CN113274989A - Preparation method of polyurethane foam-based hydrophobic adsorption material - Google Patents

Preparation method of polyurethane foam-based hydrophobic adsorption material Download PDF

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CN113274989A
CN113274989A CN202110605686.7A CN202110605686A CN113274989A CN 113274989 A CN113274989 A CN 113274989A CN 202110605686 A CN202110605686 A CN 202110605686A CN 113274989 A CN113274989 A CN 113274989A
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graphene oxide
polyurethane foam
adsorption material
material based
fluorine
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李俊
陈恒昌
刘宁莉
陶涛
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Nanjing University of Information Science and Technology
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Nanjing University of Information Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil

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Abstract

The invention discloses a preparation method of a hydrophobic adsorption material based on polyurethane foam, and innovatively provides a method for modifying polyurethane foam by using graphene oxide modified by a fluorine-containing monomer. The modified polyurethane foam prepared by the invention has the characteristics of high porosity, large specific surface area and intercommunicated hole structure, and has higher adsorption efficiency and cyclic usability.

Description

Preparation method of polyurethane foam-based hydrophobic adsorption material
Technical Field
The invention relates to a preparation method of an adsorbing material, in particular to a preparation method of a hydrophobic adsorbing material.
Background
With the high-speed development of modern industry, rural urbanization, traffic road construction and offshore oil exploitation, offshore oil leakage, discharge of industrial dye wastewater and urban domestic sewage and the like cause serious harm to surrounding water bodies. At present, the most basic and effective means for treating water pollution is to utilize an adsorption material to absorb pollutants in water so as to achieve the aim of purification.
At present, adsorbents such as coal, carbon nanorods, activated carbon, plant powder, clay, chitosan, graphene and the like have good adsorption effects on dyes, organic matters and heavy metal ions, however, the adsorbents are mostly in powder or granular form, and the operation is difficult during recovery.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of a polyurethane foam-based hydrophobic adsorption material, which is characterized in that the hydrophobic adsorption material is prepared by compounding modified graphene oxide (fluorine-containing graphene oxide) and polyurethane foam, and has the advantages of large specific surface area, stable structure, good adsorption performance and reusability.
The technical scheme is as follows: the invention relates to a preparation method of a polyurethane foam-based hydrophobic adsorption material, which comprises the following steps:
(1) mixing graphene oxide, a cross-linking agent and a fluorine-containing monomer, reacting to obtain modified graphene oxide, drying, and grinding to obtain hydrophobic graphene oxide powder;
(2) carrying out prepolymerization reaction on polyoxypropylene glycol, xylylene diisocyanate and modified graphene oxide serving as raw materials to obtain a prepolymer;
specifically, according to the mass percentage, 50% -70% of polyoxypropylene glycol (PPG), 30% -50% of Xylylene Diisocyanate (XDI) and additional modified graphene oxide are used as raw materials (1% -15% of the weight of PPG) to carry out prepolymerization reaction to obtain a prepolymer;
(3) adding stannous octoate and 1, 8-diazabicycloundecene-7-ene (DBU) as a catalyst and silicon-carbon chain type L-580 as a stabilizer into a container, stirring and mixing, adding a prepolymer at 70-80 ℃, stirring for 100-200 seconds, adding distilled water, and carrying out foaming treatment;
(4) and curing the foam subjected to the foaming treatment.
In the step (1), the cross-linking agent is an amide cross-linking agent containing hydroxyl and amino, such as hydroxymethyl acrylamide (N-MAM), and the fluorine-containing monomer is a fluorine-containing alcohol containing more than six fluorine, such as Hexafluoroisopropanol (HFIP). The dosage of the cross-linking agent is 1-12% of the mass of the graphene oxide; the mass ratio of the fluorine-containing monomer to the graphene oxide is 0.2-5: 1. Mixing the raw materials at 70-90 ℃, and reacting for 3-5 h to obtain the hydrophobic graphene oxide.
Wherein the preparation of the graphene oxide comprises the following steps: taking raw materials of natural graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid, respectively stirring in an ice bath at the temperature of below 5 ℃ and in an oil bath at the temperature of between 35 and 98 ℃ to finish an oxidation experiment, separating and purifying a mixed solution, and dialyzing until the solution is neutral.
The drying treatment comprises the following steps: and (3) carrying out ultrasonic treatment on the mixed solution for 30-60 minutes, fixing the mixed solution in a drying mould, and putting the dried mixed solution into a freeze drying box for freeze drying for 48-72 hours.
Preferably, in the step (2), the amount of the modified graphene oxide is 1 to 12 percent of the mass of the polyoxypropylene glycol. Further, the amount of the modified graphene oxide is 2-10% of the mass of the polyoxypropylene glycol.
In the step (3), the adding amount of stannous octoate is 0.1-10 wt%, the adding amount of a catalyst is 0.5-5 wt%, and the adding amount of a stabilizer is 0.5-5 wt%, based on 100% by mass of polyoxypropylene glycol (PPG). Namely: the weight ratio of the stannous octoate, the catalyst and the stabilizer to the PPG is 0.1-10%, 0.5-5% and 0.5-5%.
Wherein in the step (4), the curing time is 48-72 h.
The invention principle is as follows: the fluorine-containing graphene oxide (modified graphene oxide)/polyurethane foam composite material prepared by the invention combines the modified graphene oxide with larger specific surface area and polyurethane foam, so that the characteristics of larger specific surface area of the modified graphene oxide, high resilience, large specific surface area and intercommunicated hole structure of the polyurethane foam are kept, and the defects of easy dispersion of the graphene oxide and low gap of the polyurethane foam are overcome.
At present, the main raw materials for preparing polyurethane foam are polyether polyol and aromatic isocyanate, wherein the aromatic isocyanate mainly uses Toluene Diisocyanate (TDI) and 4, 4' -diphenylmethane diisocyanate (MDI). The polyurethane foam is easy to yellow, and when the soft foam is exposed to sunlight for a long time, the soft foam can be automatically oxidized, so that the polymer is degraded, the foam is yellow and crisp, the physical properties are reduced, and even the use value of the product is lost. The Xylylene Diisocyanate (XDI) has the characteristic of preventing the polyurethane product from yellowing, prevents the resonance phenomenon between a benzene ring and isocyanate and is relatively stable.
According to the invention, the aliphatic isocyanate XDI is used for preparing the polyurethane flexible foam (PUF), the prepared foam is not yellowed, and the performance is relatively stable. The method adopts a process of independently adding water for foaming, and obtains a relatively good formula through experiments. Water is a green foaming agent and is harmless to the environment. Modifying graphene oxide with Hexafluoroisopropanol (HFIP) and N-hydroxymethyl acrylamide (N-MAM) to obtain hydrophobic graphene oxide (MAHF-GO), and compounding with polyurethane foam to obtain novel hydrophobic foam (MAHF-GO/PUF).
The adsorbent in the prior art needs a carrier, while the polyurethane flexible foam in the invention is an excellent carrier, and particularly, the open-pore polyurethane flexible foam has the advantages of large porosity, light weight, recycling and the like, can be used for fixing the adsorbent, and has adsorption performance. The adsorbent is fixed on the polyurethane flexible foam to prepare the composite material, and the composite material is a set of the adsorption performance of the adsorbent and the structural characteristics of the polyurethane flexible foam.
Has the advantages that:
(1) compared with the prior art, the invention innovatively provides the method for modifying the polyurethane foam by using the graphene oxide modified by the fluorine-containing monomer, and the modified polyurethane foam prepared by the invention has the characteristics of high porosity, large specific surface area and intercommunicated pore structure, and is a good adsorption material.
(2) According to the invention, the fluorine-containing monomer is used for modifying graphene oxide to increase the hydrophobicity of the graphene oxide, and the graphene oxide is physically compounded with polyurethane to improve the state of the graphene oxide, so that the graphene oxide is fixed in the polyurethane and can be well recycled. The synthesized composite material not only increases the adsorption capacity of polyurethane foam, but also overcomes the defect that graphene oxide is easy to disperse.
(3) The adsorbing material is a composite material containing fluorine-containing graphene oxide and polyurethane foam, is used as a hydrophobic adsorbent, can well adsorb water-soluble organic dye molecules and oils, is good in recycling performance, and can be used as an efficient adsorbing material.
Drawings
FIG. 1 is a schematic representation of the novel hydrophobic foam (MAHF-GO/PUF) prepared in the present invention.
FIG. 2 is an infrared spectrum of PUFs, MAHF-GO, GO/PUFs and MAHF-GO/PUFs.
FIG. 3 is an electron micrograph of a MAHF-GO/PUF; (a) for 50 times magnification, (b) for 300 times magnification.
FIG. 4 is a water contact angle test chart for MAHF-GO/PUF; (a) 0s and (b) 15 s.
Fig. 5 is a comparison of the height before (a) and after (B) pressing 100 times with a ruler.
FIG. 6 is a graph of adsorption amount (A) and adsorption rate (B) of MAHF-GO/PUF on MB at different initial concentrations versus time; wherein, the graph A is MB adsorption amount, the graph B is adsorption rate, and the initial concentration of the curve a in the graph A is 10mg L-1B initial concentration of curve 15mg L-1And the initial concentration of the c curve is 20mg L-1Initial concentration of the d-curve was 30mg L-1(ii) a The curve in panel B corresponds to the same concentration as in panel a, and the panel C in the lower right of panel B represents the change in color with time.
FIG. 7 is a graph of the adsorption of MAHF-GO/PUF to MB at different temperatures.
FIG. 8 is a graph of MAHF-GO content versus oil mass (vacuum oil).
FIG. 9 shows the uptake of petroleum ether, linear silicone oil, vacuum oil by blank PUFs and MAHF-GO/PUFs.
FIG. 10 is a graph of the adsorption of MAHF-GO/PUF to petroleum ether, linear silicone oil and vacuum oil over time.
FIG. 11 is a graph comparing the vacuum oil adsorption amount of PUF and MAHF-GO/PUF after 9 cycles of regeneration.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials and reagents used in the following examples are all commercially available.
The preparation process of the hydrophobic adsorption material based on the polyurethane foam comprises the following steps:
(1) mixing graphene oxide, a cross-linking agent and a fluorine-containing monomer, reacting to obtain modified graphene oxide, reacting at the temperature of 70-90 ℃ for 3-5 h, drying after the reaction is finished, and grinding to obtain hydrophobic graphene oxide powder. Wherein the cross-linking agent is an amide cross-linking agent containing hydroxyl and amido, and the fluorine-containing monomer is fluorine-containing alcohol containing more than six fluorine; the dosage of the cross-linking agent is 1-12% of the mass of the graphene oxide; the mass ratio of the fluorine-containing monomer to the graphene oxide is 0.2-5: 1.
(2) Carrying out prepolymerization reaction on polyoxypropylene glycol, xylylene diisocyanate and modified graphene oxide serving as raw materials to obtain a prepolymer;
wherein the raw materials comprise 50 to 70 weight Percent of Polyoxypropylene Glycol (PPG) and 30 to 50 weight percent of Xylylene Diisocyanate (XDI) according to the mass percentage; the weight of the additional modified graphene oxide is 1-15% of that of PPG.
(3) Adding stannous octoate and 1, 8-diazabicycloundecene-7-ene (DBU) as a catalyst and silicon-carbon chain type L-580 as a stabilizer into a container, stirring and mixing, adding a prepolymer at 70-80 ℃, stirring for 100-200 seconds, adding distilled water, and carrying out foaming treatment;
(4) and curing the foam subjected to foaming treatment for 48-72 hours to obtain the foam.
Example 1:
preparation of hydrophobic polyurethane composite (MAHF-GO/PUF):
(1) preparing graphene oxide: taking raw materials of natural graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid, and stirring the raw materials in an oil bath at the temperature of below 5 ℃ and in an oil bath at the temperature of between 35 and 98 ℃ respectively to finish an oxidation experiment; separation and purification: centrifuging the mixed solution by a centrifuge, and dialyzing by a dialysis bag until the pH of the solution is close to neutral;
(2) modification: adding a cross-linking agent functional amide monomer and a fluorine-containing monomer into the mixed solution, and carrying out oil bath reaction for 4 hours at the temperature of 80 ℃;
wherein the cross-linking agent is hydroxymethyl acrylamide, and the fluorine-containing monomer is hexafluoroisopropanol. Wherein the dosage of the cross-linking agent is 5% of the mass of the graphene oxide; the amount of the fluorine-containing monomer is equal to the mass of the graphene oxide.
(3) And (3) freeze drying of the modified graphene oxide: the mixed solution is fixed in a drying mould after being subjected to ultrasonic treatment for 30-60 minutes, and is put into a freeze drying box for freeze drying, and the prepared modified graphene oxide foam is ground into powder for later use.
(4) Preparation of prepolymer: adding polyoxypropylene glycol into a flask connected with a circulating water type vacuum device, a condensation reflux device and a thermometer, putting the flask into an oil bath pot, carrying out vacuum drying at 120 ℃ for 3 hours, cooling to 80 ℃, and stopping vacuumizing. The circulating water vacuum pump was removed and a stirrer and Xylylene Diisocyanate (XDI) were added. After stirring at 80 ℃ for 2.5h, 1.5g of XDI was added. Prepolymerization is carried out for 1h, and the modified graphene oxide powder obtained in the step 3) is added at 0.5 h.
Wherein, the mass fraction of the polyoxypropylene glycol (PPG) in the raw materials is 60 percent and the mass fraction of the Xylylene Diisocyanate (XDI) is 40 percent according to the mass percentage; the added modified graphene oxide accounts for 10% of the weight of the PPG.
(5) Foaming: respectively adding stannous octoate, silicon-carbon chain type L-580 and 1, 8-diazabicycloundecen-7-ene DBU into a plastic cup, stirring and mixing, adding prepolymer with the temperature of 80 ℃, stirring for 100 seconds, and then adding distilled water. The foam rises rapidly.
Wherein, the adding amount of the stannous octoate in the step is 5 wt%, the adding amount of the catalyst is 5 wt%, and the adding amount of the stabilizer is 5 wt% based on the mass of the polypropylene oxide glycol (PPG) as 100%.
(6) Curing: 1 minute after the foam stopped growing, it was placed in an oven at 30 ℃ for 48 h.
As shown in figure 1A sample of the novel hydrophobic foam (MAHF-GO/PUF) prepared by the method is in a foam shape, which indicates that the modified graphene oxide/polyurethane foam is successfully prepared. FIG. 2 is an infrared spectrum of PUFs, MAHF-GO, GO/PUFs and MAHF-GO/PUFs. MAHF-GO is 1114cm-1In the form of fluorine-containing functional groups, i.e. -CF3The antisymmetric stretching vibration peak of the compound indicates that the MAHF-GO is successfully prepared by modification. GO/PUF contains not only all functional groups containing PUF but also oxygen-containing groups such as — OH bond, N ═ C ═ O, C-O-C, C-O, and carboxyl group, which are significantly increased as compared with PUF. The successful manufacture of the GO-PU foam composite material is demonstrated. MAHF-GO/PU foam has more-CF than GO/PU foam3The peak value is lower, and the composite MAHF-GO/PUF is successfully prepared. FIG. 3 is an electron microscope scanning image of MAHF-GO/PUF, from which it can be seen that MAHF-GO is loaded on XDI polyurethane flexible foam. FIG. 4 is a water contact angle test chart of the MAHF-GO/PUF, wherein the water contact angle of the MAHF-GO/PUF is 113.85 degrees, which shows that the hydrophobicity of the MAHF-GO/PUF is good. As shown in FIG. 5, which is a comparison of the height before (A) and after (B) 100 times pressing with a ruler, it can be seen that there is no significant change in the foam height, indicating the high resiliency of XDI type foam.
The adsorption effect of the adsorption material prepared in the example is tested, and the specific adsorption process is as follows:
adsorbing the methylene blue solution: taking out the cured modified graphene oxide/polyurethane foam in the step 6), putting the modified graphene oxide/polyurethane foam into a methylene blue solution with the concentration of 5-30 mg/L, measuring the absorbance in different periods, obtaining the concentration of the solution when the absorbance is minimum, and calculating the adsorption capacity.
Adsorbing oils: and (3) putting the modified graphene oxide/polyurethane foam cured in the step 6) into petroleum ether, linear silicone oil (the molecular weight is hundreds) and oil for a vacuum pump, measuring the adsorption quality in different periods, and calculating the adsorption quantity.
Example 2:
the effect test of the hydrophobic polyurethane composite material (MAHF-GO/PUF) on adsorbing Methylene Blue (MB) solutions with different concentrations:
0.25g of the hydrophobic polyurethane composite material (the content of MAHF-GO is 7 percent of the weight of PPG) prepared in example 1 is placed in 20mL of the hydrophobic polyurethane composite material with the concentration of 20mL and the concentration of 10mg L-1、15mg L-1、20mg L-1And 30mg L-1And (3) standing the MB solution, measuring the ultraviolet absorbance at 664nm at intervals, and calculating the absorbance.
FIG. 6 shows the MAHF-GO/PUF pair at an initial concentration of 10mg L-1(a)、15mg L-1(b)、20mg L-1(c) And 30mg L-1(d) The adsorption amount (A) and adsorption rate (B) of MB (m.beta.mb) are plotted against time, i.e. MAHF-GO/PUF vs. 10mg L-1、15mg L-1、20mg L-1And 30mg L-1The adsorption rates of the MB solution were 98%, 97.75%, 97.37% and 96.01%, respectively. The adsorption rate increased with time, the adsorption capacity and adsorption rate increased very quickly in the first 500min and increased slowly after 2000 min. Wherein, the lower right panel C in FIG. 6B shows the color change with time, and the maximum adsorption capacity of 2.43mg g is finally reached in 12000min-1The adsorption rate was 96.01%.
Example 3:
this example tests the effect of temperature on the adsorption of Methylene Blue (MB) solution by hydrophobic polyurethane composites (MAHF-GO/PUF):
0.25g of the MAHF-GO/PUF prepared in example 1 (the content of the MAHF-GO is 7 percent of the weight of the PPG) is put into a solution with the concentration of 30mg L-1The MB solution (2) was placed in a forced air drying oven at 293K, 303K, 313K and 333K for 48 hours to measure the absorption amount. As shown in figure 7, the adsorption amount is increased and then decreased along with the increase of the temperature, the adsorption amount to MB is maximum when the adsorption temperature is 40 ℃, and the maximum adsorption amount of MAHF-GO/PUF is 2.52mg g-1。
Example 4:
this example is a test of the effect of MAHF-GO content on the absorption of oils by MAHF-GO/PUF:
the MAHF-GO/PUF prepared in example 1 (the MAHF-GO content is 2-10% of the weight of the PPG) was placed in 50ml of vacuum oil, and the weight was measured after a while, and the oil absorption (R) was calculated at equilibrium. As shown in FIG. 8, it can be seen that the oil absorption of the MAHF-GO/PUF increases and then decreases with the increase of the content of the MAHF-GO, and reaches the maximum when the content of the MAHF-GO is 4%, and the maximum absorption of the MAHF-GO/PUF to vacuum oil is 12.6g g-1。
Example 5:
the MAHF-GO/PUF prepared in example 4 (the content of the MAHF-GO is 4% of the mass of the PPG) and a blank PUF are placed in 50ml of petroleum ether, linear silicone oil (molecular weight 200-300) and vacuum oil, the weight of the mixture is measured at intervals of several minutes, and the oil absorption (R) is calculated during balance. As can be seen from FIG. 9, the absorption amounts of the MAHF-GO/PUF to petroleum ether, linear silicone oil (molecular weight 200-300) and vacuum oil are 10.56g g-1，10.88g g-1And 12.6g g-1Compared with the blank PUF, the PUF is improved by 38.8%, 12.1% and 29.2%. As can be seen from FIG. 10, the adsorption of petroleum ether, linear silicone oil and vacuum oil by MAHF-GO/PUF increases rapidly in the first 2min, and reaches a substantial equilibrium in 10 min.
Example 6:
the MAHF-GO/PUF prepared in example 4 (the content of MAHF-GO is 4% of the mass of PPG) and a blank PUF are placed in 50ml of vacuum oil, and the weight of the blank PUF is measured after a period of time, and the oil absorption (R) is calculated at equilibrium. The process of absorbing and saturating PUF and MAHF-GO/PUF and physically extruding to remove oil is repeated for 9 times, the absorption cycle conditions of PUF and MAHF-GO/PUF are shown in figure 11, and the adsorption of PUF and MAHF-GO/PU to vacuum oil is not obviously reduced along with the increase of the cycle times. The PUF, MAHF-GO/PUF or vacuum oil pair after 9 cycles has 8.99g g-1，11.48g g-1. The XDI type MAHF-GO/PUF has good adsorption capacity and cyclic usability on oil.
Example 7:
preparation of hydrophobic polyurethane composite (MAHF-GO/PUF):
(1) preparing graphene oxide: taking raw materials of natural graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid, and stirring the raw materials in an oil bath at the temperature of below 5 ℃ and in an oil bath at the temperature of between 35 and 98 ℃ respectively to finish an oxidation experiment; separation and purification: centrifuging the mixed solution by a centrifuge, and dialyzing by a dialysis bag until the pH of the solution is close to neutral;
(2) modification: adding a cross-linking agent functional amide monomer and a fluorine-containing monomer into the mixed solution, and carrying out oil bath reaction for 5 hours at 70 ℃;
wherein the cross-linking agent is hydroxymethyl acrylamide, and the fluorine-containing monomer is hexafluoroisopropanol. Wherein the dosage of the cross-linking agent is 10 percent of the mass of the graphene oxide; the mass ratio of the fluorine-containing monomer to the graphene oxide is 0.2: 1.
(3) And (3) freeze drying of the modified graphene oxide: the mixed solution is fixed in a drying mould after being subjected to ultrasonic treatment for 30-60 minutes, and is put into a freeze drying box for freeze drying, and the prepared modified graphene oxide foam is ground into powder for later use.
(4) Preparation of prepolymer: adding polyoxypropylene glycol into a flask connected with a circulating water type vacuum device, a condensation reflux device and a thermometer, putting the flask into an oil bath pot, carrying out vacuum drying at 120 ℃ for 3 hours, cooling to 80 ℃, and stopping vacuumizing. The circulating water vacuum pump was removed and a stirrer and Xylylene Diisocyanate (XDI) were added. After stirring at 80 ℃ for 2.5h, 1.5g of XDI was added. Prepolymerization is carried out for 1h, and the modified graphene oxide powder obtained in the step 3) is added at 0.5 h.
Wherein, the mass fraction of the polyoxypropylene glycol (PPG) in the raw materials is 50 percent, and the mass fraction of the Xylylene Diisocyanate (XDI) is 50 percent; the added modified graphene oxide accounts for 1 percent of the weight of the PPG.
(5) Foaming: respectively adding stannous octoate, silicon-carbon chain type L-580 and 1, 8-diazabicycloundecen-7-ene DBU into a plastic cup, stirring and mixing, adding prepolymer with the temperature of 70 ℃, stirring for 150 seconds, and then adding distilled water. The foam rises rapidly.
Wherein, the adding amount of the stannous octoate in the step is 10 wt%, the adding amount of the catalyst is 1 wt%, and the adding amount of the stabilizer is 2 wt% based on the mass of the polypropylene oxide glycol (PPG) as 100%.
(6) Curing: 1 minute after the foam stopped growing, it was placed in an oven at 30 ℃ for 48 h.
Example 8:
preparation of hydrophobic polyurethane composite (MAHF-GO/PUF):
(1) preparing graphene oxide: taking raw materials of natural graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid, and stirring the raw materials in an oil bath at the temperature of below 5 ℃ and in an oil bath at the temperature of between 35 and 98 ℃ respectively to finish an oxidation experiment; separation and purification: centrifuging the mixed solution by a centrifuge, and dialyzing by a dialysis bag until the pH of the solution is close to neutral;
(2) modification: adding a cross-linking agent functional amide monomer and a fluorine-containing monomer into the mixed solution, and carrying out oil bath reaction for 3h at 90 ℃;
wherein the cross-linking agent is hydroxymethyl acrylamide, and the fluorine-containing monomer is hexafluoroisopropanol. Wherein the dosage of the cross-linking agent is 1 percent of the mass of the graphene oxide; the mass ratio of the fluorine-containing monomer to the graphene oxide is 5: 1.
(3) And (3) freeze drying of the modified graphene oxide: the mixed solution is fixed in a drying mould after being subjected to ultrasonic treatment for 30-60 minutes, and is put into a freeze drying box for freeze drying, and the prepared modified graphene oxide foam is ground into powder for later use.
(4) Preparation of prepolymer: adding polyoxypropylene glycol into a flask connected with a circulating water type vacuum device, a condensation reflux device and a thermometer, putting the flask into an oil bath pot, carrying out vacuum drying at 120 ℃ for 3 hours, cooling to 80 ℃, and stopping vacuumizing. The circulating water vacuum pump was removed and a stirrer and Xylylene Diisocyanate (XDI) were added. After stirring at 80 ℃ for 2.5h, 1.5g of XDI was added. Prepolymerization is carried out for 1h, and the modified graphene oxide powder obtained in the step 3) is added at 0.5 h.
Wherein, the mass fraction of the polyoxypropylene glycol (PPG) in the raw materials is 70 percent and the mass fraction of the Xylylene Diisocyanate (XDI) is 30 percent according to the mass percentage; the added modified graphene oxide accounts for 15 percent of the weight of the PPG.
(5) Foaming: respectively adding stannous octoate, silicon-carbon chain type L-580 and 1, 8-diazabicycloundecen-7-ene DBU into a plastic cup, stirring and mixing, adding prepolymer with the temperature of 80 ℃, stirring for 200 seconds, and then adding distilled water. The foam rises rapidly.
Wherein, the adding amount of the stannous octoate in the step is 0.1 wt%, the adding amount of the catalyst is 3 wt%, and the adding amount of the stabilizer is 4 wt% based on the mass of the polypropylene oxide glycol (PPG) as 100%.
(6) Curing: 1 minute after the foam stopped growing, it was placed in an oven at 30 ℃ for 72 hours.
Example 9:
preparation of hydrophobic polyurethane composite (MAHF-GO/PUF):
(1) preparing graphene oxide: taking raw materials of natural graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid, and stirring the raw materials in an oil bath at the temperature of below 5 ℃ and in an oil bath at the temperature of between 35 and 98 ℃ respectively to finish an oxidation experiment; separation and purification: centrifuging the mixed solution by a centrifuge, and dialyzing by a dialysis bag until the pH of the solution is close to neutral;
(2) modification: adding a cross-linking agent functional amide monomer and a fluorine-containing monomer into the mixed solution, and carrying out oil bath reaction for 4 hours at the temperature of 80 ℃;
wherein the cross-linking agent is hydroxymethyl acrylamide, and the fluorine-containing monomer is hexafluoroisopropanol. Wherein the dosage of the cross-linking agent is 12% of the mass of the graphene oxide; the mass ratio of the fluorine-containing monomer to the graphene oxide is 3: 1.
(3) And (3) freeze drying of the modified graphene oxide: the mixed solution is fixed in a drying mould after being subjected to ultrasonic treatment for 30-60 minutes, and is put into a freeze drying box for freeze drying, and the prepared modified graphene oxide foam is ground into powder for later use.
(4) Preparation of prepolymer: adding polyoxypropylene glycol into a flask connected with a circulating water type vacuum device, a condensation reflux device and a thermometer, putting the flask into an oil bath pot, carrying out vacuum drying at 120 ℃ for 3 hours, cooling to 80 ℃, and stopping vacuumizing. The circulating water vacuum pump was removed and a stirrer and Xylylene Diisocyanate (XDI) were added. After stirring at 80 ℃ for 2.5h, 1.5g of XDI was added. Prepolymerization is carried out for 1h, and the modified graphene oxide powder obtained in the step 3) is added at 0.5 h.
Wherein, the mass fraction of the polyoxypropylene glycol (PPG) in the raw materials is 65 percent and the mass fraction of the Xylylene Diisocyanate (XDI) is 35 percent according to the mass percentage; the added modified graphene oxide accounts for 8 percent of the weight of the PPG.
(5) Foaming: respectively adding stannous octoate, silicon-carbon chain type L-580 and 1, 8-diazabicycloundecen-7-ene DBU into a plastic cup, stirring and mixing, adding prepolymer with the temperature of 80 ℃, stirring for 100 seconds, and then adding distilled water. The foam rises rapidly.
Wherein, the adding amount of the stannous octoate in the step is 3 wt%, the adding amount of the catalyst is 0.5 wt%, and the adding amount of the stabilizer is 0.5 wt% based on the mass of the polypropylene oxide glycol (PPG) as 100%.
(6) Curing: 1 minute after the foam stopped growing, it was placed in an oven at 30 ℃ for 48 h.
The hydrophobic polyurethane composite materials prepared in the above examples 7 to 9 were tested and characterized, and the results were in accordance with example 1. The adsorbing material is a composite material containing fluorine-containing graphene oxide and polyurethane foam, is used as a hydrophobic adsorbent, can well adsorb water-soluble organic dye molecules and oils, is good in recycling performance, and can be used as an efficient adsorbing material.

Claims (10)

1. A preparation method of a hydrophobic adsorption material based on polyurethane foam is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) mixing graphene oxide, a cross-linking agent and a fluorine-containing monomer, reacting to obtain modified graphene oxide, drying, and grinding to obtain hydrophobic graphene oxide powder;
(2) carrying out prepolymerization reaction on polyoxypropylene glycol, xylylene diisocyanate and modified graphene oxide serving as raw materials to obtain a prepolymer;
(3) adding stannous octoate and 1, 8-diazabicycloundecene-7-ene (DBU) as a catalyst and silicon-carbon chain type L-580 as a stabilizer into a container, stirring and mixing, adding a prepolymer at 70-80 ℃, stirring for 100-200 seconds, adding distilled water, and carrying out foaming treatment;
(4) and curing the foam subjected to foaming treatment to obtain the foam.
2. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: the raw materials in the step (2) comprise 50 to 70 weight Percent of Polyoxypropylene Glycol (PPG) and 30 to 50 weight percent of Xylylene Diisocyanate (XDI) according to the mass percentage; the weight of the additional modified graphene oxide is 1-15% of that of PPG.
3. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (1), the cross-linking agent is an amide cross-linking agent containing hydroxyl and amino, and the fluorine-containing monomer is a fluorine-containing alcohol containing more than six fluorine.
4. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (1), the dosage of the cross-linking agent is 1-12% of the mass of the graphene oxide; the mass ratio of the fluorine-containing monomer to the graphene oxide is 0.2-5: 1.
5. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (1), the raw materials are mixed at 70-90 ℃ and react for 3-5 h to obtain the hydrophobic graphene oxide.
6. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (1), the preparation of the graphene oxide comprises: taking raw materials of natural graphite, sodium nitrate, potassium permanganate and concentrated sulfuric acid, respectively stirring in an ice bath at the temperature of below 5 ℃ and in an oil bath at the temperature of between 35 and 98 ℃ to finish an oxidation experiment, separating and purifying a mixed solution, and dialyzing until the solution is neutral.
7. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (1), the drying treatment includes: and (3) carrying out ultrasonic treatment on the mixed solution for 30-60 minutes, fixing the mixed solution in a drying mould, and putting the dried mixed solution into a freeze drying box for freeze drying for 48-72 hours.
8. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (2), the amount of the modified graphene oxide is 1-12% of the mass of the polyoxypropylene glycol.
9. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (3), the adding amount of stannous octoate is 0.1-10 wt%, the adding amount of catalyst is 0.5-5 wt%, and the adding amount of stabilizer is 0.5-5 wt%, based on the mass of polypropylene oxide glycol (PPG) as 100%.
10. The method for preparing hydrophobic adsorption material based on polyurethane foam according to claim 1, characterized in that: in the step (4), the curing time is 48-72 h.
CN202110605686.7A 2021-05-31 2021-05-31 Preparation method of polyurethane foam-based hydrophobic adsorption material Pending CN113274989A (en)

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