CN109134887B - Preparation method of polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel - Google Patents
Preparation method of polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel Download PDFInfo
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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Abstract
The invention relates to the field of polymer nano fibers, in particular to a preparation method of polyurethane nano fiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel with temperature and pH dual responses. The invention comprises the following steps: a. preparing a polyurethane nanofiber membrane by a thermally induced phase separation method; b. preparing vinyl modified silicon dioxide; c. grafting N-isopropylacrylamide and acrylic acid on the surface of the polyurethane nanofiber membrane through ultraviolet radiation to obtain the polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel. The invention has the following beneficial effects: the specific surface area and porosity of the hydrogel are greatly improved, so that the hydrogel has rapid temperature and pH response rate.
Description
Technical Field
The invention relates to a preparation method of polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel, belonging to the technical field of polymer nanofibers.
Background
The hydrogel has good biocompatibility and has stimulus response to external environments such as temperature, pH, salt concentration, magnetic field, electric field and the like, and is widely applied to the fields of drug controlled release, immobilized enzyme, gene transfer and the like. Poly (N-isopropylacrylamide) (PNIPAm) is a typical temperature-sensitive hydrogel, and PNIPAm has a low critical phase transition temperature (LCST, about 32 ℃) below which it highly swells, and above which it shrinks dramatically and the degree of swelling decreases abruptly. Because PNIPAm hydrogels contain hydrophilic amide groups and hydrophobic isopropyl groups inside, there is a hydrophilic/hydrophobic balance and LCST properties are a result of hydrophilic/hydrophobic interactions. When the temperature is lower than LCST, the amide group on the gel forms hydrogen bond with water molecule, and the gel swells to absorb water. As the temperature increases (without reaching the LCST), the association of the amide groups with the water molecules forming hydrogen bonds is progressively broken, while the interaction between the hydrophobic isopropyl groups is progressively strengthened. When the temperature reaches LCST, the hydrophobic effect of isopropyl plays a dominant role, the macromolecular network is disintegrated, macromolecular chains are mutually aggregated through the hydrophobic effect, and the hydrogel is subjected to phase transition.
The hydrogel synthesized by the traditional method has the synergistic diffusion coefficient of 10-7～10-6cm2A hydrogel material having a thickness of, for example, 2mm takes approximately 1 day to reach equilibrium with water absorption or shrinkage in response to a change in the external temperature. The PNIPAm gel which swells at room temperature is transferred into water with the temperature higher than LCST, the surface of the gel is firstly subjected to phase separation to form a compact surface layer, and the release of water molecules is hindered, so that the response rate of the gel is very slow. Such slow response rates greatly limit their applications. In order to improve the response rate, researchers have adopted methods such as reducing the size of the gel, preparing porous structures, introducing graft chains or forming interpenetrating network structures. The phase transition temperature of the PNIPAm gel prepared by the methods is the same as that of the common PNIPAm gel, and the PNIPAm gel can not meet the requirement of 37 ℃ of a human body at about 33 ℃. The LCST of PNIPAm gel can be increased by copolymerization with hydrophilic monomers, but the temperature sensitivity of the gel is reduced. Therefore, it is required to prepare a temperature-sensitive hydrogel having both a suitable phase transition temperature and a fast response property.
Disclosure of Invention
The invention aims to provide a preparation method of polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel.
The invention is realized by the following technical scheme:
a preparation method of polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel comprises the following steps:
respectively preparing a polyurethane nanofiber membrane and vinyl modified silicon dioxide;
dissolving N-isopropylacrylamide, acrylic acid, N' -methylene-bisacrylamide and ammonium persulfate in distilled water, adding the vinyl modified silica, uniformly dispersing, adding the polyurethane nanofiber membrane activated by benzophenone, and irradiating by using ultraviolet light under the protection of nitrogen to perform polymerization reaction to obtain the polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel;
the polyurethane nanofiber membrane is prepared by a thermally induced phase separation method, and the vinyl modified silicon dioxide is prepared by reacting vinyl triethoxysilane with silicon dioxide.
Preferably, the preparation method of the polyurethane nanofiber membrane comprises the following steps:
dissolving polyurethane in an N, N' -dimethylformamide solvent to obtain a polyurethane solution;
and quenching the polyurethane solution at the temperature of between 40 ℃ below zero and 10 ℃ below zero for 120 to 180min, and removing the N, N' -dimethylformamide solvent to obtain the polyurethane nanofiber membrane.
Preferably, the concentration of the polyurethane solution is 6-10 g/mL.
Preferably, the preparation method of the vinyl modified silica comprises the following steps:
preparing an ethanol solution of vinyl triethoxysilane and an ethanol dispersion of silicon dioxide respectively;
adding the ethanol solution of the vinyl triethoxysilane into the ethanol dispersion liquid of the silicon dioxide, carrying out ultrasonic treatment for 2 hours, and then carrying out centrifugal separation, ethanol washing and vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide;
the preparation method of the ethanol solution of the vinyl triethoxysilane comprises the following steps: dissolving vinyl triethoxysilane in ethanol, wherein the preparation method of the ethanol dispersion liquid of silicon dioxide comprises the following steps: dispersing silicon dioxide in ethanol.
Preferably, the mass ratio of the vinyltriethoxysilane to the silicon dioxide is 1: 1.
preferably, the mass ratio of the N-isopropylacrylamide, the acrylic acid, the N, N' -methylenebisacrylamide, the ammonium persulfate and the vinyl-modified silica is 50: (2-4): 1: 1: (1-2).
Preferably, the mass ratio of the N-isopropylacrylamide to the polyurethane fiber membrane is 5: 1, the radiation time is 20-60 min.
Preferably, the activation method of the polyurethane nanofiber membrane comprises the following steps:
and (3) dissolving the polyurethane nanofiber membrane in acetone solution of benzophenone for 5min, taking out, and drying in vacuum for later use.
Preferably, the acetone solution of benzophenone has a benzophenone mass fraction of 4%.
The mechanism of the invention is as follows:
firstly, preparing a PU nanofiber membrane by a thermally induced phase separation method, and then capturing active hydrogen on the surface of the PU nanofiber membrane by benzophenone to enable the surface of the PU nanofiber membrane to form free radicals. Then grafting N-isopropyl acrylamide and acrylic acid onto the PU fiber membrane by an ultraviolet radiation polymerization method. The monomer is grafted to the nanofiber membrane, so that the porosity and the specific surface area of the hydrogel are mainly improved, the diffusion of water molecules is facilitated, and the response rate of the hydrogel is improved. When the traditional PNIPAm hydrogel shrinks and loses water, a thicker hydrophobic layer is formed on the surface of the gel firstly, and the outward diffusion of internal water molecules is hindered. The hydrophilic acrylic monomer is copolymerized to the gel, so that the hydrophilicity of the whole network is improved, the formation of the hydrophobic compact layer can be damaged, and the response rate is greatly improved. The addition of acrylic acid raises the phase transition temperature of the hydrogel, making it more suitable for the temperature of the human body, and the addition of acrylic acid makes the gel not only temperature-responsive but also pH-responsive. The vinyl modified silicon dioxide is added into a reaction system, so that the gel forms a discontinuous network pore structure, the porosity is improved, and the temperature response rate is greatly improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyurethane nanofiber membrane is prepared by a thermally induced phase separation method, the process is simple, the yield is high, and the method is very suitable for industrial production;
2. n-isopropyl acrylamide is grafted to the surface of a polyurethane nanofiber membrane with biocompatibility, so that the volume size of gel is reduced, the specific surface area and porosity are increased, and the temperature response rate is greatly improved;
3. the addition of the comonomer acrylic acid improves the temperature response rate of the gel, improves the phase transition temperature and has pH responsiveness;
4. the addition of the vinyl modified silicon dioxide forms a discontinuous network pore structure, so that the porosity is improved, and the temperature response rate is greatly improved.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron micrograph of a hydrogel prepared in example 1 of the present invention;
FIG. 2 is a graph showing the change of swelling ratio of hydrogels prepared in example 1, comparative example 1 and comparative example 2 according to the present invention with temperature;
FIG. 3 is a graph showing the swelling ratio of hydrogels prepared in example 1 and comparative example 2 according to the present invention as a function of pH;
FIG. 4 deswelling kinetics curves for hydrogels prepared according to the present invention, example 1, comparative example 1 and comparative example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
1) Preparation of polyurethane nanofiber membrane
6g of polyurethane was dissolved in 100ml of N, N' -dimethylformamide and dissolved by magnetic stirring at 50 ℃ to give a clear and transparent solution. Pouring 5mL of the solution into a culture dish with the diameter of 7cm, putting the culture dish into a refrigerator with preset temperature of-10 ℃, and quenching for 80 min. And (3) quickly taking out the culture dish after quenching is finished, adding 200mL of ethanol into the culture dish for extraction, removing the N, N' -dimethylformamide, changing the ethanol once every 6 hours, and continuously changing the ethanol for 5 times. And (5) freeze-drying the sample for 24 hours to obtain the polyurethane nanofiber membrane.
2) Preparation of vinyl-modified silica
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
3) Preparation of polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel (PU-g-P (NIPAm-co-AA))
Dissolving 4g of benzophenone in 96g of acetone, soaking the polyurethane fiber membrane in the benzophenone solution, taking out after 5min, and drying in vacuum for later use. 100mg of N-isopropylacrylamide, 4mg of acrylic acid, 2mg of N, N' -methylenebisacrylamide and 2mg of ammonium persulfate were dissolved in 50mL of distilled water, and 2mg of vinyl-modified silica was added thereto. Soaking 20mg of polyurethane fiber membrane in the mixed solution, introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 50cm, and radiating for 20 min. After the reaction is finished, washing the obtained product with distilled water, and freeze-drying to obtain the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel.
Fiber diameter in PU-g-P (NIPAm-co-AA) fiber membrane hydrogel320 + -110 nm, as shown in FIG. 1. The porosity and the specific surface area were 95.2% and 14.22m, respectively2(ii) in terms of/g. The swelling ratio of the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 36.9g/g, as shown in figure 2. As can be seen from the figure, the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel begins to rapidly lose water at 30 ℃, reaches the equilibrium at about 40 ℃, and has good temperature sensitivity near 36.4 ℃.
Fig. 3 shows the relationship between the pH value of the hydrogel and the swelling ratio, and it can be seen that the PU-g-P (NIPAm-co-AA) fibrous membrane hydrogel suddenly increased at pH 4.2 to a maximum of 39.04g/g at pH 7.8. And then gradually decreases as the pH increases. It is shown that the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel shows good pH responsiveness. However, the PU-g-PNIPAm fiber membrane hydrogel (prepared in comparative example 2) was almost non-responsive to pH. Mainly because hydrophilic acrylic acid is grafted in a PU-g-P (NIPAm-co-AA) fiber membrane hydrogel system, the pKa of the acrylic acid is 4.25, when the pH value of the solution is lower than the pKa of the acrylic acid, carboxyl groups in the polymer are not ionized, and the hydrogel is in a relatively contracted state, so that the swelling rate of the hydrogel is low. When the pH value in the solution is increased and is larger than the pKa of acrylic acid, -COOH is dissociated into-COO-，-COO-More hydrophilic and due to-COO-The electrostatic repulsion causes the molecular chains to be stretched, and thus the swelling ratio is increased. However, when the pH value of the system is more than 8, the swelling ratio is rather decreased. Mainly because the dissociation of-COOH is dynamic equilibrium, too high pH value causes too high ionic strength of the solution system and leads to the reduction of swelling ratio. The PU-g-P (NIPAm-co-AA) fiber membrane hydrogel prepared by the invention has temperature and pH dual-response characteristics.
FIG. 4 is a hydrogel deswelling kinetic curve, showing that the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel reaches 64.9% of the dehydration rate within 1min and reaches an equilibrium after about 9min, which shows that the hydrogel has a rapid temperature response rate.
Example 2
1) Preparation of polyurethane nanofiber membrane
7g of polyurethane was dissolved in 100ml of N, N' -dimethylformamide and dissolved by magnetic stirring at 50 ℃ to give a clear and transparent solution. Pouring 5mL of the solution into a culture dish with the diameter of 7cm, putting the culture dish into a refrigerator with the preset temperature of-30 ℃, and quenching for 80 min. And (3) quickly taking out the culture dish after quenching is finished, adding 200mL of ethanol into the culture dish for extraction, removing the N, N' -dimethylformamide, changing the ethanol once every 6 hours, and continuously changing the ethanol for 5 times. And (5) freeze-drying the sample for 24 hours to obtain the polyurethane nanofiber membrane.
2) Preparation of vinyl-modified silica
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
3) Polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid)
Preparation of (PU-g-P (NIPAm-co-AA)) hydrogel
Dissolving 4g of benzophenone in 96g of acetone, soaking the polyurethane fiber membrane in the benzophenone solution, taking out after 5min, and drying in vacuum for later use. 100mg of N-isopropylacrylamide, 8mg of acrylic acid, 2mg of N, N' -methylenebisacrylamide and 2mg of ammonium persulfate were dissolved in 50mL of distilled water, and 4mg of vinyl-modified silica was added thereto. Soaking 20mg of polyurethane fiber membrane in the mixed solution, introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 50cm, and radiating for 20 min. After the reaction is finished, washing the obtained product with distilled water, and freeze-drying to obtain the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel.
The fiber diameter of the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 280 +/-120 nm, and the porosity and the specific surface area are 91.6 percent and 13.19m respectively2(ii) in terms of/g. The swelling ratio of PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 36.7g/g, and the dehydration rate in 1min reaches 65.2%.
Example 3
1) Preparation of polyurethane nanofiber membrane
7g of polyurethane was dissolved in 100ml of N, N' -dimethylformamide and dissolved by magnetic stirring at 50 ℃ to give a clear and transparent solution. Pouring 5mL of the solution into a culture dish with the diameter of 7cm, putting the culture dish into a refrigerator with preset-20 ℃, and quenching for 100 min. And (3) quickly taking out the culture dish after quenching is finished, adding 200mL of ethanol into the culture dish for extraction, removing the N, N' -dimethylformamide, changing the ethanol once every 6 hours, and continuously changing the ethanol for 5 times. And (5) freeze-drying the sample for 24 hours to obtain the polyurethane nanofiber membrane.
2) Preparation of vinyl-modified silica
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
3) Polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid)
Preparation of (PU-g-P (NIPAm-co-AA)) hydrogel
Dissolving 4g of benzophenone in 96g of acetone, soaking the polyurethane fiber membrane in the benzophenone solution, taking out after 5min, and drying in vacuum for later use. 100mg of N-isopropylacrylamide, 6mg of acrylic acid, 2mg of N, N' -methylenebisacrylamide and 2mg of ammonium persulfate were dissolved in 50mL of distilled water, and 3mg of vinyl-modified silica was added. Soaking 20mg of polyurethane fiber membrane in the mixed solution, introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 50cm, and radiating for 20 min. After the reaction is finished, washing the obtained product with distilled water, and freeze-drying to obtain the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel.
The fiber diameter of the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 330 +/-109 nm, and the porosity and the specific surface area are 93.19 percent and 15.11m respectively2(ii) in terms of/g. The swelling ratio of PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 30.6g/g, and the dehydration rate in 1min reaches 66.1%.
Example 4
1) Preparation of polyurethane nanofiber membrane
7g of polyurethane was dissolved in 100ml of N, N' -dimethylformamide and dissolved by magnetic stirring at 50 ℃ to give a clear and transparent solution. Pouring 5mL of the solution into a culture dish with the diameter of 7cm, putting the culture dish into a refrigerator with preset temperature of-10 ℃, and quenching for 100 min. And (3) quickly taking out the culture dish after quenching is finished, adding 200mL of ethanol into the culture dish for extraction, removing the N, N' -dimethylformamide, changing the ethanol once every 6 hours, and continuously changing the ethanol for 5 times. And (5) freeze-drying the sample for 24 hours to obtain the polyurethane nanofiber membrane.
2) Preparation of vinyl-modified silica
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
3) Polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid)
Preparation of (PU-g-P (NIPAm-co-AA)) hydrogel
Dissolving 4g of benzophenone in 96g of acetone, soaking the polyurethane fiber membrane in the benzophenone solution, taking out after 5min, and drying in vacuum for later use. 100mg of N-isopropylacrylamide, 6mg of acrylic acid, 2mg of N, N' -methylenebisacrylamide and 2mg of ammonium persulfate were dissolved in 50mL of distilled water, and 2mg of vinyl-modified silica was added thereto. Soaking 20mg of polyurethane fiber membrane in the mixed solution, introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 50cm, and radiating for 40 min. After the reaction is finished, washing the obtained product with distilled water, and freeze-drying to obtain the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel.
The fiber diameter of the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 310 +/-94 nm, the porosity and the specific surface area are respectively 92.9 percent and 16.19m2(ii) in terms of/g. The swelling ratio of PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 34.5g/g, and the dehydration rate within 1min reaches 62.9%.
Example 5
1) Preparation of polyurethane nanofiber membrane
9g of polyurethane was dissolved in 100ml of N, N' -dimethylformamide and dissolved by magnetic stirring at 50 ℃ to give a clear and transparent solution. Pouring 5mL of the solution into a culture dish with the diameter of 7cm, putting the culture dish into a refrigerator with the preset temperature of-30 ℃, and quenching for 120 min. And (3) quickly taking out the culture dish after quenching is finished, adding 200mL of ethanol into the culture dish for extraction, removing the N, N' -dimethylformamide, changing the ethanol once every 6 hours, and continuously changing the ethanol for 5 times. And (5) freeze-drying the sample for 24 hours to obtain the polyurethane nanofiber membrane.
2) Preparation of vinyl-modified silica
1g of vinyltriethoxysilane was dissolved in 15mL of ethanol, and 1g of silica was ultrasonically dispersed in 10mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
3) Polyurethane nanofiber membrane grafted poly (N-isopropylacrylamide-co-acrylic acid)
Preparation of (PU-g-P (NIPAm-co-AA)) hydrogel
Dissolving 4g of benzophenone in 96g of acetone, soaking the polyurethane fiber membrane in the benzophenone solution, taking out after 5min, and drying in vacuum for later use. 100mg of N-isopropylacrylamide, 8mg of acrylic acid, 2mg of N, N' -methylenebisacrylamide and 2mg of ammonium persulfate were dissolved in 50mL of distilled water, and 4mg of vinyl-modified silica was added thereto. Soaking 20mg of polyurethane fiber membrane in the mixed solution, introducing N into the system2And (4) protecting. And starting an ultraviolet light source (a 500W high-pressure mercury lamp), radiating for 50cm, and radiating for 60 min. After the reaction is finished, washing the obtained product with distilled water, and freeze-drying to obtain the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel.
The fiber diameter of the PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 301 +/-110 nm, and the porosity and the specific surface area are 95.1 percent and 18.11m respectively2(ii) in terms of/g. The swelling ratio of PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is 38.1g/g, and the dehydration rate in 1min reaches 69.22%.
Comparative example 1
The difference from the embodiment 1 is that: step 1) dissolving polyurethane in an N, N' -dimethylformamide solvent to form a clear and transparent solution, and then directly adopting a tape casting film forming method to obtain a polyurethane tape casting film. The subsequent steps are the same as example 1, and finally the polyurethane casting film graft poly (N-isopropylacrylamide-co-acrylic acid)
(PU-g-P (NIPAm-co-AA)) cast film hydrogels. The porosity and specific surface area of the PU-g-P (NIPAm-co-AA) casting film hydrogel are 49.2 percent and 1.74m respectively2(ii) in terms of/g. Compared with the hydrogel of the casting film, the porosity and the specific surface area of the hydrogel of the nanofiber film are greatly improved.
The swelling ratio of the PU-g-P (NIPAm-co-AA) cast film hydrogel to the swelling equilibrium was 18.8g/g, as shown in FIG. 2. The water removal rate of the PU-g-P (NIPAm-co-AA) casting film hydrogel within 1min was only 18.11%, as shown in FIG. 4. Compared with the hydrogel of the casting film, the swelling ratio of the hydrogel of the fiber film is greatly improved. The water removal rate within 1min is also greatly improved. The PU-g-P (NIPAm-co-AA) fiber membrane hydrogel is proved to have a faster temperature response rate.
Comparative example 2
The difference from the embodiment 1 is that: and 3) in the preparation process of the PU-g-P (NIPAm-co-AA) hydrogel, the adding amount of the acrylic acid is 0, and the PU-g-PNIPAm fiber membrane hydrogel is obtained. The fiber diameter of the PU-g-PNIPAm fiber membrane hydrogel is 311 +/-125 nm, the porosity and the specific surface area are 93.1 percent and 14.01m2(ii) in terms of/g. The swelling ratio of the PU-g-PNIPAm fiber membrane hydrogel when reaching the swelling equilibrium is 24.5g/g, as shown in FIG. 2. The dehydration rate of the PU-g-PNIPAm fiber membrane hydrogel in 1min is 59.8%. The PU-g-PNIPAm fiber membrane hydrogel was not responsive to pH as shown in FIG. 3.
Comparative example 3
The difference from example 1 is that in step 3) preparation of PU-g-P (NIPAm-co-AA) hydrogel, the amount of vinyl modified silica added is 0. The diameter of the hydrogel fiber of the PU-g-P (NIPAm-co-AA) fiber membrane is 330 +/-180 nm, and the porosity and the specific surface area are respectively 90.1 percent and 15.2m2The swelling ratio of the hydrogel to the swelling equilibrium was 23.5 g/g. The hydrogel had a water removal rate of 35.5% in 1 min. The modified silica is added mainly to make the gel form a discontinuous mesh structure. Thereby increasing the swelling ratio and having faster response to temperature.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. Polyurethane nanofiber membrane grafted poly (A) (B)N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that it comprises the following steps:
respectively preparing a polyurethane nanofiber membrane and vinyl modified silicon dioxide;
will be provided withN-isopropylacrylamide, acrylic acid,N, N’Dissolving methylene bisacrylamide and ammonium persulfate in distilled water, adding the vinyl modified silica, uniformly dispersing, adding the polyurethane nanofiber membrane activated by benzophenone, and irradiating by using ultraviolet light under the protection of nitrogen to perform polymerization reaction to obtain the polyurethane nanofiber membrane graft polymer (A)N-isopropylacrylamide-co-acrylic acid) hydrogel;
the polyurethane nanofiber membrane is prepared by a thermally induced phase separation method, and the vinyl modified silicon dioxide is prepared by reacting vinyl triethoxysilane with silicon dioxide;
the preparation method of the polyurethane nanofiber membrane comprises the following steps:
dissolving polyurethane inN,N’-dimethylformamide solvent to obtain a polyurethane solution;
quenching the polyurethane solution at-40 to-10 ℃ for 120-180 min, and removingN,N’-dimethylformamide solvent, obtaining said polyurethane nanofibrous membrane;
the concentration of the polyurethane solution is 6-9 g/100 mL.
2. The polyurethane nanofiber membrane-grafted poly(s) of claim 1N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that the vinyl-modified silica is prepared by:
preparing an ethanol solution of vinyl triethoxysilane and an ethanol dispersion of silicon dioxide respectively;
adding the ethanol solution of the vinyl triethoxysilane into the ethanol dispersion liquid of the silicon dioxide, carrying out ultrasonic treatment for 2 hours, and then carrying out centrifugal separation, ethanol washing and vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide;
the preparation method of the ethanol solution of the vinyl triethoxysilane comprises the following steps: dissolving vinyl triethoxysilane in ethanol, wherein the preparation method of the ethanol dispersion liquid of silicon dioxide comprises the following steps: dispersing silicon dioxide in ethanol.
3. The polyurethane nanofiber membrane-grafted poly(s) of claim 2N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that the mass ratio of vinyltriethoxysilane to silica is 1: 1.
4. the polyurethane nanofiber membrane-grafted poly(s) of claim 1N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that it is obtained by a process for the preparation of said hydrogelN-isopropylacrylamide, acrylic acid,N, N’-the mass ratio of methylene bisacrylamide, ammonium persulfate and vinyl-modified silica is 50: (2-4): 1: 1: (1-2).
5. The polyurethane nanofiber membrane-grafted poly(s) of claim 1N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that it is obtained by a process for the preparation of said hydrogelN-The mass ratio of the isopropyl acrylamide to the polyurethane fiber membrane is 5: 1, the radiation time is 20-60 min.
6. The polyurethane nanofiber membrane-grafted poly(s) of claim 1N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that the activation method of the polyurethane nanofiber membrane is:
and (3) dissolving the polyurethane nanofiber membrane in acetone solution of benzophenone for 5min, taking out, and drying in vacuum for later use.
7. The polyurethane nanofiber membrane-grafted poly(s) (of claim 6)N-isopropylacrylamide-co-acrylic acid) hydrogel, characterized in that the mass fraction of benzophenone in the acetone solution of benzophenone is 4%.
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