CN115947888A - Preparation method of rapid temperature-sensitive response polyacrylamide composite hydrogel - Google Patents
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- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 19
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 56
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 28
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 28
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention relates to the technical field of intelligent high polymer materials, in particular to a quick temperature-sensitive response polyacrylamide composite water-condensationA method for preparing the glue. The method firstly passes through nano SiO 2 MPS-SiO preparation with methacryloxypropyl trimethoxy silane 2 Nano-microspheres; then copolymerizing with N-isopropyl acrylamide to obtain N-isopropyl acrylamide (PNIPAM) grafted SiO 2 Nano-microspheres; then reacting with acrylamide to obtain the polyacrylamide composite hydrogel. The preparation method does not relate to complex equipment, the raw materials are low in price, and the process is simple and easy to implement; the prepared material has quick response to temperature change, obvious change of gel transparency and stable size and shape.
Description
Technical Field
The invention relates to the technical field of intelligent high polymer materials, in particular to a preparation method of a quick temperature-sensitive response polyacrylamide composite hydrogel.
Background
The hydrogel is a novel functional polymer material with a three-dimensional network structure, can still maintain certain shape and mechanical property after absorbing water and swelling, has good water retention and biocompatibility, and is widely applied to the fields of agriculture, water treatment, food industry, biomedicine and the like. The intelligent hydrogel can respond to external environment changes (such as temperature, electromagnetic field, light, pH value, ionic strength and the like) and generate corresponding performance changes, and has wide application prospects in the aspects of tissue engineering, wound management, soft/micro robots, biosensing detection and the like.
The temperature-sensitive hydrogel has mild stimulation conditions and easy realization of response behaviors, thereby attracting wide interests in academia and industry. Taking poly (N-isopropylacrylamide) (PNIPAM) hydrogel as an example, the Low Critical Solution Temperature (LCST) of the hydrogel is about 32 ℃, and the hydrogel can respond to the change of phase of human body temperature to swell/shrink, so that the hydrogel brings about a plurality of changes of mechanical properties, transparency and the like, and has been widely researched and practically applied.
At present, with the development of multi-component monomer copolymerization, nano composite reinforcement, topological network structure design and other strategies, the mechanical property and biocompatibility of the temperature-sensitive hydrogel are continuously improved, and application breakthrough is continuously achieved in the frontier fields of controllable drug release, intelligent optical components and the like, but the conventional centimeter-level temperature-sensitive hydrogel still has the general defect of overlong response time, and particularly in the swelling process with limited water diffusion kinetics, the equilibrium time is usually required to be several hours. In addition, the response process of the existing temperature-sensitive hydrogel is accompanied by swelling/shrinking, the volume size change is obvious, the performance failure and the structure instability of the hydrogel are easily caused, and the accurate use of the hydrogel in a limited space is limited. The promotion of the response rate and the dimensional stability of the temperature-sensitive hydrogel becomes a key for the development of the leading-edge application of the temperature-sensitive hydrogel.
Therefore, the invention provides the quick temperature-sensitive response composite hydrogel with stable size and the preparation method thereof, and the preparation method has important practical significance and application value.
Disclosure of Invention
The invention aims to solve the problems involved in the background technology and provides a preparation method of a rapid temperature-sensitive response polyacrylamide composite hydrogel. The material prepared by the method has high dimensional stability, can quickly respond to the change of self transparency of temperature, and has short synthetic route and simple process.
Specifically, the invention adopts the following technical scheme:
a preparation method of quick temperature-sensitive response polyacrylamide composite hydrogel comprises the following steps:
(1) 1.0-2.0g of nano SiO 2 Dispersing in 70-100 mL ethanol, adding 0.5-1.0 mL Methacryloxypropyltrimethoxysilane (MPS), reacting at 30-40 deg.C for 5 hr, centrifuging, cleaning, and freezingDrying to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2-0.5g of MPS-SiO 2 Dissolving the nano-microspheres and 1.0-3.0 g of N-isopropylacrylamide (NIPAM) in 100 mL of deionized water for copolymerization, centrifugally purifying after the copolymerization is finished, washing and freeze-drying to obtain poly-N-isopropylacrylamide (PNIPAM) grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano-microspheres into 2.0-4.0 mol/L Acrylamide (AM) solution, mixing uniformly, and grafting SiO with PNIPAM 2 The addition amount of the nano-microspheres is 10-30% of the mass of acrylamide; and then, adding a cross-linking agent and an initiator into the system, and reacting for 24 hours at room temperature to prepare the quick temperature-sensitive response polyacrylamide composite hydrogel.
Preferably, in step (3), PNIPAM is grafted onto SiO 2 The addition amount of the nano-microspheres is 25-30% of the mass of the AM.
Preferably, the cross-linking agent is N, N' -Methylene Bisacrylamide (MBAA), and the addition amount of the cross-linking agent is 0.002: 1 according to the molar mass ratio of the MBAA to the acrylamide.
Preferably, the initiator is Ammonium Persulfate (APS), and the addition amount of the initiator is 0.01: 1 according to the molar mass ratio of APS: AM to acrylamide.
Preferably, the preparation method comprises the following steps:
(1) 1.0g of nano SiO 2 Dispersing in 70mL ethanol, adding 0.53mL methacryloylpropyl trimethoxy silane (MPS), reacting at 30 deg.C for 5 hr, centrifuging, cleaning, and lyophilizing to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano-microspheres and 1.0-3.0 g of N-isopropylacrylamide (NIPAM) in 100 mL of deionized water for copolymerization, centrifugally purifying, washing and freeze-drying to obtain the poly-N-isopropylacrylamide (PNIPAM) grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano-microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, and grafting SiO by PNIPAM 2 The nanometer microballoons account for 30 percent of acrylamide by mass, and then N, N 'is added'And (3) reacting a Methylene Bisacrylamide (MBAA) cross-linking agent and an Ammonium Persulfate (APS) initiator at room temperature for 24 hours to prepare the Polyacrylamide (PAM) composite hydrogel.
The PAM composite hydrogel prepared by the invention utilizes SiO 2 The enhancement of the nano particles obviously improves the mechanical property of the nano particles; simultaneous SiO 2 The reversible phase change of the PNIPAM layer on the surface of the nano particle realizes the temperature response of the composite gel.
In the temperature response process, water molecules are carried out on the PAM gel matrix and the PNIPAM layer in situ
The transmission process saves the process of exchanging the conventional temperature sensitive gel with external substances, so that the quick response to the temperature can be realized.
In the temperature rise process, the hydrogel can be reversibly changed from transparent to opaque within less than 5 s, so that the hydrogel has wide application prospect in temperature-sensitive detection/sensing devices and intelligent optical devices.
In addition, the hydrogel is stable in size in the temperature response process, potential application risks caused by performance failure and structural instability of a gel device are avoided, and the application performance of the gel is further improved.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method does not relate to complex equipment, the raw materials are low in price, and the process is simple and easy to implement;
the prepared material has quick response to temperature change, obvious change of gel transparency and stable size and shape;
the application prospect is good, and the material is expected to be applied to biomedicine, flexible intelligent devices and intelligent optical components.
Drawings
FIG. 1 shows commercially pure SiO 2 Microsphere and PNIPAM grafted SiO prepared by the invention 2 Scanning Electron Microscope (SEM) photographs of the nanospheres. In a is pure SiO 2 Microspheres, in b is PNIPAM grafted SiO 2 And (4) nano microspheres.
FIG. 2 shows the gelling process of PAM composite hydrogel prepared by the present invention. In a, AM solution and in b, PAM gel are used.
FIG. 3 shows a PAM composite hydrogel prepared in example 1 of the present invention. PAM gel is adopted in the step a at normal temperature, and PAM gel is adopted in the step b after heating.
FIG. 4 is a graph of the ultraviolet absorption spectrum of the PAM composite gel prepared by the present invention before and after temperature response.
FIG. 5 is a schematic diagram of the preparation of PAM composite hydrogels according to the present invention.
FIG. 6 is a mechanical property test chart of the PAM composite hydrogel prepared by the present invention.
Detailed Description
Representative embodiments will now be further refined. It should be understood that the following description is not intended to limit the embodiments to one preferred embodiment. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the embodiments as defined by the appended claims.
Example 1: a quick temperature-sensitive response polyacrylamide composite hydrogel is prepared by the following steps:
(1) 1.0g of commercially available nano SiO 2 (see FIG. 1 a, S104596, shanghai Aladdin Co.) by dispersing in 70mL ethanol, adding 0.53mL MPS, reacting at 30 deg.C for 5 hr, centrifuging, washing, and lyophilizing to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano-microspheres and 1.0g of NIPAM in 100 mL of deionized water, copolymerizing for 5 hours at 75 ℃, centrifugally purifying, washing for 5 times by using the deionized water, and freeze-drying to obtain PNIPAM grafted SiO 2 Nanospheres (see fig. 1 b);
(3) Grafting PNIPAM to SiO 2 Adding the nano microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, wherein the addition amount of the nano microspheres is 10 wt% of the mass of the acrylamide, then adding a cross-linking agent and an initiator into the system, wherein the addition amount of the cross-linking agent N, N' -Methylene Bisacrylamide (MBAA) is 0.002: 1 according to the molar mass ratio of MBAA: AM to the acrylamide, the addition amount of the initiator Ammonium Persulfate (APS) is 0.01: 1 according to the molar mass ratio of APS: AM to the acrylamide, injecting the mixed solution into a reaction tank, and reacting at room temperature for 24 hours to obtain the Polyacrylamide (PAM) composite hydrogel. (see fig. 2 b).
(4) The PAM composite hydrogel has a remarkable change of transparency after being heated, and is changed from a semitransparent state (shown in figure 3 a) to a completely opaque state (shown in figure 3 b). The UV absorption spectrum before and after the gel temperature response (as shown in FIG. 4) shows a great difference in transmittance between the two. Adding PNIPAM grafted SiO with different contents 2 The PAM composite gel of the nano-microsphere has obvious difference in mechanical property and is positively correlated with the addition amount of the microsphere (as shown in figure 5). All this is due to the rational design of PAM complex gels (see figure 6).
Example 2: a quick temperature-sensitive response polyacrylamide composite hydrogel is prepared by the following steps:
(1) 1.0g of commercially available nano SiO 2 (S104596, shanghai Allantin Co., ltd.) was dispersed in 70mL of ethanol, 0.53mL of MPS was added, the reaction was carried out at 30 ℃ for 5 hours, centrifuged, washed and lyophilized to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano-microspheres and 2.0g of NIPAM in 100 mL of deionized water, copolymerizing for 5 hours at 75 ℃, centrifugally purifying, washing for 5 times by using the deionized water, and freeze-drying to obtain PNIPAM grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, wherein the addition amount of the nano microspheres is 10 wt% of the mass of the acrylamide, then adding a cross-linking agent and an initiator into the system, wherein the addition amount of the cross-linking agent N, N' -Methylene Bisacrylamide (MBAA) is 0.002: 1 according to the molar mass ratio of MBAA: AM to the acrylamide, the addition amount of the initiator Ammonium Persulfate (APS) is 0.01: 1 according to the molar mass ratio of APS: AM to the acrylamide, injecting the mixed solution into a reaction tank, and reacting at room temperature for 24 hours to obtain the Polyacrylamide (PAM) composite hydrogel. .
Example 3: a quick temperature-sensitive response polyacrylamide composite hydrogel is prepared by the following steps:
(1) 1.0g of commercially available nano SiO 2 (S104596, shanghai Alatin Co.) dispersed in 70mL ethanol, adding 0.53mL MPS, reacting at 30 deg.C for 5 hr, centrifuging, washing, and lyophilizing to obtain final productMPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano-microspheres and 3.0 g of NIPAM in 100 mL of deionized water, copolymerizing for 5 hours at 75 ℃, centrifugally purifying, washing for 5 times by using the deionized water, and freeze-drying to obtain PNIPAM grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, wherein the addition amount of the nano microspheres is 10 wt% of the mass of the acrylamide, then adding a cross-linking agent and an initiator into the system, wherein the addition amount of the cross-linking agent N, N' -Methylene Bisacrylamide (MBAA) is 0.002: 1 according to the molar mass ratio of MBAA: AM to the acrylamide, the addition amount of the initiator Ammonium Persulfate (APS) is 0.01: 1 according to the molar mass ratio of APS: AM to the acrylamide, injecting the mixed solution into a reaction tank, and reacting at room temperature for 24 hours to obtain the Polyacrylamide (PAM) composite hydrogel.
Example 4: a quick temperature-sensitive response polyacrylamide composite hydrogel is prepared by the following steps:
(1) 1.0g of commercially available nano SiO 2 (S104596, shanghai Alatidine company) in 70mL ethanol, adding 0.53mL MPS, reacting at 30 deg.C for 5 hr, centrifuging, cleaning, and lyophilizing to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano-microspheres and 1.0g of NIPAM in 100 mL of deionized water, copolymerizing for 5 hours at 75 ℃, centrifugally purifying, washing for 5 times by using the deionized water, and freeze-drying to obtain PNIPAM grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, wherein the addition amount of the nano microspheres is 20 wt% of the mass of the acrylamide, then adding a cross-linking agent and an initiator into the system, wherein the addition amount of the cross-linking agent N, N' -Methylene Bisacrylamide (MBAA) is 0.002: 1 according to the molar mass ratio of MBAA: AM to the acrylamide, the addition amount of the initiator Ammonium Persulfate (APS) is 0.01: 1 according to the molar mass ratio of APS: AM to the acrylamide, injecting the mixed solution into a reaction tank, and reacting at room temperature for 24 hours to obtain the Polyacrylamide (PAM) composite hydrogel.
Example 5: a quick temperature-sensitive response polyacrylamide composite hydrogel is prepared by the following steps:
(1) 1.0g of commercially available nano SiO 2 (S104596, shanghai Alatidine company) in 70mL ethanol, adding 0.53mL MPS, reacting at 30 deg.C for 5 hr, centrifuging, cleaning, and lyophilizing to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano-microspheres and 1.0g of NIPAM in 100 mL of deionized water, copolymerizing for 5 hours at 75 ℃, centrifugally purifying, washing for 5 times by using the deionized water, and freeze-drying to obtain PNIPAM grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, wherein the addition amount of the nano microspheres is 30 wt% of the mass of the acrylamide, then adding a cross-linking agent and an initiator into the system, wherein the addition amount of the cross-linking agent N, N' -Methylene Bisacrylamide (MBAA) is 0.002: 1 according to the molar mass ratio of MBAA: AM to the acrylamide, the addition amount of the initiator Ammonium Persulfate (APS) is 0.01: 1 according to the molar mass ratio of APS: AM to the acrylamide, injecting the mixed solution into a reaction tank, and reacting at room temperature for 24 hours to obtain the Polyacrylamide (PAM) composite hydrogel.
Example 6: a quick temperature-sensitive response polyacrylamide composite hydrogel is prepared by the following steps:
(1) Adding a cross-linking agent and an initiator into 2.0 mol/L Acrylamide (AM) solution, wherein the addition amount of the cross-linking agent N, N' -methylene-bis-acrylamide (MBAA) is 0.002: 1 according to the molar mass ratio of MBAA to AM to acrylamide, the addition amount of the initiator Ammonium Persulfate (APS) is 0.01: 1 according to the molar mass ratio of APS to AM to acrylamide, and injecting the mixed solution into a reaction tank to react for 24 hours at room temperature to prepare the Polyacrylamide (PAM) hydrogel.
The hydrogel products prepared in the above examples were subjected to performance tests.
The method is mainly used for testing the temperature response speed, and the specific process of the test is as follows:
cutting the PAM composite gel into small blocks with the size of 10 multiplied by 2 mm, completely immersing the PAM composite gel into hot water at 75 ℃, immediately starting timing, ending timing when the gel is completely opaque, and expressing the response speed by the time required by the transparency transition of the gel; the volume change before and after the gel response was also measured and recorded, and the test results are shown in table 1 below.
The volume change rate (R) in Table 1 was calculated from the following equation.
Wherein V 1 Volume of gel after temperature response, V 0 The original volume of the gel.
From table 1, it can be seen that the PAM composite hydrogel materials prepared by the present invention all exhibit rapid temperature response and excellent dimensional stability.
It will be apparent to those skilled in the art that certain modifications, combinations, and variations can be made in light of the above teachings.
Claims (5)
1. A preparation method of rapid temperature-sensitive response polyacrylamide composite hydrogel is characterized by comprising the following steps: the method comprises the following steps:
(1) 1.0-2.0g of nano SiO 2 Dispersing in 70-100 mL ethanol, adding 0.5-1.0 mL Methacryloxypropyltrimethoxysilane (MPS), reacting at 30-40 deg.C for 5 hr, centrifuging, cleaning, and lyophilizing to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2-0.5g of MPS-SiO 2 Dissolving the nano-microspheres and 1.0-3.0 g of N-isopropylacrylamide (NIPAM) in 100 mL of deionized water for copolymerization, centrifugally purifying after the copolymerization is finished, washing and freeze-drying to obtain poly-N-isopropylacrylamide (PNIPAM) grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 The nano-microsphere is added to the solution with the concentration of 2.0-40 mol/L Acrylamide (AM) solution is mixed evenly, PNIPAM is grafted with SiO 2 The addition amount of the nano-microspheres is 10-30% of the mass of acrylamide; and then, adding a cross-linking agent and an initiator into the system, and reacting for 24 hours at room temperature to prepare the quick temperature-sensitive response polyacrylamide composite hydrogel.
2. The method of claim 1, wherein: PNIPAM grafting SiO in step (3) 2 The addition amount of the nano-microspheres is 25-30% of the mass of the AM.
3. The method according to claim 1 or 2, characterized in that: the cross-linking agent is N, N' -Methylene Bisacrylamide (MBAA), and the addition amount of the cross-linking agent is 0.002: 1 according to the molar mass ratio of MBAA to AM to acrylamide.
4. The method according to claim 1 or 2, characterized in that: the initiator is Ammonium Persulfate (APS), and the addition amount of the initiator is 0.01: 1 according to the molar mass ratio of APS to AM to acrylamide.
5. The method of claim 1, wherein: the method comprises the following steps:
(1) 1.0g of nano SiO 2 Dispersing in 70mL ethanol, adding 0.53mL methacryloylpropyl trimethoxy silane (MPS), reacting at 30 deg.C for 5 hr, centrifuging, cleaning, and lyophilizing to obtain MPS-SiO 2 Nano-microspheres;
(2) 0.2 g of MPS-SiO 2 Dissolving the nano microspheres and 1.0-3.0 g of N-isopropylacrylamide (NIPAM) in 100 mL of deionized water for copolymerization, centrifugally purifying, washing and freeze-drying to obtain the poly-N-isopropylacrylamide (PNIPAM) grafted SiO 2 Nano-microspheres;
(3) Grafting PNIPAM to SiO 2 Adding the nano-microspheres into 2.0 mol/L Acrylamide (AM) solution, uniformly mixing, and grafting SiO by PNIPAM 2 The nano-microsphere is 30% of acrylamide by mass, and then an N, N' -Methylene Bisacrylamide (MBAA) cross-linking agent and an Ammonium Persulfate (APS) primer are addedAnd (3) reacting the hair agent for 24 hours at room temperature to prepare the Polyacrylamide (PAM) composite hydrogel.
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