CN115073705A - Method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting ion coagulation method and application thereof - Google Patents

Method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting ion coagulation method and application thereof Download PDF

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CN115073705A
CN115073705A CN202210846846.1A CN202210846846A CN115073705A CN 115073705 A CN115073705 A CN 115073705A CN 202210846846 A CN202210846846 A CN 202210846846A CN 115073705 A CN115073705 A CN 115073705A
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cyclodextrin
polyurethane composite
waterborne polyurethane
composite sponge
beta
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CN115073705B (en
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岳明明
张海涛
马上鸿
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Shandong Dexin Leather Co ltd
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Shandong Dexin Leather Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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Abstract

The invention provides a method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting an ion coagulation method, which comprises prepolymerization, neutralization, dispersion and coagulation. The beta-cyclodextrin is introduced into a hydrophilic network structure of the aqueous polyurethane, then the hydrophilic chain extender of ethylene diamine ethyl sodium sulfonate is combined to prepare beta-cyclodextrin/aqueous polyurethane composite emulsion, the cyclodextrin/aqueous polyurethane composite sponge with the content of the beta-cyclodextrin is prepared by utilizing an ion coagulation method, the adsorption capacity to methylene blue and alkaline pink dye is increased along with the increase of adsorption time and the initial concentration of the dye, and when the initial concentration of the methylene blue is 5-50 mg/L, the removal rate to the methylene blue is 90.19-97.60%; when the initial concentration of the alkaline pink is 5-50 mg/L, the removal rate of the alkaline pink is 60.52-95.03%.

Description

Method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting ion coagulation method and application thereof
Technical Field
The invention relates to a technology for preparing cyclodextrin/waterborne polyurethane composite sponge by an ion coagulation method and application thereof, belonging to the field of adsorption separation.
Background
With the development of various industries, people produce and use a plurality of organic dyes, but the dyes bring visual enjoyment and convenience, and simultaneously, a large amount of dyes are randomly discharged into the environment, thereby causing serious influence on the health of living beings and human beings. For many years, various methods have been used to remove organic dyes from wastewater, such as degradation, adsorption, membrane separation, chemical oxidation, precipitation, extraction, electrochemistry, and the like. Among them, the adsorption method is considered to be the most common and effective method because of its high efficiency, simple design, and easy operation, and therefore, the development of a novel adsorbent is very critical to the effective removal of dyes. Experiments of a plurality of people prove that modification by introducing or changing functional groups on the original adsorbent plays an important role in improving the adsorption performance of the dye.
Beta-cyclodextrin has a special cavity structure with 'inner hydrophobicity and outer hydrophilicity', can contain nonpolar guest molecules with various proper sizes to form an inclusion compound to achieve an adsorption effect, and active hydroxyl (-OH) of an outer ring of the beta-cyclodextrin can be modified by various functional groups, so that the beta-cyclodextrin is further endowed with special properties, but the beta-cyclodextrin is low in water solubility and limited in application in a formula. The water-based polyurethane takes water as a dispersion medium, has excellent water solubility, and has the advantages of no toxicity, environmental protection and the like due to the hydrophilic network structure. Combining the advantages of both is expected to be an attractive and potentially viable option for removing various contaminants from water.
In the prior art, no report of cyclodextrin/waterborne polyurethane composite sponge is found.
Ion coagulation is commonly used for detecting hepatitis B surface antigen and is not reported in relevant documents of polyurethane and waterborne polyurethane preparation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting an ion coagulation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting an ion coagulation method comprises prepolymerization, neutralization, dispersion and coagulation.
The following is a further improvement of the above technical solution:
the dispersion method comprises the steps of dispersing the neutralized waterborne polyurethane prepolymer into a beta-CD aqueous solution in a state that the shearing speed is gradually increased from 390-1900 r/min to 1700-1900r/min, reducing the speed to 700-900r/min after shearing at 1700-1900r/min for 4-6 min at a high speed, then dropwise adding an A50 aqueous solution, dispersing for 29-31min, standing and curing for 11-13h to obtain the beta-cyclodextrin/waterborne polyurethane composite emulsion.
The mass concentration of the beta-CD in the beta-CD aqueous solution is 0.30-0.46%; in the A50 aqueous solution, the mass concentration of A50 is 49-50%; the molar ratio of the A50 to the DMPA is 1.2-1.3: 1; the mass ratio of the beta-CD to the A50 is 1-7: 5.8-6.0.
And (3) performing coagulation, namely dropwise adding the beta-cyclodextrin/waterborne polyurethane composite emulsion into a hydrochloric acid solution with the pH =1 for coagulation for 23-25h, filtering to remove hydrochloric acid, adding deionized water for replacement and purification for 23-25h, and finally performing freeze drying to obtain the composite sponge.
The volume ratio of the beta-cyclodextrin/waterborne polyurethane composite emulsion to the hydrochloric acid solution is 1: 9-11.
And (3) prepolymerization, adding DMPA, PPG-2000 and HDI into a container in sequence, stirring and preheating, and heating to the temperatureAt 87-90 ℃, adding BiR once respectively at 0.5 h, 2 h and 3.5 h 3 And continuously reacting for 1h at constant temperature, wherein the viscosity is not more than 200 mPas.
The molar ratio of the DMPA to the PPG-2000 to the HDI is 1:1: 3; BiR per addition 3 The mass ratio to DMPA was 1: 190-195.
And (3) neutralizing, cooling to 54-56 ℃, adding TEA (TEA acid) for neutralization to form salt for 19-21 min to obtain the aqueous polyurethane prepolymer, wherein the viscosity is controlled not to exceed 200 mPa & s in the neutralization process.
The molar ratio of TEA to DMPA was 1: 1.
The cyclodextrin/waterborne polyurethane composite sponge prepared by the method is applied to treatment of dye wastewater.
The invention has the following beneficial effects:
1) the invention introduces a special cavity structure of 'inner hydrophobic and outer hydrophilic' of beta-cyclodextrin into a hydrophilic network structure of aqueous polyurethane, then combines a hydrophilic chain extender of ethylene diamine ethyl sodium sulfonate to prepare beta-cyclodextrin/aqueous polyurethane composite emulsion, and utilizes an ion coagulation method to prepare the cyclodextrin/aqueous polyurethane composite sponge with the content of the beta-cyclodextrin, the adsorption capacity to methylene blue and alkaline peach red dye is increased along with the increase of adsorption time and initial concentration of the dye, and when the initial concentration of the methylene blue is 5-50 mg/L, the removal rate to the methylene blue is 90.19-97.60%; when the initial concentration of the alkaline pink is 5-50 mg/L, the removal rate of the alkaline pink is 60.52-95.03%; therefore, the composite sponge can effectively remove the dye in water, and has potential application prospect in dye wastewater treatment.
2) The invention adopts the technology of preparing the cyclodextrin/waterborne polyurethane composite sponge by using the ionic coagulation method, simplifies the preparation and adsorption processes, improves the adsorption capacity and the cost benefit, and the prepared cyclodextrin/waterborne polyurethane composite sponge not only shows excellent adsorption performance to methylene blue and basic pink dye, but also has certain reproducibility, thereby bringing certain theoretical significance and reference value for the practical application of the cyclodextrin/waterborne polyurethane composite sponge in the field of adsorption separation.
3) The invention develops a technology for preparing cyclodextrin/waterborne polyurethane composite sponge by an ion coagulation method, and waterborne polyurethane replaces solvent type polyurethane, and the material prepared by the method is a non-toxic and easily-degradable environment-friendly material, so that the excellent structural characteristics of the solvent type polyurethane are retained, and the use of Volatile Organic Compounds (VOCs) such as N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Tetrahydrofuran (THF) and the like is reduced to the maximum extent. In addition, the cyclodextrin/waterborne polyurethane composite sponge prepared by the technology has an excellent porous structure and a large specific surface area, and a large amount of functional groups also provide enough active sites. Most importantly, due to the good elasticity, the cyclodextrin/waterborne polyurethane composite sponge can realize the recycling of materials, and the characteristics of light weight, low price and high chemical stability are beneficial to the wide application of the cyclodextrin/waterborne polyurethane composite sponge in the field of water treatment.
4) The adsorption equilibrium time of the composite sponge for methylene blue dye is 6 hours, and the adsorption equilibrium time for basic pink dye is 3.5 hours.
5) The composite sponge can be desorbed and regenerated, and has the resolution ratio of 53.87-76.61% on methylene blue and the resolution ratio of 12.48-31.02% on alkaline pink.
Drawings
FIG. 1 is a diagram of the synthesis process of cyclodextrin/aqueous polyurethane composite emulsion of the present invention;
FIG. 2 is an infrared spectrum of the aqueous polyurethane emulsion and the cyclodextrin/aqueous polyurethane composite emulsion of the present invention;
FIG. 3 is a scanning electron microscope (a: WPU-CD) of the cyclodextrin/waterborne polyurethane composite sponge 0 ；b：WPU-CD 1 ；c：WPU-CD 3 ；d：WPU-CD 5 ；e：WPU-CD 7 ）；
FIG. 4 is a thermogravimetric analysis of a cyclodextrin/aqueous polyurethane composite sponge of the present invention;
FIG. 5 is a graph of the effect of the initial concentration of the present invention on the adsorption of methylene blue dye on the surface of a cyclodextrin/aqueous polyurethane composite sponge;
FIG. 6 is a graph showing the effect of initial concentration on the adsorption of basic pink dye on the surface of a cyclodextrin/aqueous polyurethane composite sponge according to the present invention;
FIG. 7 is a graph showing the effect of adsorption time on the adsorption of methylene blue dye on the surface of a cyclodextrin/aqueous polyurethane composite sponge according to the present invention;
FIG. 8 is a graph showing the effect of adsorption time on the adsorption of basic pink dye on the surface of a cyclodextrin/aqueous polyurethane composite sponge according to the present invention;
FIG. 9 is a graph of the fitted kinetics of adsorption of a methylene blue dye by a cyclodextrin/aqueous polyurethane composite sponge according to the present invention;
FIG. 10 is a graph of the cyclodextrin/aqueous polyurethane composite sponge fitting the adsorption kinetics of basic pink dye;
FIG. 11 is a comparison graph of the desorption effect of the cyclodextrin/waterborne polyurethane composite sponge adsorbing methylene blue and basic pink dye according to the invention.
Detailed Description
Example 1: WPU-CD 0 Preparation of (2)
1) Drying
The PPG-2000 and part of the instrument are put into an oven in advance for drying and dewatering, the temperature is set to be 85 ℃, and the time duration is at least 2 hours.
2) Prepolymerization
DMPA (3.35 g, 0.025 mol), PPG-2000 (50 g, 0.025 mol) and HDI (12.6 g, 0.075 mol) were added sequentially to a 150mL three-necked flask, placed in a 70 ℃ oil bath and preheated with stirring, the temperature was raised to 88 ℃ and then one drop of BiR was added at each of 0.5 h, 2 h and 3.5 h 3 (0.0175 g), continuously reacting for 1h at constant temperature for 4.5 h, and adding NMP to reduce the viscosity if the viscosity is higher than 200 mPa & s in the reaction process; the whole reaction process controls the reaction temperature to be 88 ℃ and the viscosity not to exceed 200 mPas.
3) Neutralization
The heating device is closed, the temperature is reduced to 55 ℃, TEA (2.525 g, 0.025 mol) is added for neutralization and salification for 20 min, and the prepolymer is obtained. Adding acetone to reduce viscosity if viscosity rises during cooling and neutralization; the neutralization process controls the viscosity not to exceed 200 mPas.
4) Dispersing
First, A50 (5.85 g, 0032 mol) was weighed and diluted with 6 g deionized water to give an aqueous A50 solution.
The specific process of dispersion is as follows:
and (3) dispersing the neutralized prepolymer into 218.97 g of deionized water under the condition that the shearing speed is gradually increased to 1800r/min from 400 r/min, shearing at 1800r/min for 5 min at a high speed, then reducing the speed to 800r/min, then dropwise adding an A50 aqueous solution, and timing from the shearing speed of 400 r/min, wherein the dispersion time is 30 min. And finally, standing and curing for 12 hours to obtain the aqueous polyurethane emulsion.
5) Coagulation and sedimentation
At normal temperature, a syringe is used for sucking 30mL of waterborne polyurethane emulsion, the waterborne polyurethane emulsion is dropwise added into 300 mL of hydrochloric acid solution with pH =1 for coagulation for 24 h, then hydrochloric acid is filtered and removed, deionized water is added for replacement and purification for 24 h (water is replaced for multiple times in the middle), and finally, WPU-CD is obtained through freeze drying 0 。
Example 2: WPU-CD 1 Preparation of
1) Drying
The PPG-2000 and part of the instrument are put into an oven in advance for drying and dewatering, the temperature is set to be 85 ℃, and the time duration is at least 2 hours.
2) Prepolymerization
DMPA (3.35 g, 0.025 mol), PPG-2000 (50 g, 0.025 mol) and HDI (12.6 g, 0.075 mol) were added sequentially to a 150mL three-necked flask, placed in a 70 ℃ oil bath with stirring and pre-heated, the temperature was raised to 88 ℃, and then one drop of BiR was added at 0.5 h, 2 h and 3.5 h, respectively 3 (0.0175 g), continuously reacting for 1h at constant temperature for 4.5 h, and adding NMP to reduce the viscosity if the viscosity is higher than 200 mPa & s in the reaction process; the whole reaction process controls the reaction temperature to be 88 ℃ and the viscosity not to exceed 200 mPas.
3) Neutralization
Closing the heating device, cooling to 55 ℃, adding TEA (2.525 g, 0.025 mol) for neutralization and salifying for 20 min to obtain a prepolymer, and adding acetone to reduce viscosity when the viscosity is higher than 200 mPa & s in the cooling and neutralization processes; the neutralization process controls the viscosity not to exceed 200 mPas.
4) Dispersing
First, 1 g of β -CD was dissolved in 218.97 g of deionized water to give an aqueous solution of β -CD, and A50 (5.85 g, 0032 mol) was weighed and diluted with 6 g of deionized water to give an aqueous solution of A50.
The specific process of dispersion is as follows:
dispersing the neutralized prepolymer into a beta-CD aqueous solution under the condition that the shearing speed is gradually increased to 1800r/min from 400 r/min, shearing at the high speed of 1800r/min for 5 min, then reducing the speed to 800r/min, then dropwise adding an A50 aqueous solution, co-dispersing for 30 min, standing and curing for 12 h to obtain the beta-cyclodextrin/waterborne polyurethane composite emulsion.
5) Coagulation and sedimentation
Absorbing 30mL of beta-cyclodextrin/waterborne polyurethane composite emulsion by using a syringe, dropwise adding the beta-cyclodextrin/waterborne polyurethane composite emulsion into 300 mL of hydrochloric acid solution with pH =1 for coagulation for 24 h, filtering to remove hydrochloric acid, adding deionized water for replacement and purification for 24 h (replacing water for multiple times), and finally performing freeze drying to obtain WPU-CD 1 。
Preparation of WPU-CD 3 、WPU-CD 5 And WPU-CD 7 The procedure of (2) was the same as above except that the amount of beta-CD was varied as shown in Table 1.
TABLE 1 preparation of WPU-CD with different beta-CD contents X Raw material dosage ratio of
Figure DEST_PATH_IMAGE001
According to the method, five cyclodextrin/waterborne polyurethane composite emulsions and cyclodextrin/waterborne polyurethane composite sponges are prepared. The basic performance characterization of the synthesized cyclodextrin/waterborne polyurethane composite emulsion is carried out by the Size, Zeta potential, viscosity and solid content tests, and is shown in Table 2.
TABLE 2
Figure 642269DEST_PATH_IMAGE002
Pouring a proper amount of waterborne polyurethane emulsion or cyclodextrin/waterborne polyurethane composite emulsion into a polytetrafluoroethylene template, naturally air-drying to form a film, and performing structural characterization on the film by using FTIR (see figure 2); observing the morphological structure of the cyclodextrin/waterborne polyurethane composite sponge by using a scanning electron microscope (see figure 3); gradually heating the cyclodextrin and the cyclodextrin/waterborne polyurethane composite sponge from room temperature to 600 ℃ at a speed of 10 ℃/min under a nitrogen atmosphere of 50 mL/min by a thermogravimetric analyzer to represent the thermal stability (see figure 4);
the influence of the cyclodextrin content, the adsorption time and the initial concentration of the dye on the adsorption performance of the cyclodextrin/waterborne polyurethane composite sponge is determined by an ultraviolet visible light photometer, and the desorption regeneration performance of the cyclodextrin/waterborne polyurethane composite sponge is tested (see figures 5-11).
Analysis of FIG. 2 shows that the reaction of beta-CD with isocyanate has occurred and has been grafted into the aqueous polyurethane.
Scanning electron microscope results of five beta-cyclodextrin modified waterborne polyurethane composite materials with the same magnification times (multiplied by 500) are shown in figure 3, and five adsorbing materials have obvious porous network structures, wherein WPU-CD 3 The pore size of (a) is larger, so that it is more favorable for the adsorbate to contact the adsorption site, and the adsorption rate is faster, which is consistent with the subsequent adsorption kinetics results.
As can be seen in fig. 4, the maximum mass loss occurs for β -CD around 300 ℃, and the mass loss occurs for all five composite adsorbent materials between 300 ℃ and 400 ℃ due to the cleavage of the urethane groups attached between β -CD and the isocyanate.
In order to study the relationship between adsorption time and adsorption amount, 50mL of methylene blue and basic pink solution with initial concentration of 5mg/L are respectively added into a 100 mL beaker, then 100mg of adsorbent is respectively added, the mixture is continuously stirred at room temperature, samples are taken at different times (5, 15, 30, 45, 60, 75, 90, 105, 120, 150, 180, 210, 240, 270, 300, 330 and 360 min), the samples are filtered by a filter with 0.22 pm, the absorbance of the samples is measured by an ultraviolet spectrophotometer, and finally the specific concentration is obtained by a standard curve equation, and the adsorption amount is calculated; in order to study the influence of different adsorbate concentrations, 50 mg/L methylene blue and basic pink stock solutions are prepared respectively, then the stock solutions are diluted respectively to different concentrations, the concentration gradients are 5mg/L, 10 mg/L, 15 mg/L, 20 mg/L, 25 mg/L, 30 mg/L, 35 mg/L, 40 mg/L, 45 mg/L and 50 mg/L, 20mg of the adsorbent (the composite sponge) is added into 10 mL of the methylene blue and basic pink solutions with the concentration gradients respectively at room temperature, the mixture is continuously stirred for 24 hours after being sealed by a sealing film, the sample is sampled and filtered by a 0.22 pm filter head, and the residual concentration is measured by an ultraviolet spectrophotometer to calculate the equilibrium adsorption amount.
As shown in fig. 5 to 8, the adsorption amounts of the five cyclodextrin/aqueous polyurethane composite sponges to the methylene blue and basic pink dyes increase with the increase of the initial concentrations of the dyes and the adsorption time, and the five cyclodextrin/aqueous polyurethane composite sponges have the adsorption characteristics of the porous adsorbent in two stages of a fast stage and a slow stage, but have different adsorption effects and adsorption rates to the methylene blue and basic pink dyes.
The adsorption equilibrium time for methylene blue dye was 6 h (see fig. 7) and for basic pink dye was 3.5 h (see fig. 8) for each of the complex sponges.
The removal rate of the cyclodextrin/waterborne polyurethane composite sponge on methylene blue and basic pink in the adsorption equilibrium time is shown in table 3.
TABLE 3
Figure 497093DEST_PATH_IMAGE003
WPU-CD as shown in Table 3 3 The adsorption effect on methylene blue is the best, and the removal rate can reach 99.03%. WPU-CD 0 The removal effect on basic pink dye is the worst, and the removal rate is only 50.59%.
The removal rate of the cyclodextrin/waterborne polyurethane composite sponge on methylene blue at different initial concentrations of the methylene blue is shown in table 4.
TABLE 4
Figure 276830DEST_PATH_IMAGE004
As shown in Table 4, WPU-CD was obtained when the initial concentration of methylene blue was 10 mg/L 3 The removal effect on methylene blue is the best, the removal rate is 97.60 percent, and the WPU-CD is 0 The removal effect on methylene blue is the worst, and the removal rate is only 88.05 percent;
the removal rate of the cyclodextrin/waterborne polyurethane composite sponge for basic pink at different initial concentrations of the basic pink is shown in table 5.
TABLE 5
Figure DEST_PATH_IMAGE005
As shown in Table 5, WPU-CD was measured at an initial concentration of 5mg/L of basic pink 3 The adsorption amount of the basic pink is 2.352 mg/g, the removal rate is 95.03 percent, and the WPU-CD is 0 The adsorption capacity to the alkaline pink is 1.867 mg/g, and the removal rate is only 61.05%.
In conclusion, the adsorption effect of the five cyclodextrin/waterborne polyurethane composite sponges on methylene blue dye is superior to that of basic pink dye, and the WPU-CD (waterborne polyurethane-polyvinyl chloride) 3 The best adsorption effect.
The parameters of the cyclodextrin/waterborne polyurethane composite sponge for methylene blue dye adsorption kinetics fitting are shown in the table 6.
TABLE 6
Figure 78564DEST_PATH_IMAGE006
The parameters of the cyclodextrin/waterborne polyurethane composite sponge for dynamic fitting of the basic pink dye adsorption are shown in table 7.
TABLE 7
Figure DEST_PATH_IMAGE007
The experimental data are fitted through a kinetic equation, and as can be seen from fig. 9, fig. 10, table 6 and table 7, the simulated secondary kinetic model is more in line with the adsorption of methylene blue and basic pink dyes on the surface of the cyclodextrin/aqueous polyurethane composite sponge, which indicates that the adsorption of five cyclodextrin/aqueous polyurethane composite sponges on the methylene blue and basic pink dyes is a chemical process.
As can be seen from figure 11, the five cyclodextrin/waterborne polyurethane composite sponges prepared by the technology can be desorbed and regenerated, but the cyclodextrin/waterborne polyurethane sponge adsorbing the methylene blue dyeThe ester composite sponge has better desorption effect. Wherein, WPU-CD 7 The highest desorption rate of methylene blue is 76.61 percent; WPU-CD 3 The desorption rate of (2) was 64.33%, which was the second place.
The comparison of the data shows that the cyclodextrin/waterborne polyurethane composite sponge is successfully prepared by using an ion coagulation method, the material shows excellent adsorption performance to methylene blue and basic pink dye, and has certain reproducibility, namely WPU-CD 3 The adsorption effect on methylene blue and basic pink dye is the best, the maximum removal rate can reach 99.03%, the technology for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ion coagulation method simplifies the preparation process, improves the adsorption capacity and the cost benefit of the adsorbent, and is expected to bring certain theoretical significance and reference value for dye wastewater treatment in practical application.

Claims (10)

1. A method for preparing cyclodextrin/waterborne polyurethane composite sponge by adopting an ion coagulation method is characterized by comprising the following steps: the method comprises prepolymerization, neutralization, dispersion and coagulation.
2. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 1, wherein the ionic coagulation method comprises the following steps: the dispersion method comprises the steps of dispersing the neutralized waterborne polyurethane prepolymer into a beta-CD aqueous solution in a state that the shearing speed is gradually increased from 390-1900 r/min to 1700-1900r/min, reducing the speed to 700-900r/min after shearing at 1700-1900r/min for 4-6 min at a high speed, then dropwise adding an A50 aqueous solution, dispersing for 29-31min, standing and curing for 11-13h to obtain the beta-cyclodextrin/waterborne polyurethane composite emulsion.
3. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 1, wherein the method comprises the following steps: the mass concentration of the beta-CD in the beta-CD aqueous solution is 0.30-0.46%; in the A50 aqueous solution, the mass concentration of A50 is 49-50%; the molar ratio of the A50 to the DMPA is 1.2-1.3: 1; the mass ratio of the beta-CD to the A50 is 1-7: 5.8-6.0.
4. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 1, wherein the ionic coagulation method comprises the following steps: and (3) performing coagulation, namely dropwise adding the beta-cyclodextrin/waterborne polyurethane composite emulsion into a hydrochloric acid solution with the pH =1 for coagulation for 23-25h, filtering to remove hydrochloric acid, adding deionized water for replacement and purification for 23-25h, and finally performing freeze drying to obtain the composite sponge.
5. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 4, wherein the ionic coagulation method comprises the following steps: the volume ratio of the beta-cyclodextrin/waterborne polyurethane composite emulsion to the hydrochloric acid solution is 1: 9-11.
6. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 1, wherein the ionic coagulation method comprises the following steps: the prepolymerization comprises the steps of sequentially adding DMPA, PPG-2000 and HDI into a container, stirring and preheating, raising the temperature to 87-90 ℃, and then respectively adding BiR once in 0.5 h, 2 h and 3.5 h 3 And continuously reacting for 1 hour at constant temperature, wherein the viscosity is not more than 200 mPas.
7. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 6, wherein the ionic coagulation method comprises the following steps: the molar ratio of the DMPA to the PPG-2000 to the HDI is 1:1: 3; BiR per addition 3 The mass ratio to DMPA was 1: 190-195.
8. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 1, wherein the ionic coagulation method comprises the following steps: and (3) neutralizing, cooling to 54-56 ℃, adding TEA (TEA acid) for neutralization to form salt for 19-21 min to obtain the aqueous polyurethane prepolymer, wherein the viscosity is controlled not to exceed 200 mPa & s in the neutralization process.
9. The method for preparing the cyclodextrin/waterborne polyurethane composite sponge by the ionic coagulation method according to claim 8, wherein the ionic coagulation method comprises the following steps: the molar ratio of TEA to DMPA was 1: 1.
10. The use of a cyclodextrin/aqueous polyurethane composite sponge prepared according to the method of claim 1 for treating dye wastewater.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006083379A (en) * 2004-08-20 2006-03-30 Meiwa Kasei Kk Globular cyclodextrin polymer, method for producing the same, and adsorbent containing the same
CN102816291A (en) * 2012-08-14 2012-12-12 江苏大学 One-step preparation method and application of beta-cyclodextrin/polyurethane porous foaming material
CN106475079A (en) * 2016-10-25 2017-03-08 昆明理工大学 Polyurethane foam surface is coupled sorbing material of beta cyclodextrin and its preparation method and application
CN113350578A (en) * 2021-04-14 2021-09-07 山东德信皮业有限公司 Method for repairing damage of dermis based on electrostatic spinning technology

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006083379A (en) * 2004-08-20 2006-03-30 Meiwa Kasei Kk Globular cyclodextrin polymer, method for producing the same, and adsorbent containing the same
CN102816291A (en) * 2012-08-14 2012-12-12 江苏大学 One-step preparation method and application of beta-cyclodextrin/polyurethane porous foaming material
CN106475079A (en) * 2016-10-25 2017-03-08 昆明理工大学 Polyurethane foam surface is coupled sorbing material of beta cyclodextrin and its preparation method and application
CN113350578A (en) * 2021-04-14 2021-09-07 山东德信皮业有限公司 Method for repairing damage of dermis based on electrostatic spinning technology

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