Interpenetrating network hydrogel and preparation method thereof

Abstract

The invention belongs to the technical field of hydrogel, and relates to interpenetrating network hydrogel and a preparation method thereof. The invention provides a preparation method of interpenetrating network hydrogel. The preparation method comprises the following steps: mixing a compound shown as a formula (I), a compound shown as a formula (II) and water, heating and stirring to obtain a first network solution; mixing and stirring the first network solution, a compound shown in a formula (III) and a compound shown in a formula (IV), adding an initiator, and reacting to obtain an interpenetrating network hydrogel prepolymer; the mass ratio of the first network solution to the compound shown in the formula (III) to the compound shown in the formula (IV) is (10-18): (15-20): (25-35); the interpenetrating network hydrogel prepolymer is dried and purified, and a swelled interpenetrating network hydrogel product is obtained; the adsorbent shows excellent adsorption performance in the field of dye wastewater treatment.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogels and relates to an interpenetrating network hydrogel and a preparation method thereof. Background Art

[0002] Dyes have the characteristics of good water solubility, bright colors, light and wash resistance, etc., and are widely used in the fields of textiles, cosmetics, papermaking, etc. Dye wastewater has carcinogenicity and mutagenicity, which can cause serious harm to the kidneys, livers, brains, etc. of humans and animals. Moreover, dye wastewater contains a large amount of harmful substances such as organic matter and heavy metals, seriously polluting the water body, resulting in the turbidity and peculiar smell of the water body, and even affecting the balance of the water body ecosystem. The discharge of dye wastewater will waste a large amount of water resources. In areas with water resource shortages, the discharge of dye wastewater will seriously affect the sustainable utilization of water resources. Therefore, how to treat the pollution of dye wastewater has become an important issue in the current industry development.

[0003] At present, the common treatment methods for dye wastewater include coagulation sedimentation method, membrane separation method, biodegradation method, chemical oxidation method, adsorption method, etc. Among them, the adsorption method with low cost and easy operation is one of the technologies with good development prospects in the treatment of dye wastewater. Hydrogel is a polymer with a specific three-dimensional network structure. The unique polymer network structure and abundant functional groups on the molecular chain can adsorb dye pollutants with high capacity, making it show excellent performance in the treatment of dye wastewater. Summary of the Invention

[0004] The purpose of the present invention is to provide an interpenetrating network hydrogel and a preparation method thereof. The unique three-dimensional network structure of the interpenetrating network hydrogel prepared by the present invention has a high adsorption capacity and can show excellent adsorption performance in the field of dye wastewater treatment.

[0005] Based on the above purpose, the present application solves this need in the field by providing a preparation method of an interpenetrating network hydrogel.

[0006] On the one hand, the present invention relates to a preparation method of an interpenetrating network hydrogel, and the preparation method includes:

[0007] Mix a compound of formula (Ⅰ), a compound of formula (Ⅱ) and water, heat and stir to obtain a first network solution; the first network solution includes 10% - 18% of the compound of formula (Ⅰ), 1% - 5% of the compound of formula (Ⅱ) and the remaining water;

[0008] Mix the first network solution, a compound of formula (Ⅲ) and a compound of formula (Ⅳ), stir and then add an initiator, and react to obtain an interpenetrating network hydrogel prepolymer; the mass ratio of the first network solution, the compound of formula (Ⅲ) and the compound of formula (Ⅳ) is 10 - 18:15 - 20:25 - 35;

[0009] Dry and purify the interpenetrating network hydrogel prepolymer to obtain the swollen interpenetrating network hydrogel product;

[0010] The structural formulas of the compound of formula (I), the compound of formula (II), the compound of formula (III) and the compound of formula (IV) are as follows:

[0011]

[0012] For the compound of formula (I), m is an integer ranging from 500 to 2400;

[0013] For the compound of formula (II), R1 is a C1-C4 hydrocarbon group;

[0014] For the compound of formula (III), 0 ≤ n ≤ 12 and n is an integer;

[0015] For the compound of formula (IV), R 2 is a hydrogen group or a methyl group, and R 3 is a C1-C 18 hydrocarbon group or a C2-C4 hydroxy-containing hydrocarbon group.

[0016] Furthermore, in the preparation method of the interpenetrating network hydrogel provided by the present invention, in the step of mixing the compound of formula (I), the compound of formula (II) and water, heating and stirring to obtain the first network solution, the heating temperature is 95-100 °C, stirring for 4-6 h to obtain the first network solution, and cooling to room temperature.

[0017] Furthermore, in the preparation method of the interpenetrating network hydrogel provided by the present invention, in the step of mixing the first network solution, the compound of formula (III) and the compound of formula (IV), stirring and then adding an initiator to react to obtain the interpenetrating network hydrogel prepolymer, the first network solution, the compound of formula (III) and the compound of formula (IV) are mixed and stirred for 15-20 min and then the initiator is added, and stirring and reacting for 1-2 h to obtain the interpenetrating network hydrogel prepolymer.

[0018] Furthermore, in the preparation method of the interpenetrating network hydrogel provided by the present invention, the mass of the added initiator accounts for 1-2% of the total mass of the compound of formula (III) and the compound of formula (IV).

[0019] Furthermore, in the preparation method of the interpenetrating network hydrogel provided by the present invention, in the step of drying and purifying the interpenetrating network hydrogel prepolymer, the interpenetrating network hydrogel prepolymer is dried at 60-70 °C, and after drying, it is put into distilled water for purification treatment for 48-96 h to obtain the swollen interpenetrating network hydrogel product.

[0020] Preferably, in the preparation method of the interpenetrating network hydrogel provided by the present invention, R1 of the compound of formula (II) is a C1-C2 hydrocarbon group.

[0021] Furthermore, an interpenetrating network hydrogel according to the present invention is prepared by the above preparation method.

[0022] On the other hand, the interpenetrating network hydrogel prepared by the present invention forms a hydrogel product with a unique three-dimensional network structure through the synergistic effect between monomers. This hydrogel has excellent adsorption performance and can be applied to the treatment of dye wastewater.

[0023] The present invention has the following beneficial effects or advantages compared with the prior art:

[0024] Based on the harm of dye wastewater to the environment and human body, through molecular design, the present invention combines a first polymer network and a second polymer network to design an interpenetrating network hydrogel product with controllable and adjustable molecular structure. This type of hydrogel has low economic cost, simple preparation process and excellent adsorption performance. The interpenetrating network hydrogel prepared by the present invention forms a hydrogel product with a unique three-dimensional network structure through the synergistic effect between monomers. Especially when the ratio of the two monomers in the first polymer network is 5:1 and the ratio of the two monomers in the second polymer network is 1:2, the resulting hydrogel network structure can interact with dye particles through hydrogen bonds, ionic bonds and van der Waals forces, and can efficiently adsorb dye particles. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is the infrared spectrum diagram of the interpenetrating network hydrogel. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] Next, the technical solutions of the present invention will be described in conjunction with the embodiments. However, the present invention is not limited to the following embodiments.

[0027] In order to enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and drawings, but the embodiments cited are not intended to limit the present invention.

[0028] In the following embodiments, the experimental methods and detection methods are all conventional methods unless otherwise specified; the reagents and materials can all be purchased on the market unless otherwise specified.

[0029] Embodiment

[0030] Embodiment 1

[0031] This embodiment provides a preparation method of an interpenetrating network hydrogel, including the following steps:

[0032] Weigh 2.25 g of the compound of formula (I) and 0.45 g of the compound of formula (II); add the above two substances into a three-necked flask, add distilled water, stir and heat in a constant temperature water bath, control the temperature at 98 °C, stir for 5 h to obtain the first network solution, and cool to room temperature;

[0033] Take 15 g of the obtained first network solution, add 16 g of the compound of formula (III) and 32 g of the compound of formula (IV) into the three-necked flask in sequence. After stirring for 18 min, add 0.72 g of potassium persulfate dropwise thereto, and stir and react for 1.5 h to obtain an interpenetrating network hydrogel prepolymer;

[0034] Pour the obtained interpenetrating network hydrogel prepolymer into a cylindrical mold, dry it at 65 °C, and then put the dried sample into distilled water for purification treatment for 70 h to obtain the swollen interpenetrating network hydrogel product.

[0035] The structural formulas of the compound of formula (I), the compound of formula (II), the compound of formula (III) and the compound of formula (IV) are as follows:

[0036]

[0037] Example 2

[0038] This example provides a preparation method of an interpenetrating network hydrogel, which includes the following steps:

[0039] Weigh 1 g of the compound of formula (I) and 0.1 g of the compound of formula (II); add the above two substances into a three-necked flask, add distilled water, stir and heat in a constant temperature water bath, control the temperature at 95 °C, stir for 4 h to obtain the first network solution, and cool to room temperature;

[0040] Take 10 g of the obtained first network solution, add 15 g of the compound of formula (III) and 25 g of the compound of formula (IV) into the three-necked flask in sequence. After stirring for 15 min, add 0.4 g of potassium persulfate dropwise thereto, and stir and react for 1 h to obtain an interpenetrating network hydrogel prepolymer.

[0041] Pour the obtained interpenetrating network hydrogel prepolymer into a cylindrical mold, dry it at 60 °C, and then put the dried sample into distilled water for purification treatment for 48 h to obtain the swollen interpenetrating network hydrogel product.

[0042] The structural formulas of the compound of formula (I), the compound of formula (II), the compound of formula (III) and the compound of formula (IV) are as follows:

[0043]

[0044] Example 3

[0045] This embodiment provides a method for preparing an interpenetrating network hydrogel, comprising the following steps:

[0046] Taking 3.24 g of the compound of formula (Ⅰ) and 0.9 g of the compound of formula (Ⅱ) by mass percentage; adding the above two substances into a three-necked flask, adding distilled water, stirring and heating in a constant temperature water bath, controlling the temperature at 100 °C, stirring for 6 h to obtain the first network solution, and cooling to room temperature;

[0047] Weighing 18 g of the obtained first network solution, 20 g of the compound of formula (Ⅲ) and 35 g of the compound of formula (Ⅳ) are successively added into the three-necked flask. After stirring for 17 min, 1.1 g of potassium persulfate is added dropwise thereto, and the mixture is stirred and reacted for 1.5 h to obtain an interpenetrating network hydrogel prepolymer.

[0048] Pouring the obtained interpenetrating network hydrogel prepolymer into a cylindrical mold, drying at 70 °C, and then putting the dried sample into distilled water for purification treatment for 96 h to obtain a swollen interpenetrating network hydrogel product.

[0049] The structural formulas of the compound of formula (Ⅰ), the compound of formula (Ⅱ), the compound of formula (Ⅲ) and the compound of formula (Ⅳ) are as follows:

[0050]

[0051] Example 4

[0052] This embodiment provides a method for preparing an interpenetrating network hydrogel, which is different from Example 1 in that hydrogels are prepared using compounds with different structures. Specifically, the structural formulas of the compound of formula (Ⅰ), the compound of formula (Ⅱ), the compound of formula (Ⅲ) and the compound of formula (Ⅳ) are as follows:

[0053]

[0054] Example 5

[0055] This embodiment provides a method for preparing an interpenetrating network hydrogel, which is different from Example 1 in that hydrogels are prepared using compounds with different structures. Specifically, the structural formulas of the compound of formula (Ⅰ), the compound of formula (Ⅱ), the compound of formula (Ⅲ) and the compound of formula (Ⅳ) are as follows:

[0056]

[0057] Example 6

[0058] This embodiment provides a method for preparing an interpenetrating network hydrogel, comprising the following steps:

[0059] Weigh 1 g of the compound of formula (I) and 0.1 g of the compound of formula (II); add the above two substances into a three-necked flask, add distilled water, stir and heat in a constant temperature water bath, control the temperature at 95 °C, stir for 4 h to obtain the first network solution, and cool to room temperature;

[0060] Take 8 g of the obtained first network solution, add 13 g of the compound of formula (III) and 23 g of the compound of formula (IV) into the three-necked flask in sequence. After stirring for 15 min, add 0.4 g of potassium persulfate dropwise thereto, and stir and react for 1 h to obtain an interpenetrating network hydrogel prepolymer;

[0061] Pour the obtained interpenetrating network hydrogel prepolymer into a cylindrical mold, dry it at 60 °C, and then put the dried sample into distilled water for purification treatment for 48 h to obtain the swollen interpenetrating network hydrogel product.

[0062] The structural formulas of the compound of formula (I), the compound of formula (II), the compound of formula (III) and the compound of formula (IV) are as follows:

[0063]

[0064]

[0065] Example 7

[0066] This example provides a preparation method of an interpenetrating network hydrogel, including the following steps:

[0067] Take 3.24 g of the compound of formula (I) and 0.9 g of the compound of formula (II) by mass percentage; add the above two substances into a three-necked flask, add distilled water, stir and heat in a constant temperature water bath, control the temperature at 100 °C, stir for 6 h to obtain the first network solution, and cool to room temperature;

[0068] Weigh 20 g of the first network solution obtained in step S1, add 25 g of the compound of formula (III) and 38 g of the compound of formula (IV) into the three-necked flask in sequence. After stirring for 17 min, add 1.1 g of potassium persulfate dropwise thereto, and stir and react for 1.5 h to obtain an interpenetrating network hydrogel prepolymer.

[0069] Pour the obtained interpenetrating network hydrogel prepolymer into a cylindrical mold, dry it at 70 °C, and then put the dried sample into distilled water for purification treatment for 96 h to obtain the swollen interpenetrating network hydrogel product.

[0070] The structural formulas of the compound of formula (I), the compound of formula (II), the compound of formula (III) and the compound of formula (IV) are as follows:

[0071]

[0072] Example 8

[0073] This example provides the structure and performance testing of the prepared interpenetrating network hydrogel product:

[0074] Infrared spectroscopy test: Using the IRP Restige-21 infrared spectrometer from Shimadzu Corporation of Japan, with potassium bromide as the background, in the scanning wavelength range of 500 cm -1 to 4000 cm -1 at a resolution of 4 cm -1 and scanning 32 times to characterize the structure of the interpenetrating network hydrogel product.

[0075] It can be seen from the infrared spectrum that the stretching vibration absorption peak of -OH appears at 3450 cm -1 and the asymmetric stretching vibration peaks of -CH3 and -CH2 are at 2969 - 2892 cm -1 . The stretching vibration absorption peak of -C=O in compounds (III) and (IV) is at 1650 cm -1 , the stretching vibration absorption peak of C=N in compound (II) appears at 1685 cm -1 , the symmetric stretching vibration absorption peak of -C-O-C after the cross-linking reaction appears at 1068 cm -1 , and at the same time, the stretching vibration absorption peak of C=C in compounds (III) and (IV) does not appear at 1680 cm -1 , indicating that compounds (III) and (IV) have completely reacted under the initiation of the initiator.

[0076] Adsorption rate and adsorption capacity test: Respectively add the interpenetrating network hydrogels prepared in Examples 1 - 7 into a 20 mg / L methylene blue dye solution, place it in a constant temperature oscillator and oscillate for 24 h, then use a UV spectrometer to measure the absorbance of the dye solution before and after adsorption, and calculate the adsorption rate (E, %) and the maximum adsorption capacity (Qe, mg / g). The calculation formulas for the adsorption rate (E, %) and the maximum adsorption capacity (Qe, mg / g) are as follows:

[0077]

[0078] where ρ0 is the initial mass concentration of the methylene blue solution before adsorption (mg / L), ρ e is the mass concentration of the methylene blue solution after adsorption equilibrium (mg / L), m is the mass of the interpenetrating network hydrogel (g), and V is the volume of the methylene blue solution (L).

[0079] Test item Example 1 Example 2 Example 3 Example 4 Example 5 E / ％ 98.86 84.12 86.97 92.69 91.15 <![CDATA[Q e / (mg / g)]]> 65.37 56.31 58.82 62.43 61.21 Example 6 Example 7 E / ％ 75.23 71.45 <![CDATA[Q e / (mg / g)]]> 46.13 43.56

[0080] From the above performance test data, it can be seen that through the formulation design and molecular structure design of the present invention, the interpenetrating network hydrogels prepared in Examples 1-5 control the ratio of monomer components and specific molecules, and the adsorption rate of dye particles reaches more than 84%, and the maximum adsorption capacity is not less than 56%. Examples 6-7 are superior to Examples 1-5. It can be seen from this that the hydrogels prepared with the monomer component ratios of Examples 6-7 have lower adsorption rates and adsorption capacities. Therefore, controlling the ratio of monomer components and the structure of specific molecules can obtain hydrogels with higher adsorption rates and adsorption capacities.

[0081] In the first network, the ratio of the two monomers is 5:1. In the second network, when the ratio of the two monomers is 1:2, under this condition, by the synergistic effect of the first network and the second network, an interpenetrating network hydrogel product is prepared, which can efficiently adsorb dye particles, and the adsorption rate can reach 98.86%, and the maximum adsorption capacity is 65.37 mg / g. The present invention has successfully prepared a hydrogel product with a unique three-dimensional network structure. Through the action of hydrogen bonds, ionic bonds and van der Waals forces between the hydrogel network structure and dye particles during the adsorption of dyes, excellent adsorption of dye ions is achieved.

[0082] As described above, the present invention can be preferably implemented. The above examples are only descriptions of the preferred embodiments of the present invention and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various changes and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the present invention.

Claims

1. A preparation method of an interpenetrating network hydrogel, characterized in that, The preparation method includes the following steps: Mix the compound of formula (Ⅰ), the compound of formula (Ⅱ) and water, heat and stir to obtain a first network solution; the first network solution includes 10% - 18% of the compound of formula (Ⅰ), 1% - 5% of the compound of formula (Ⅱ) and the remaining water; Mix the first network solution, the compound of formula (Ⅲ) and the compound of formula (Ⅳ), stir, and then add an initiator, and react to obtain an interpenetrating network hydrogel prepolymer; the mass ratio of the first network solution, the compound of formula (Ⅲ) and the compound of formula (Ⅳ) is 10 - 18:15 - 20:25 - 35; Dry and purify the interpenetrating network hydrogel prepolymer to obtain a swollen interpenetrating network hydrogel product; The structural formulas of the compound of formula (Ⅰ), the compound of formula (Ⅱ), the compound of formula (Ⅲ) and the compound of formula (Ⅳ) are as follows: For the compound of formula (Ⅰ), m is an integer ranging from 500 to 2400; R1 of the compound of formula (Ⅱ) is a hydrocarbon group with 1 - 4 carbon atoms; For the compound of formula (Ⅲ), 0 ≤ n ≤ 12 and n is an integer; In the compound of formula (IV), R2 is a hydrogen group or a methyl group, and R3 is a C1-C 18 hydrocarbon group or a C2-C4 hydrocarbon group with a hydroxyl group.

2. The preparation method of the hydrogel according to claim 1, characterized in that, In the step of mixing the compound of formula (Ⅰ), the compound of formula (Ⅱ) and water, heating and stirring to obtain a first network solution, the heating temperature is 95 - 100 °C, stir for 4 - 6 h to obtain a first network solution, and then cool to room temperature.

3. The preparation method of the hydrogel according to claim 1, characterized in that, In the step of mixing the first network solution, the compound of formula (Ⅲ) and the compound of formula (Ⅳ), stirring and then adding an initiator to react to obtain an interpenetrating network hydrogel prepolymer, the first network solution, the compound of formula (Ⅲ) and the compound of formula (Ⅳ) are mixed and stirred for 15 - 20 min, then add an initiator, and stir and react for 1 - 2 h to obtain an interpenetrating network hydrogel prepolymer.

4. The preparation method of the hydrogel according to claim 1, characterized in that, The mass of the added initiator accounts for 1% - 2% of the total mass of the compound of formula (Ⅲ) and the compound of formula (Ⅳ).

5. The preparation method of the hydrogel according to claim 1, wherein In the step of drying and purifying the interpenetrating network hydrogel prepolymer, the interpenetrating network hydrogel prepolymer is dried at 60 - 70 °C, and after drying, it is put into distilled water for purification treatment for 48 - 96 h to obtain a swollen interpenetrating network hydrogel product.

6. The preparation method of the hydrogel according to claim 1, wherein R1 of the compound of formula (Ⅱ) is a hydrocarbon group with 1 - 2 carbon atoms.

7. An interpenetrating network hydrogel prepared by the preparation method according to any one of claims 1 - 6.

8. Use of the interpenetrating network hydrogel according to claim 7 in treating dye wastewater.

Images