CN109826015B - temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof - Google Patents
temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109826015B CN109826015B CN201910093161.2A CN201910093161A CN109826015B CN 109826015 B CN109826015 B CN 109826015B CN 201910093161 A CN201910093161 A CN 201910093161A CN 109826015 B CN109826015 B CN 109826015B
- Authority
- CN
- China
- Prior art keywords
- temperature
- dual
- sensitive
- response
- hyperbranched polyamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention provides a temperature-sensitive/pH dual-response intelligent nanofiber material and a preparation method and application thereof, wherein hyperbranched polyamine is simultaneously modified by two temperature-sensitive monomers, namely 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate, and then the hyperbranched polyamine is grafted on cellulose nanofibers to prepare the temperature-sensitive/pH dual-response intelligent nanofiber material with good pH responsiveness and temperature responsiveness, the material can realize intelligent conversion of super-hydrophilic and super-hydrophobic, super-oleophilic and super-oleophobic under the stimulus response conditions of temperature and pH respectively, and the low critical solution temperature of the material can be controllably adjusted within the range of 37-50 ℃. The temperature-sensitive/pH dual-response intelligent nanofiber material can be widely applied to the fields of drug slow release, oil-water separation and the like.
Description
Technical Field
The invention belongs to the technical field of nanofiber modification, and particularly relates to a temperature-sensitive/pH dual-response intelligent nanofiber material as well as a preparation method and application thereof.
Background
Responsive smart materials are attracting increasing attention due to the fact that smart responsive surfaces have switchable wettability. Due to their outstanding properties in numerous applications (controlled drug delivery, cell encapsulation, oil/water separation, microfluidic channels and sensors), and at the same time, with the constant development of scientific technology and surface chemistry, more and more smart surfaces with switchable water and/or oil wettability have been developed. As for the change mechanism, the wettability transformation of the surface may be achieved by reversible changes in the surface chemical composition and/or the surface morphology of the stimulus-sensitive material in response to a corresponding external stimulus, such as light irradiation, temperature, pH, solvent, ions, electric field, etc.
The wettability of the surface of the single-response material responds to a stimulus, so that the interconversion between super-hydrophobic/super-hydrophilic and super-oleophobic/super-oleophilic properties is realized, and the practical application of the single-response material in many fields is limited, so that the research of the double-response/multi-response material has great significance. The responsiveness of common dual-response/multi-response materials is temperature/pH response, light/temperature response, solvent/pH response, and the like. The controlled wettability mechanisms of the materials on the surface are mutually restricted and complement each other. Cao et al successfully prepared thermally and pH dual controllable oil/water separation materials by photoinitiated free radical polymerization of dimethylaminoethyl methacrylate (DMAEMA). The PDMAEMA hydrogel coating network exhibits superhydrophilicity and underwater superoleophobicity at certain temperatures and pH. Due to the dual responsiveness of PDMAEMA hydrogels, the prepared networks can selectively separate water from oil/water mixtures by adjusting the temperature or pH, and allow the water and oil to be collected separately through the network in an orderly fashion. Water can be passed through the prepared screen at 55 ℃ (pH 7) and pH less than 13 (T25 ℃) while the oil remains on the screen. When the temperature is higher than 55 ℃ or the pH is higher than 13, the water retention capacity of the PDMAEMA hydrogel is remarkably reduced, and the swelling volume is reduced. Thus, the oil can permeate through the mesh and collect. Wu et al established a self-cleaning system on cotton fabrics with intelligent control and reusable oil/water separation by Atom Transfer Radical Polymerization (ATRP) initiated by the surface of 2-dimethylaminoethyl methacrylate (DMAEMA). The fabric exhibits high pH and thermal load, which is largely dependent on PDMAEMA grafting. By adjusting the pH or temperature, the fabric changes from being super hydrophilic (WCA ≈ 0 °) to highly hydrophobic (WCA ≈ 130 °), so the material is suitable for separating oil/water mixtures rich in moisture or oil. Specifically, as the temperature or pH increases, the fabric changes from hydrophilic to hydrophobic. The transition temperature was about 45 ℃ and the transition pH was about 7. The fabric reaches super-hydrophilicity at low pH or low temperature and hydrophobicity at high pH or high pH, but the super-hydrophobicity is difficult to reach. The fabric can absorb oil more than 4 times of its own weight and is reversibly released in acidic water, making the fabric easily recyclable.
Compared with a single-response intelligent surface, the double-response/multi-response wettability material surface has more advantages, such as functions, principles, applicable environments and the like. However, when the dual-response/multi-response wettability material is prepared, different stimuli and external interference have great influence on the wettability expression of the dual-response/multi-response wettability material, and the traditional dual-response intelligent material cannot have good pH responsiveness and temperature responsiveness at the same time.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a temperature-sensitive/pH dual-response intelligent nanofiber material and a preparation method thereof. According to the invention, hyperbranched polyamine is modified by two temperature-sensitive monomers of 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate, and then grafted on cellulose nanofiber to prepare the temperature-sensitive/pH dual-response intelligent nanofiber material with good pH responsiveness and temperature responsiveness, the material can realize intelligent conversion of super-hydrophilic and super-hydrophobic, super-oleophilic and super-oleophobic under the stimulus response conditions of temperature and pH respectively, and the low critical solution temperature of the material can be controllably adjusted within the range of 37-50 ℃.
The invention aims to provide a temperature-sensitive/pH dual-response intelligent nanofiber material;
the invention also aims to provide a preparation method of the temperature-sensitive/pH dual-response intelligent nanofiber material;
the invention further aims to provide application of the temperature-sensitive/pH dual-response intelligent nanofiber material.
The above object of the present invention is achieved by the following technical solutions:
the temperature-sensitive/pH dual-response intelligent nanofiber material is an intelligent nanofiber functional material with pH and temperature dual responses, and is prepared by taking carboxylated cellulose nanofibers as a matrix and carrying out chemical reaction on the carboxylated cellulose nanofibers and a pH and temperature dual-response polymer.
The carboxylated cellulose nanofiber is a cellulose nanofiber with three hydroxyl groups of cellulose carboxylated, and is prepared by oxidizing paper pulp fibers with sodium periodate to prepare dialdehyde fibers and then oxidizing with TEMPO.
The pH and temperature dual-response polymer is a hyperbranched polyamine polymer simultaneously modified by two temperature-sensitive monomers and is prepared by the addition reaction of the two temperature-sensitive monomers and hyperbranched polyamine; the two temperature-sensitive monomers are 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate.
The paper pulp fiber is bagasse pulp fiber, eucalyptus pulp fiber, bamboo pulp fiber, masson pine pulp fiber or wheat straw pulp fiber.
The preparation method of the temperature-sensitive/pH dual-response intelligent nanofiber material comprises the following steps:
s1, preparing dialdehyde fibers: adopting sodium periodate to selectively oxidize hydroxyl groups on C2 and C3 of cellulose structural units of the paper pulp fiber into aldehyde groups to prepare dialdehyde fiber;
s2, preparation of carboxylated cellulose nanofibers: oxidizing aldehyde groups on C2 and C3 and hydroxyl on C6 of cellulose structural units of dialdehyde fibers into carboxyl by using a TEMPO reagent to prepare carboxylated cellulose nanofibers;
s3, preparing a pH and temperature dual response polymer: performing addition reaction on C (C) on ethyl 2- (2-methoxyethoxy) methacrylate and oligo (ethylene glycol) methyl ether methacrylate and amino of hyperbranched polyamine to prepare a pH and temperature dual-response polymer of the hyperbranched polyamine simultaneously modified by two temperature-sensitive monomers;
s4, preparing a temperature-sensitive/pH dual-response intelligent nanofiber material: and performing polycondensation reaction on the carboxyl of the carboxylated cellulose nanofiber and the amino of the pH and temperature dual-response polymer to prepare the temperature-sensitive/pH dual-response intelligent nanofiber material.
The preparation of the dialdehyde fiber in the step S1 comprises the following specific operations: adding a potassium hydrogen phthalate buffer solution into the paper pulp fibers, then adding sodium periodate, stirring and reacting for 3.5-4.5 h at the temperature of 30-40 ℃, finally adding ethylene glycol to terminate the reaction, washing and drying to obtain dialdehyde fibers; the mass ratio of the paper pulp fibers to the sodium periodate is 4: 2-3.
The preparation of the carboxylated cellulose nanofiber in the step S2 comprises the following specific operations: adding a sodium phosphate buffer solution into dialdehyde fibers, stirring uniformly at 55-65 ℃, then adding TEMPO, adding a sodium hypochlorite solution, then adding sodium chlorite, oxidizing for 15-17 h, adding ethanol for quenching, washing and drying to obtain carboxylated cellulose nanofibers; the mass ratio of the dialdehyde fibers to the TEMPO is 400: 6-7.
The oxidation degree is regulated and controlled by controlling the reaction conditions in the steps S1 and S2, so that the carboxyl content of the prepared carboxylated cellulose nanofiber is 6-10 mmol/g, if the oxidation degree is low, the carboxyl content is low, reaction sites provided for the next step are few, the grafting ratio of the pH and temperature dual-response polymer is low, the good temperature and pH dual-response property is difficult to be achieved, and if the oxidation degree is too high, the cellulose nanofiber is seriously degraded, and the strength of the cellulose nanofiber is lost. Therefore, controlling the oxidation degree is one of the key technologies.
The preparation method of the hyperbranched polyamine in the step S3 comprises the following steps: mixing polyethylene polyamine and anhydrous methanol, introducing nitrogen, adding a mixed solution of methyl acrylate and the anhydrous methanol into a mixed solution of the polyethylene polyamine and the anhydrous methanol at the temperature of 0 ℃ under the stirring condition, then reacting for 24 hours at the temperature of 5 ℃ to obtain a hyperbranched polyamine precursor, evaporating the hyperbranched polyamine precursor at the temperature of 70 ℃ for 2 hours to remove the solvent methanol, and then sequentially heating to the temperature of 100 ℃, 120 ℃ and 150 ℃ for 1.5 hours respectively to obtain hyperbranched polyamine; the volume ratio of the polyethylene polyamine to the methyl acrylate is 1: 1; the polyethylene polyamine is ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The branching degree of the hyperbranched polyamine is regulated and controlled by regulating and controlling the species of the polyethylene polyamine, and the branching structure of the hyperbranched polyamine is beneficial to the chemical modification of two temperature-sensitive monomers on the hyperbranched polyamine.
The preparation of the step S3pH and the temperature dual response polymer comprises the following specific operations: dissolving hyperbranched polyamine in methanol to prepare hyperbranched polyamine solution, dissolving 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate in methanol to prepare temperature-sensitive monomer solution, uniformly mixing the temperature-sensitive monomer solution and the hyperbranched polyamine solution at 55-65 ℃, reacting for 10-30 h at 60-80 ℃, and freeze-drying after the reaction is finished to obtain the pH and temperature dual-response polymer. The mass ratio of the hyperbranched polyamine to the total mass of the 2- (2-methoxyethoxy) ethyl methacrylate and the oligo (ethylene glycol) methyl ether methacrylate is 1: 1-2, wherein the mass ratio of the 2- (2-methoxyethoxy) ethyl methacrylate to the oligo (ethylene glycol) methyl ether methacrylate is 1-3: 1. The low critical solution temperature of the pH and temperature dual response polymer is regulated and controlled by regulating and controlling the mass ratio of the two temperature-sensitive monomers. The substitution degree of primary amino on the hyperbranched polyamine is regulated to be 50% -80% by regulating the mass ratio of the hyperbranched polyamine to the two temperature-sensitive monomers, 20% -50% of the primary amino is reserved, and sufficient reaction sites are provided for the next polycondensation reaction of the carboxylated cellulose nanofiber and the pH and temperature dual-response polymer, so that the grafting rate of the pH and temperature dual-response polymer on the cellulose nanofiber is regulated, and the controllable regulation of the pH responsiveness and temperature responsiveness range of the temperature-sensitive/pH dual-response intelligent nanofiber material is realized.
The preparation of the multi-responsiveness intelligent nanofiber functional material of the step S4 specifically comprises the following operations: mixing and dispersing a pH and temperature dual-response polymer and carboxylated cellulose nanofibers in water, carrying out ultrasonic treatment for 25-35 min, and reacting for 4-12 h at 100-140 ℃ to obtain a temperature-sensitive/pH dual-response intelligent nanofiber material; the mass ratio of the pH and temperature dual-response polymer to the carboxylated cellulose nanofibers is 1-100: 1.
The temperature-sensitive/pH dual-response intelligent nanofiber material has good pH responsiveness and temperature responsiveness, and the low critical solution temperature of the temperature-sensitive/pH dual-response intelligent nanofiber material can be controllably adjusted within the range of 37-50 ℃, so that the temperature-sensitive/pH dual-response intelligent nanofiber material can be widely applied to the fields of drug slow release, oil-water separation and the like, and the application of the temperature-sensitive/pH dual-response intelligent nanofiber material in the aspects of drug slow release or oil-water separation is also within the protection range of the temperature-sensitive/pH dual-response intelligent.
The invention has the following beneficial effects:
(1) according to the invention, after two temperature-sensitive monomers are used for simultaneously modifying hyperbranched polyamine, the hyperbranched polyamine is grafted on the cellulose nanofiber, so that the prepared temperature-sensitive/pH dual-response intelligent nanofiber material has good pH responsiveness and temperature responsiveness simultaneously, and the defect that the traditional dual-response intelligent material cannot have good pH responsiveness and temperature responsiveness simultaneously is overcome. The pH responsiveness of the temperature-sensitive/pH dual-response intelligent nanofiber material can reach: when the pH value is 1-5, the water contact angle is 0-80 degrees, and the oil contact angle is 120-159 degrees; when the pH value is 9-13, the water contact angle is 130-159 DEG, and the oil contact angle is 0-70 deg. The temperature-sensitive responsiveness can be achieved: when the temperature is lower than the low critical solution temperature, the water contact angle is 0-80 degrees, and the oil contact angle is 120-159 degrees; when the temperature is higher than the low critical solution temperature, the water contact angle is 130-159 degrees, and the oil contact angle is 0-70 degrees. The pH responsiveness of the material can reach the following best: when the pH value is 1, the water contact angle is 0 degrees, and the oil contact angle is 159 degrees; when the pH value is 12, the water contact angle is 159 degrees, and the oil contact angle is 0 degrees; the temperature-sensitive responsiveness can be best achieved by: when the temperature is lower than the low critical solution temperature, the water contact angle is 0 degree, and the oil contact angle is 159 degrees; the water contact angle is 159 ℃ and the oil contact angle is 0 ℃ at a temperature higher than the lower critical solution temperature.
(2) According to the invention, two temperature-sensitive monomers are simultaneously and chemically modified on hyperbranched polyamine, wherein the low critical solution temperature of 2- (2-methoxyethoxy) ethyl methacrylate is 28 ℃, the low critical solution temperature of oligo (ethylene glycol) methyl ether methacrylate is 90 ℃, the low critical solution temperature (37-50 ℃) of a pH and temperature dual-response polymer is regulated by regulating the mass ratio (1-3: 1) of 2- (2-methoxyethoxy) ethyl methacrylate to oligo (ethylene glycol) methyl ether methacrylate, and the temperature-sensitive/pH dual-response intelligent nanofiber material is grafted on cellulose nanofibers, so that the controllable regulation of the low critical solution temperature of the temperature-sensitive/pH dual-response intelligent nanofiber material is realized.
(3) According to the invention, the paper pulp fiber is doubly oxidized by sodium periodate and TEMPO, so that the prepared carboxylated cellulose nanofiber has higher content of reactive active sites (carboxyl), the grafting rate of the pH and temperature double-response polymer on the cellulose nanofiber is higher, and the good double-response performance of the temperature-sensitive/pH double-response intelligent nanofiber material can be realized. The substitution degree of primary amino groups on the hyperbranched polyamine is regulated to be 50% -80% by regulating the mass ratio (1: 1-2) of the hyperbranched polyamine to the two temperature-sensitive monomers, 20% -50% of the primary amino groups are reserved, and sufficient reaction sites are provided for the next step of polycondensation reaction of the carboxylated cellulose nanofibers and the pH and temperature dual-response polymer, so that the grafting rate of the pH and temperature dual-response polymer on the cellulose nanofibers is regulated, and the controllable regulation of the pH responsiveness and temperature responsiveness range of the temperature-sensitive/pH dual-response intelligent nanofiber material is realized.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the invention thereto. It is within the scope of the present invention to make simple modifications or alterations to the methods, procedures or conditions of the present invention without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
The preparation method of the temperature-sensitive/pH dual-response intelligent nanofiber material comprises the following specific steps:
preparing dialdehyde fibers: taking 4g of oven-dried eucalyptus pulp fiber into a conical flask, adding 200mL of potassium hydrogen phthalate buffer (0.05M, pH value is 3), adding 2.4g of sodium periodate, wrapping with tinfoil, stirring for 4h at 35 ℃, adding 10mL of glycol to terminate the reaction, filtering, washing and drying the product to obtain the dialdehyde fiber.
Preparing carboxylated cellulose nano-fibers: to 2g of dialdehyde fiber, 180mL of sodium phosphate buffer solution (0.05M, pH 6.8) was added, and the suspension was stirred in a 500rmp and 60 ℃ sealed flask, then 0.032g TEMPO was added, 1.69M, 1.183mL sodium hypochlorite solution was added, 2.1307g sodium chlorite was added, oxidation was performed for 16h, 5mL ethanol was added for quenching, washing, and drying to obtain carboxylated cellulose nanofibers.
Preparing hyperbranched polyamine: mixing 50mL of ethylenediamine and 100mL of anhydrous methanol, introducing nitrogen, adding a solution of 50mL of methyl acrylate and 50mL of anhydrous methanol into a solution of ethylenediamine and anhydrous methanol under the conditions of 0 ℃ and stirring, then reacting at 5 ℃ for 24 hours to obtain a hyperbranched polyamine precursor, evaporating the hyperbranched polyamine precursor at 70 ℃ for 2 hours to remove the solvent methanol, and then sequentially heating to 100 ℃, 120 ℃ and 150 ℃ for 1.5 hours to obtain the hyperbranched polyamine.
Preparing a pH and temperature dual response polymer: dissolving 2g of hyperbranched polyamine in 20mL of methanol to prepare a hyperbranched polyamine solution, dissolving 3g of 2- (2-methoxyethoxy) ethyl methacrylate and 1g of oligo (ethylene glycol) methyl ether methacrylate in 40mL of methanol to prepare a temperature-sensitive monomer solution, uniformly mixing the temperature-sensitive monomer solution and the hyperbranched polyamine solution at 60 ℃, reacting for 20 hours at 70 ℃, and after the reaction is finished, freezing and drying to obtain the pH and temperature dual-response polymer.
Preparing a multi-responsiveness intelligent nanofiber functional material: mixing and dispersing 1g of pH and temperature dual-response polymer and 0.02g of carboxylated cellulose nano-fiber in 30mL of water, carrying out ultrasonic treatment for 30min, reacting for 8h at 120 ℃, then washing for several times by using distilled water, and drying for 12h at 60 ℃ to prepare the temperature-sensitive/pH dual-response intelligent nano-fiber material, wherein the low critical solution temperature of the material is 37 ℃.
Example 2
The preparation method of the temperature-sensitive/pH dual-response intelligent nanofiber material comprises the following specific steps:
preparing dialdehyde fibers: taking 4g of oven-dried bagasse pulp fiber, adding 200mL of potassium hydrogen phthalate buffer (0.05M, pH value is 3) into a conical flask, adding 2.0g of sodium periodate, wrapping with tinfoil, stirring at 30 ℃ for 3.5h, adding 10mL of ethylene glycol to terminate the reaction, filtering, washing and drying the product to obtain the dialdehyde fiber.
Preparing carboxylated cellulose nano-fibers: to 2g of dialdehyde fiber, 180mL of sodium phosphate buffer solution (0.05M, pH 6.8) was added, and the suspension was stirred in a 500rmp and 55 ℃ sealed flask, then 0.030g TEMPO was added, 1.69M, 1.183mL sodium hypochlorite solution was added, 2.1307g sodium chlorite was added, oxidation was performed for 15h, 5mL ethanol was added for quenching, washing, and drying to obtain carboxylated cellulose nanofibers.
Preparing hyperbranched polyamine: mixing 50mL of triethylene tetramine and 100mL of anhydrous methanol, introducing nitrogen, adding a solution of 50mL of methyl acrylate mixed with 50mL of anhydrous methanol into a solution of triethylene tetramine mixed with anhydrous methanol at 0 ℃ under the condition of stirring, then reacting for 24 hours at 5 ℃ to obtain a hyperbranched polyamine precursor, evaporating the hyperbranched polyamine precursor at 70 ℃ for 2 hours to remove the solvent methanol, and then sequentially raising the temperature to 100 ℃, 120 ℃ and 150 ℃ for reacting for 1.5 hours respectively to obtain the hyperbranched polyamine.
Preparing a pH and temperature dual response polymer: dissolving 2g of hyperbranched polyamine in 20mL of methanol to prepare a hyperbranched polyamine solution, dissolving 2g of 2- (2-methoxyethoxy) ethyl methacrylate and 1g of oligo (ethylene glycol) methyl ether methacrylate in 30mL of methanol to prepare a temperature-sensitive monomer solution, uniformly mixing the temperature-sensitive monomer solution and the hyperbranched polyamine solution at 55 ℃, reacting at 60 ℃ for 10 hours, and after the reaction is finished, freezing and drying to obtain the pH and temperature dual-response polymer.
Preparing a multi-responsiveness intelligent nanofiber functional material: mixing and dispersing 1g of pH and temperature dual-response polymer and 1.00g of carboxylated cellulose nano-fiber in 50mL of water, carrying out ultrasonic treatment for 25min, reacting for 4h at 100 ℃, then washing for several times by using distilled water, and drying for 12h at 60 ℃ to prepare the temperature-sensitive/pH dual-response intelligent nano-fiber material, wherein the low critical solution temperature of the material is 42 ℃.
Example 3
The preparation method of the temperature-sensitive/pH dual-response intelligent nanofiber material comprises the following specific steps:
preparing dialdehyde fibers: putting 4g of oven-dried bamboo pulp fiber into a conical flask, adding 200mL of potassium hydrogen phthalate buffer (0.05M, pH 3), adding 3.0g of sodium periodate, wrapping with tinfoil, stirring at 40 ℃ for 4.5h, adding 10mL of ethylene glycol to terminate the reaction, filtering, washing and drying the product to obtain the dialdehyde fiber.
Preparing carboxylated cellulose nano-fibers: to 2g of dialdehyde fiber was added 180mL of sodium phosphate buffer (0.05M, pH 6.8), and the suspension was stirred in a 500rmp, 65 ℃ sealed flask, then 0.035g TEMPO was added, 1.69M, 1.183mL sodium hypochlorite solution was added, 2.1307g sodium chlorite was added, oxidation was carried out for 17h, 5mL ethanol was added for quenching, washing and drying to obtain carboxylated cellulose nanofibers.
Preparing hyperbranched polyamine: mixing 50mL of tetraethylenepentamine and 100mL of anhydrous methanol, introducing nitrogen, adding a mixed solution of 50mL of methyl acrylate and 50mL of anhydrous methanol into a mixed solution of tetraethylenepentamine and anhydrous methanol at 0 ℃ under the stirring condition, then reacting for 24 hours at 5 ℃ to obtain a hyperbranched polyamine precursor, evaporating the hyperbranched polyamine precursor at 70 ℃ for 2 hours to remove the solvent methanol, and then sequentially heating to 100 ℃, 120 ℃ and 150 ℃ for respective reactions for 1.5 hours to obtain the hyperbranched polyamine.
Preparing a pH and temperature dual response polymer: dissolving 2g of hyperbranched polyamine in 20mL of methanol to prepare a hyperbranched polyamine solution, dissolving 1g of 2- (2-methoxyethoxy) ethyl methacrylate and 1g of oligo (ethylene glycol) methyl ether methacrylate in 20mL of methanol to prepare a temperature-sensitive monomer solution, uniformly mixing the temperature-sensitive monomer solution and the hyperbranched polyamine solution at 65 ℃, reacting at 80 ℃ for 30 hours, and after the reaction is finished, freezing and drying to obtain the pH and temperature dual-response polymer.
Preparing a multi-responsiveness intelligent nanofiber functional material: mixing and dispersing 1g of pH and temperature dual-response polymer and 0.01g of carboxylated cellulose nano-fiber in 25mL of water, carrying out ultrasonic treatment for 35min, reacting for 12h at 140 ℃, then washing for several times by using distilled water, and drying for 12h at 60 ℃ to prepare the temperature-sensitive/pH dual-response intelligent nano-fiber material, wherein the low critical solution temperature of the material is 50 ℃.
Example 4
The temperature-sensitive/pH dual-response intelligent nanofiber materials prepared in the embodiments 1 to 3 are subjected to pH responsiveness and temperature responsiveness performance tests, and the results are shown in tables 1 and 2.
TABLE 1
TABLE 2
The results of tables 1 and 2 show that the temperature-sensitive/pH dual-response intelligent nanofiber material prepared by the invention has good pH responsiveness and temperature responsiveness, and the pH responsiveness of the material can reach as follows: when the pH value is 1-5, the water contact angle is 0-80 degrees, and the oil contact angle is 120-159 degrees; when the pH value is 9-13, the water contact angle is 130-159 DEG, and the oil contact angle is 0-70 deg. The temperature-sensitive responsiveness can be achieved: when the temperature is lower than the low critical solution temperature, the water contact angle is 0-80 degrees, and the oil contact angle is 120-159 degrees; when the temperature is higher than the low critical solution temperature, the water contact angle is 130-159 degrees, and the oil contact angle is 0-70 degrees. Therefore, the temperature-sensitive/pH dual-response intelligent nanofiber material disclosed by the invention can realize intelligent conversion of super-hydrophilicity and super-hydrophobicity, super-lipophilicity and super-lipophobicity under the stimulus response conditions of temperature and pH respectively.
Claims (9)
1. A temperature-sensitive/pH dual-response intelligent nanofiber material is characterized in that the temperature-sensitive/pH dual-response intelligent nanofiber material is an intelligent nanofiber functional material with dual pH and temperature responses, and is prepared by taking carboxylated cellulose nanofibers as a matrix and carrying out chemical reaction on the carboxylated cellulose nanofibers and a pH and temperature dual-response polymer;
the carboxylated cellulose nanofiber is a cellulose nanofiber with three hydroxyl groups of cellulose carboxylated, and is prepared by oxidizing paper pulp fibers with sodium periodate to prepare dialdehyde fibers and then oxidizing with TEMPO;
the pH and temperature dual-response polymer is a hyperbranched polyamine polymer simultaneously modified by two temperature-sensitive monomers and is prepared by the addition reaction of the two temperature-sensitive monomers and hyperbranched polyamine; the two temperature-sensitive monomers are 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate.
2. The temperature-sensitive/pH dual-responsive intelligent nanofiber material of claim 1, wherein the pulp fibers are bagasse pulp fibers, eucalyptus pulp fibers, bamboo pulp fibers, masson pine pulp fibers, or wheat straw pulp fibers.
3. A preparation method of a temperature-sensitive/pH dual-response intelligent nanofiber material is characterized by comprising the following steps:
s1, preparing dialdehyde fibers: adopting sodium periodate to selectively oxidize hydroxyl groups on C2 and C3 of cellulose structural units of the paper pulp fiber into aldehyde groups to prepare dialdehyde fiber;
s2, preparation of carboxylated cellulose nanofibers: oxidizing aldehyde groups on C2 and C3 and hydroxyl on C6 of cellulose structural units of dialdehyde fibers into carboxyl by using a TEMPO reagent to prepare carboxylated cellulose nanofibers;
s3, preparing a pH and temperature dual response polymer: c = C on 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate and amino of the hyperbranched polyamine are subjected to addition reaction to prepare a pH and temperature dual response polymer of the hyperbranched polyamine simultaneously modified by two temperature-sensitive monomers;
s4, preparing a temperature-sensitive/pH dual-response intelligent nanofiber material: and performing polycondensation reaction on the carboxyl of the carboxylated cellulose nanofiber and the amino of the pH and temperature dual-response polymer to prepare the temperature-sensitive/pH dual-response intelligent nanofiber material.
4. The preparation method according to claim 3, wherein the step S1 of preparing the dialdehyde fiber is specifically performed by: adding a potassium hydrogen phthalate buffer solution into the paper pulp fibers, then adding sodium periodate, stirring and reacting for 3.5-4.5 h at the temperature of 30-40 ℃, finally adding ethylene glycol to terminate the reaction, washing and drying to obtain dialdehyde fibers; the mass ratio of the paper pulp fibers to the sodium periodate is 4: 2-3.
5. The preparation method according to claim 3, wherein the step S2 of preparing the carboxylated cellulose nanofibers is carried out by the following steps: adding a sodium phosphate buffer solution into dialdehyde fibers, stirring uniformly at 55-65 ℃, then adding TEMPO, adding a sodium hypochlorite solution, then adding sodium chlorite, oxidizing for 15-17 h, adding ethanol for quenching, washing and drying to obtain carboxylated cellulose nanofibers; the mass ratio of the dialdehyde fibers to the TEMPO is 400: 6-7.
6. The method according to claim 3, wherein the hyperbranched polyamine in step S3 is prepared by: mixing polyethylene polyamine and anhydrous methanol, introducing nitrogen, adding a mixed solution of methyl acrylate and the anhydrous methanol into a mixed solution of the polyethylene polyamine and the anhydrous methanol at the temperature of 0 ℃ under the stirring condition, then reacting for 24 hours at the temperature of 5 ℃ to obtain a hyperbranched polyamine precursor, evaporating the hyperbranched polyamine precursor at the temperature of 70 ℃ for 2 hours to remove the solvent methanol, and then sequentially heating to the temperature of 100 ℃, 120 ℃ and 150 ℃ for 1.5 hours respectively to obtain hyperbranched polyamine; the volume ratio of the polyethylene polyamine to the methyl acrylate is 1: 1; the polyethylene polyamine is ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylenepentamine, and the branching degree of the hyperbranched polyamine is regulated and controlled by regulating and controlling the type of the polyethylene polyamine.
7. The preparation method according to claim 3, wherein the step S3 is carried out by specifically preparing the pH and temperature dual response polymer: dissolving hyperbranched polyamine in methanol to prepare hyperbranched polyamine solution, dissolving 2- (2-methoxyethoxy) ethyl methacrylate and oligo (ethylene glycol) methyl ether methacrylate in methanol to prepare temperature-sensitive monomer solution, uniformly mixing the temperature-sensitive monomer solution and the hyperbranched polyamine solution at the temperature of 55-65 ℃, reacting for 10-30 hours at the temperature of 60-80 ℃, and after the reaction is finished, freezing and drying to obtain a pH and temperature dual-response polymer; the mass ratio of the hyperbranched polyamine to the total mass of the 2- (2-methoxyethoxy) ethyl methacrylate and the oligo (ethylene glycol) methyl ether methacrylate is 1: 1-2, wherein the mass ratio of the 2- (2-methoxyethoxy) ethyl methacrylate to the oligo (ethylene glycol) methyl ether methacrylate is 1-3: 1, and the low critical solution temperature of the pH and temperature dual response polymer is regulated and controlled by regulating and controlling the mass ratio of the two temperature sensitive monomers.
8. The preparation method according to claim 3, wherein the step S4 of preparing the multi-responsive intelligent nanofiber functional material comprises the following specific operations: mixing and dispersing a pH and temperature dual-response polymer and carboxylated cellulose nanofibers in water, carrying out ultrasonic treatment for 25-35 min, and reacting for 4-12 h at 100-140 ℃ to obtain a temperature-sensitive/pH dual-response intelligent nanofiber material; the mass ratio of the pH and temperature dual-response polymer to the carboxylated cellulose nanofibers is 1-100: 1.
9. The application of the temperature-sensitive/pH dual-response intelligent nanofiber material as defined in any one of claims 1-2 or the temperature-sensitive/pH dual-response intelligent nanofiber material prepared by the preparation method of the temperature-sensitive/pH dual-response intelligent nanofiber material as defined in any one of claims 3-8 in drug slow release or oil-water separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910093161.2A CN109826015B (en) | 2019-01-30 | 2019-01-30 | temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910093161.2A CN109826015B (en) | 2019-01-30 | 2019-01-30 | temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109826015A CN109826015A (en) | 2019-05-31 |
| CN109826015B true CN109826015B (en) | 2021-03-26 |
Family
ID=66863025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910093161.2A Active CN109826015B (en) | 2019-01-30 | 2019-01-30 | temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109826015B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110923850B (en) * | 2019-12-06 | 2022-08-26 | 东华大学 | Dual-response color-changing polylactic acid fiber and preparation and application thereof |
| CN111389381B (en) * | 2020-04-14 | 2021-01-05 | 广西大学 | Near-infrared low-temperature desorption type intelligent adsorption material and preparation method and application thereof |
| CN111335040B (en) * | 2020-04-14 | 2021-02-19 | 广西大学 | Biomass-based stepped dual-temperature/pH/near-infrared stimulus-responsive intelligent nanofiber and preparation method and application thereof |
| CN112354019B (en) * | 2020-11-02 | 2023-06-02 | 天津科技大学 | Preparation method of pH driven artificial muscle flexible composite material |
| CN112899814B (en) * | 2021-02-03 | 2022-12-06 | 广西大学 | Bionic fiber functional material and preparation method and application thereof |
| CN113198429B (en) * | 2021-04-30 | 2022-04-01 | 深圳信息职业技术学院 | Method for preparing aerogel-like environment functional material by green solvent and application thereof |
| CN114506164B (en) * | 2021-12-27 | 2024-07-12 | 中钞设计制版有限公司 | Plate material, printing plate, preparation method of printing plate and printing method |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701051A (en) * | 2009-10-28 | 2010-05-05 | 东北师范大学 | Hydrogel with pH sensibility and temperature sensibility and preparation method thereof |
| CN101857666A (en) * | 2010-05-13 | 2010-10-13 | 中科院广州化学有限公司 | Cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof |
| CN104804142A (en) * | 2015-04-13 | 2015-07-29 | 中国科学院化学研究所 | Multi-responsive HPC (hydroxy propyl cellulose) grafted copolymer as well as preparation method and application thereof |
| CN105777992A (en) * | 2016-01-28 | 2016-07-20 | 河南省科学院能源研究所有限公司 | Alkoxyl etherified environmental response type nano cellulose grafted copolymer and preparation method thereof |
| CN105968268A (en) * | 2016-05-23 | 2016-09-28 | 长春理工大学 | Polymer as well as preparation method thereof and application thereof to being used as temperature-sensitive medicine-carrying material |
| CN106397674A (en) * | 2016-09-23 | 2017-02-15 | 中山大学 | Temperature-sensitive postoperative adhesion cellulose modifying material and preparation method and application thereof |
| CN106821963A (en) * | 2016-12-28 | 2017-06-13 | 浙江理工大学 | A kind of method of utilization cellulose base temperature and the load of pH sensitive hydrogels and slow releasing pharmaceutical |
| CN108929412A (en) * | 2018-07-10 | 2018-12-04 | 南昌大学 | A kind of preparation method of the adhesiveness injection aquagel of temperature-responsive |
| CN109134914A (en) * | 2018-07-12 | 2019-01-04 | 厦门大学 | A kind of preparation method of dual-sensitivity cellulose base aeroge |
-
2019
- 2019-01-30 CN CN201910093161.2A patent/CN109826015B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701051A (en) * | 2009-10-28 | 2010-05-05 | 东北师范大学 | Hydrogel with pH sensibility and temperature sensibility and preparation method thereof |
| CN101857666A (en) * | 2010-05-13 | 2010-10-13 | 中科院广州化学有限公司 | Cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof |
| CN104804142A (en) * | 2015-04-13 | 2015-07-29 | 中国科学院化学研究所 | Multi-responsive HPC (hydroxy propyl cellulose) grafted copolymer as well as preparation method and application thereof |
| CN105777992A (en) * | 2016-01-28 | 2016-07-20 | 河南省科学院能源研究所有限公司 | Alkoxyl etherified environmental response type nano cellulose grafted copolymer and preparation method thereof |
| CN105968268A (en) * | 2016-05-23 | 2016-09-28 | 长春理工大学 | Polymer as well as preparation method thereof and application thereof to being used as temperature-sensitive medicine-carrying material |
| CN106397674A (en) * | 2016-09-23 | 2017-02-15 | 中山大学 | Temperature-sensitive postoperative adhesion cellulose modifying material and preparation method and application thereof |
| CN106821963A (en) * | 2016-12-28 | 2017-06-13 | 浙江理工大学 | A kind of method of utilization cellulose base temperature and the load of pH sensitive hydrogels and slow releasing pharmaceutical |
| CN108929412A (en) * | 2018-07-10 | 2018-12-04 | 南昌大学 | A kind of preparation method of the adhesiveness injection aquagel of temperature-responsive |
| CN109134914A (en) * | 2018-07-12 | 2019-01-04 | 厦门大学 | A kind of preparation method of dual-sensitivity cellulose base aeroge |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109826015A (en) | 2019-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109826015B (en) | temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof | |
| CN109881489B (en) | Multi-responsiveness intelligent nanofiber functional material and preparation method and application thereof | |
| Li et al. | Synthesis, characterization and swelling behavior of superabsorbent wheat straw graft copolymers | |
| US3083118A (en) | Method of depositing a polymer of olefinically unsaturated monomer within a polymeric material and the resulting product | |
| Chen et al. | Synthesis and characterization of temperature/pH dual sensitive hemicellulose-based hydrogels from eucalyptus APMP waste liquor | |
| TWI376441B (en) | Moisture transferring paper and process for producing the same | |
| Yu et al. | Preparation, swelling behaviors and fertilizer-release properties of sodium humate modified superabsorbent resin | |
| CN110123528B (en) | Paper diaper with excellent water absorption and locking antibacterial performance and processing technology thereof | |
| CN110409186B (en) | Green light induction controlled hydrophilic/hydrophobic intelligent surface material and preparation method and application thereof | |
| CN113605094B (en) | Antibacterial degradable composite fiber and preparation method thereof | |
| CN105153456A (en) | Photonic crystal material with humidity response allochroic characteristic and preparing method thereof | |
| CN107519540A (en) | A kind of implantable fibroin/bacteria cellulose/graphene composite conductive film of high tensile flexible printing opacity | |
| CN112695411B (en) | Preparation method of temperature response type nanofiber dressing | |
| CN111875742A (en) | Preparation method of hydrophilic bacterial cellulose, hydrophilic bacterial cellulose and application | |
| Lokhande et al. | A new approach in the production of non-wood-based cellullosic superabsorbents through the pan grafting method | |
| CN112007203A (en) | Ultra-thin type super absorbent paper diaper core | |
| CN109281161B (en) | Preparation method of multifunctional viscose fiber composite material | |
| CN111826809A (en) | Preparation method of non-woven fabric material for paper diapers | |
| CN1142952C (en) | Polyacrylonitrile polymer treatment | |
| Yang et al. | Separation and recovery of alkali cellulose wastewater with high concentration of salts by cross-linked poly (vinyl alcohol)/polytetrafluoroethylene ultrafiltration membrane | |
| CN111925480A (en) | Preparation method of hydrophobic bacterial cellulose, hydrophobic bacterial cellulose and application | |
| CN114507454B (en) | Nano zinc oxide polymer composite material and preparation method thereof | |
| CN104826507A (en) | Albumen dewatering separation and purification membrane taking cellulosic fiber as base material | |
| Rebelo et al. | Biocompatible Cellulose-Based Superabsorbents for Personal Care Products | |
| CN116856193B (en) | Lignocellulose-based coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |