and the test was repeated three times for the average.

(40) Calculation Formula of Oil Absorption Rate:
Q=(m.sub.2−m.sub.1)/m.sub.1

(41) Where: Q denotes the oil absorption rate (g/g); m.sub.1 denotes the mass (g) of dry oil-absorbing material; and m.sub.2 denotes the mass (g) of oil-absorbing material after oil absorption.

(42) Calculation Formula of Regeneration Rate:
R=Q′/Q

(43) Where: R denotes the regeneration rate (%); Q denotes the oil absorption rate (g/g) of the first oil absorption; and Q′ denotes the oil absorption rate (g/g) of the Nth oil absorption.

(44) The oil absorption rates of the materials prepared in Embodiments 1-6 in various oil products are shown in Table 1 below:

(45) TABLE-US-00001 crude oil diesel gasoline engine oil peanut oil oil absorption oil absorption oil absorption oil absorption oil absorption Item rate (2 min) rate (2 min) rate (2 min) rate (2 min) rate (2 min) Embodiment 1 121 g/g 113 g/g 117 g/g 124 g/g 119 g/g Embodiment 2 120 g/g 113 g/g 119 g/g 125 g/g 120 g/g Embodiment 3 123 g/g 115 g/g 117 g/g 123 g/g 119 g/g Embodiment 4 122 g/g 114 g/g 118 g/g 127 g/g 118 g/g Embodiment 5 121 g/g 117 g/g 116 g/g 124 g/g 120 g/g Embodiment 6 123 g/g 116 g/g 117 g/g 125 g/g 119 g/g

(46) It can be concluded from the data in Table 1 that the adsorption layers of the materials prepared by the present disclosure are a chemically grafted hydrophobic lipophilic reagent (hexadecylamine), and the grafting rate of the reagent on the fiber is higher than 115%, realizing the superhydrophobic-superlipophilic performance of the absorption layer, with a water contact angle >150° and an oil contact angle <10°, so the materials have very high adsorption capacity and fast adsorptivity for the variety of oil products, and their adsorption capacities are greater than 112 g/g within 2 minutes.

(47) After oil absorption, it is regenerated by mechanical compression, and after repeated 10 times, the oil absorption rate is shown in Table 2 below:

(48) TABLE-US-00002 crude oil diesel gasoline engine oil peanut oil oil oil oil oil oil absorption absorption absorption absorption absorption rate regeneration rate regeneration rate regeneration rate regeneration rate regeneration Item (2 min) rate (2 min) rate (2 min) rate (2 min) rate (2 min) rate Embod- 114 94.2% 105 92.9% 109 93.2% 117 94.4% 111 93.3% iment g/g g/g g/g g/g g/g 1 Embod- 111 92.5% 103 91.2% 110 92.4% 116 92.8% 110 91.7% iment g/g g/g g/g g/g g/g 2 Embod- 115 93.5% 106 92.2% 109 93.2% 115 93.5% 111 93.3% iment g/g g/g g/g g/g g/g 3 Embod- 115 94.3% 106 93.0% 109 92.4% 120 94.5% 110 93.2% iment g/g g/g g/g g/g g/g 4 Embod- 113 93.4% 108 92.3% 107 92.2% 116 93.5% 112 94.2% iment g/g g/g g/g g/g g/g 5 Embod- 114 92.7% 107 92.2% 108 92.3% 116 92.8% 111 93.3% iment g/g g/g g/g g/g g/g 6

(49) It can be concluded from the data in Table 2 that the materials of the present disclosure can be regenerated by compression after adsorption, and after being regenerated by mechanical compression, after repeated 10 times, their regeneration rates are higher than 90%, and they can still maintain a good adsorption effect.

(50) 2. Test of Contact Angle of the Intelligent Response Layer Prepared in Embodiments 1-6:

(51) The intelligent response layers prepared in Embodiments 1-6 were soaked in treatment solutions of different pH for 30 minutes, respectively, and after taking out, they were dried at 60° C. for 12 hours to obtain samples treated with treatment solutions of different pH.

(52) TABLE-US-00003 Sample Treatment for sample Sample 1 The intelligent response layer prepared in Embodiment 1 was treated with HCl aqueous solution with pH <7 Sample 2 The intelligent response layer prepared in Embodiment 1 was treated with NaOH aqueous solution with pH >7 Sample 3 The intelligent response layer prepared in Embodiment 2 was treated with HCl aqueous solution with pH <7 Sample 4 The intelligent response layer prepared in Embodiment 2 was treated with NaOH aqueous solution with pH >7 Sample 5 The intelligent response layer prepared in Embodiment 3 was treated with HCl aqueous solution with pH <7 Sample 6 The intelligent response layer prepared in Embodiment 3 was treated with NaOH aqueous solution with pH >7 Sample 7 The intelligent response layer prepared in Embodiment 4 was treated with HCl aqueous solution with pH <7 Sample 8 The intelligent response layer prepared in Embodiment 4 was treated with NaOH aqueous solution with pH >7 Sample 9 The intelligent response layer prepared in Embodiment 5 was treated with HCl aqueous solution with pH <7 Sample 10 The intelligent response layer prepared in Embodiment 5 was treated with NaOH aqueous solution with pH >7 Sample 11 The intelligent response layer prepared in Embodiment 6 was treated with HCl aqueous solution with pH <7 Sample 12 The intelligent response layer prepared in Embodiment 6 was treated with NaOH aqueous solution with pH >7

(53) The contact angle test results of the above samples 1-12 are shown in Table 3 below:

(54) TABLE-US-00004 Water Oil Sample contact angle contact angle Sample 1  8° 157° Sample 2 156°  8° Sample 3  8° 158° Sample 4 159°  8° Sample 5  6° 158° Sample 6 159°  6° Sample 7 157°  7° Sample 8  7° 157° Sample 9 165°  6° Sample 10  6° 163° Sample 11 162°  8° Sample 12  8° 162°

(55) The test results show that the intelligent response layers of the materials show good pH response performance, and their intelligent response layers have the intelligent response performance of superhydrophilic-superoleophobic (water contact angle <10°, oil contact angle >150°) and superhydrophobic-superlipophilic (water contact angle >150°, oil contact angle <10°) to pH. By cleverly conceiving and designing the combination of two groups with opposite pH response properties (amino group and carboxyl group), and thereby designing the required response performance according to application requirements, surface properties of the intelligent response layer can switch between superhydrophilic-superoleophobic and superhydrophobic-superlipophilic. That is, it can realize superhydrophilic-superoleophobic under acidic conditions and superhydrophobic-superlipophilic under alkaline conditions, and can also realize superhydrophobic-superlipophilic under acidic conditions and superhydrophilic-superoleophobic under alkaline conditions. It provides convenience for the application of materials in the field of emulsified oil separation.

(56) 3. Adsorption Effect Test of the Materials Prepared in Embodiments 1-6 on Emulsified Oil:

(57) The materials prepared in Embodiments 1-6 were soaked in treatment solutions of different pH for 30 minutes, respectively, and after taking out, they were dried at 60° C. for 12 hours to obtain samples treated with treatment solutions of different pH. The emulsified oil was put into a dry beaker, the sample was put into the beaker containing the emulsified oil, after 2 minutes' standing and adsorption under normal temperature conditions, the material was taken out for standing and draining, and weighed, and the oil absorption rate thereof was calculated.

(58) TABLE-US-00005 Sample Treatment for sample Sample 1' The material prepared in Embodiment 1 was treated with HCl aqueous solution with pH <7 Sample 2' The material prepared in Embodiment 1 was treated with NaOH aqueous solution with pH >7 Sample 3' The material prepared in Embodiment 2 was treated with HCl aqueous solution with pH<7 Sample 4' The material prepared in Embodiment 2 was treated with NaOH aqueous solution with pH >7 Sample 5' The material prepared in Embodiment 3 was treated with HCl aqueous solution with pH <7 Sample 6' The material prepared in Embodiment 3 was treated with NaOH aqueous solution with pH >7 Sample 7' The material prepared in Embodiment 4 was treated with HCl aqueous solution with pH <7 Sample 8' The material prepared in Embodiment 4 was treated with NaOH aqueous solution with pH >7 Sample 9' The material prepared in Embodiment 5 was treated with HCl aqueous solution with pH <7 Sample 10' The material prepared in Embodiment 5 was treated with NaOH aqueous solution with pH >7 Sample 11' The material prepared in Embodiment 6 was treated with HCl aqueous solution with pH <7 Sample 12' The material prepared in Embodiment 6 was treated with NaOH aqueous solution with pH >7

(59) The oil absorption rates of the above samples 1′, 3′, 5′, 8′, 10′, 12′ in the oil-in-water emulsified diesel are shown in Table 4 below:

(60) TABLE-US-00006 Oil-in-water emulsified diesel (containing 90 wt % water) Item oil absorption rate (2 min) Sample 1' 112 g/g Sample 3' 112 g/g Sample 5' 114 g/g Sample 8' 113 g/g Sample 10' 113 g/g Sample 12' 112 g/g

(61) The oil absorption rates of the above samples 2′, 4′, 6′, 7′, 9′, 11′ in the water-in-oil emulsified diesel are shown in Table 5 below:

(62) TABLE-US-00007 Water-in-oil emulsified diesel (containing 5 wt % water) Item oil absorption rate (2 min) Sample 2' 112 g/g Sample 4' 113 g/g Sample 6' 113 g/g Sample 7' 112 g/g Sample 9' 115 g/g Sample 11' 114 g/g

(63) The test results show that the materials show good pH response performance, and their intelligent response layers have the intelligent response performance of superhydrophilic-superoleophobic (water contact angle <10°, oil contact angle >150°) and superhydrophobic-superlipophilic (water contact angle >150°, oil contact angle <10°) to pH. For demulsification of the emulsified oil, the superhydrophilic-superoleophobic property of the material realizes the demulsification of the oil-in-water O/W type emulsified oil, the superhydrophilic-superoleophobic property realizes the demulsification of the water-in-oil W/O type emulsified oil. After emulsified oil is demulsified, the oil can be adsorbed, and the adsorption capacity can be greater than 112 g/g within 2 minutes.