阅读说明：本技术 聚氨酯泡沫负载疏水改性花生壳复合材料及其制备方法 (Polyurethane foam loaded hydrophobic modified peanut shell composite material and preparation method thereof ) 是由 任龙芳 汤正 余思杰 于 2021-07-27 设计创作，主要内容包括：本发明公开了聚氨酯泡沫负载疏水改性花生壳复合材料及其制备方法,属于聚合物复合材料油水分离领域。为达到疏水改性的目的,本发明提供的方法为：首先利用长碳链的十六烷基三甲氧基硅烷对预处理后的花生壳粉末进行接枝改性；然后将疏水改性花生壳粉末与端异氰酸酯基聚氨酯预聚体和水混合搅拌,发泡固化后,得到疏水的聚氨酯泡沫负载改性花生壳粉末复合材料。本发明制备的聚氨酯泡沫/改性花生壳粉末复合材料具有良好的疏水性、稳定性和再生性,能够有效提高聚氨酯泡沫的油水分离能力。(The invention discloses a polyurethane foam loaded hydrophobic modified peanut shell composite material and a preparation method thereof, and belongs to the field of oil-water separation of polymer composite materials. In order to achieve the aim of hydrophobic modification, the method provided by the invention comprises the following steps: firstly, utilizing hexadecyl trimethoxy silane with a long carbon chain to carry out graft modification on the pretreated peanut shell powder; and then mixing and stirring the hydrophobic modified peanut shell powder, the isocyanate-terminated polyurethane prepolymer and water, and foaming and curing to obtain the hydrophobic polyurethane foam load modified peanut shell powder composite material. The polyurethane foam/modified peanut shell powder composite material prepared by the invention has good hydrophobicity, stability and reproducibility, and can effectively improve the oil-water separation capability of polyurethane foam.)

1. The polyurethane foam loaded hydrophobic modified peanut shell composite material and the preparation method thereof are characterized by comprising the following steps:

the method comprises the following steps: placing 2-4 parts by mass of the pretreated peanut shell powder into an ethanol solution of hexadecyl trimethoxy silane, stirring and reacting for 1-4 hours at 40-50 ℃, and then filtering, washing and drying to obtain hydrophobically modified peanut shell powder;

step two: mixing the hydrophobically modified peanut shell powder, the polyurethane prepolymer and water, stirring at the rotating speed of 800-1000 rpm for 40-60 s to uniformly mix the mixture, then quickly transferring the mixture to an evaporation pan, foaming and curing at room temperature, taking out the mixture, cutting the polyurethane foam into blocks with proper sizes, respectively cleaning the blocks with water and absolute ethyl alcohol for 2-3 times, and drying the blocks in an oven at the temperature of 60-70 ℃ to obtain the polyurethane foam loaded hydrophobically modified peanut shell powder composite material.

2. The method of claim 1, wherein the pre-treating of the peanut shell powder comprises crushing the washed peanut shells through a 300 mesh screen.

3. The method according to claim 2, wherein the volume ratio of the components in the ethanol solution of hexadecyltrimethoxysilane in the first step is hexadecyltrimethoxysilane: water: the absolute ethyl alcohol is 2-4: 5: 43-41.

4. The method according to claim 3, wherein the ethanol solution of hexadecyltrimethoxysilane in the first step is magnetically stirred at 40 ℃ for 6-24 hours.

5. The preparation method of claim 4, wherein the polyurethane prepolymer in the second step is an isocyanate-terminated prepolymer, and the mass ratio of the hydrophobically modified peanut shell powder to the polyurethane prepolymer to water is as follows: 1-4: 20: 30-50.

6. The polyurethane foam-supported hydrophobically modified peanut shell powder composite prepared by the preparation method of claims 1-5.

7. Use of the composite material according to claim 6 in oil-water separation.

Technical Field

The invention belongs to the field of oil-water separation of polymer composite materials, and relates to a polyurethane foam loaded hydrophobic modified peanut shell composite material and a preparation method thereof.

Background

In recent years, ship oil spill accidents frequently occur, which bring disastrous consequences to marine environment, cause damage to ecological environment, pollution to seaside scenic spots, fire and other problems, and become very serious environmental, economic and social problems; the problems of ocean oil spill and organic reagent leakage need to be solved.

The chemically synthesized oil absorption material has good oleophylic hydrophobicity, high oil absorption speed and high oil absorption multiplying power, and has the defects of oil leakage under pressure, difficult biodegradation and high price; the inorganic oil absorption material has wide source, high oil absorption multiplying power, simple and convenient preparation method and easy operation, but has the problems of low cyclic utilization rate, poor oil-water selectivity, poor floatability and difficult disposal. The synthetic material polyurethane foam has a three-dimensional porous structure, high porosity and excellent elastic performance, and can be repeatedly used as a durable oil absorption material. However, the polyurethane foam has hydrophilic groups on the surface, so that the selectivity of the polyurethane foam is poor when oil-water separation is carried out, and hydrophobic modification is needed.

Disclosure of Invention

The invention aims to provide a polyurethane foam loaded hydrophobically modified peanut shell composite material and a preparation method thereof, and solves the problems of poor oil absorption effect, high manufacturing cost and the like of the existing oil absorption material.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the polyurethane foam loaded hydrophobic modified peanut shell composite material and the preparation method thereof comprise the following steps:

the method comprises the following steps: placing 2-4 parts of the pretreated peanut shell powder into an ethanol solution of hexadecyl trimethoxy silane, stirring and reacting for 1-4 hours at 40-50 ℃, and then filtering, washing and drying to obtain hydrophobically modified peanut shell powder;

step two: mixing the hydrophobically modified peanut shell powder, the polyurethane prepolymer and water, stirring at the rotating speed of 800-1000 rpm for 40-60 s to uniformly mix the mixture, then quickly transferring the mixture to an evaporation pan, foaming and curing at room temperature, taking out the mixture, cutting the polyurethane foam into blocks with proper sizes, respectively cleaning the blocks with water and absolute ethyl alcohol for 2-3 times, and drying the blocks in an oven at the temperature of 60-70 ℃ to obtain the polyurethane foam loaded hydrophobically modified peanut shell powder composite material.

Furthermore, the pretreated peanut shell powder is prepared by crushing the cleaned peanut shell and sieving the crushed peanut shell with a 300-mesh sieve.

Further, in the first step, the volume ratio of the components in the ethanol solution of the hexadecyl trimethoxy silane is that the hexadecyl trimethoxy silane: water: the absolute ethyl alcohol is 2-4: 5: 43-41.

Further, in the step one, the ethanol solution of hexadecyl trimethoxy silane is stirred magnetically at 40 ℃ for 6-24 hours in advance.

Further, in the second step, the polyurethane prepolymer is an isocyanate-terminated prepolymer, and the mass ratio of the hydrophobically modified peanut shell powder to the polyurethane prepolymer to water is as follows: 1-4: 20: 30-50.

The polyurethane foam loaded hydrophobic modified peanut shell powder composite material prepared by the preparation method.

The composite material is applied to oil-water separation.

Compared with the prior art, the invention has the following beneficial effects:

1. the biomass material peanut shell used in the invention is rich in hydroxyl groups which are easy to modify, firstly, the peanut shell powder is subjected to hydrophobic modification, and then the peanut shell powder is loaded on polyurethane foam, so that the hydrophobicity of the polyurethane foam is improved, and the oil-water separation capability of the polyurethane foam is improved.

2. The invention reasonably utilizes resources, the peanut shells are cheap and easy to obtain, the waste is recycled, and the consumption of raw materials can be reduced to a certain extent; the invention takes water as the foaming agent, is green and environment-friendly, and promotes the development of eco-friendly materials; the preparation process is simple, and the natural foaming can be realized only by mixing and stirring the corresponding materials.

Drawings

FIG. 1 is an infrared spectrum of peanut shell powder before and after hydrophobic modification;

fig. 2 is an infrared spectrum of original polyurethane foam (PUF) and modified peanut shell powder/polyurethane prepolymer 1/10 composite foam (PSP-PUF-10);

FIG. 3 is a scanning electron microscope image of the PUF and PSP-PUF-10;

FIG. 4 shows the water contact angle of the PUF and PSP-PUF-10.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The method mainly comprises two invention points: firstly, preparing peanut shell powder through hydrophobic modification; secondly, loading polyurethane foam. The following are detailed separately:

the preparation method of the peanut shell powder with hydrophobic modification comprises the following steps:

and (4) crushing the cleaned peanut shells, and screening the crushed peanut shells through a 300-mesh screen for later use.

Putting a certain amount of peanut shell powder into an ethanol solution of hexadecyl trimethoxy silane, magnetically stirring for 1-4 h at 40-50 ℃, filtering a reaction system after the reaction is finished, repeatedly cleaning with absolute ethyl alcohol, and drying in a 70 ℃ oven.

Further, the volume ratio of each component of the ethanol solution of the hexadecyl trimethoxy silane is that the hexadecyl trimethoxy silane: water: and (3) anhydrous ethanol is 2-4: 5: 43-41, and stirring at 40 ℃ and 80rpm for 6-24 hours.

A polyurethane foam loading method comprising:

step one, mixing a certain amount of polyurethane prepolymer, modified peanut shell powder and water, and violently stirring for 40-60 s to obtain a uniform mixed solution;

and step two, quickly pouring the mixed solution into an evaporation dish, foaming and curing at room temperature to obtain the polyurethane foam loaded hydrophobic modified peanut shell powder composite material, cutting the composite material into blocks with proper sizes, and then placing the blocks into an oven at 60-70 ℃ for drying.

Further, the mass ratio of the components in the step one is that the modified peanut shell powder: a polyurethane prepolymer: 1-4% of water: 20: 30-50, wherein the polyurethane prepolymer is an isocyanate-terminated polyurethane prepolymer.

Example 1:

the method comprises the following steps: washing peanut shell with tap water for 3 times, then washing with distilled water for 2 times, removing impurities, and oven drying at 70 deg.C. Pulverizing dried peanut shell with pulverizer, cleaning, removing soluble substance, and drying. The dried peanut shell powder is screened through a 300 mesh screen for future use.

5mL of distilled water was added to 43mL of ethanol, the pH was adjusted to about 5 with 0.1mol/L HCl, 2mL of hexadecyltrimethoxysilane was added, and the mixture was stirred at 40 ℃ for 12 hours. Adding 2g of sieved peanut shell powder, reacting for 2 hours at the temperature, filtering the reactant, washing with absolute ethyl alcohol for three times, and transferring the peanut shell powder to a 70 ℃ oven for drying to obtain the hydrophobically modified peanut shell powder.

Step two: the modified peanut shell powder comprises the following components in percentage by mass: a polyurethane prepolymer: water 1: 10: and 20, respectively weighing 10g of polyurethane prepolymer, weighing 20g of water and 1g of modified peanut shell powder, stirring and mixing for 40s at room temperature in a three-neck flask, quickly transferring the reactants to an evaporation dish, foaming and curing for 10min at room temperature, cutting the reactant into a cube of 2 x 2cm3, respectively ultrasonically cleaning for 3 times by using distilled water and absolute ethyl alcohol, and finally drying in an oven at 60 ℃ to obtain the polyurethane foam loaded hydrophobic modified peanut shell powder composite material.

When the adsorption device is used, kerosene and water to be adsorbed and separated are mixed in a beaker, then a piece of composite foam is placed in the beaker, the composite foam is taken out after adsorption is saturated, the mass of the composite foam before and after adsorption is respectively weighed, and the adsorption capacity is calculated.

During regeneration, the adsorbed kerosene is extruded out and collected, and then the composite foam is placed in absolute ethyl alcohol for repeated extrusion to replace the residual kerosene. And (3) drying the cleaned composite foam in a 60 ℃ drying oven for the next oil-water separation experiment.

Example 2:

the method comprises the following steps: washing peanut shell with tap water for 3 times, then washing with distilled water for 2 times, removing impurities, and oven drying at 70 deg.C. Pulverizing dried peanut shell with pulverizer, cleaning, removing soluble substance, and drying. The dried peanut shell powder is screened through a 300 mesh screen for future use.

5mL of distilled water was added to 42mL of ethanol, the pH was adjusted to about 5 with 0.1mol/L HCl, 3mL of hexadecyltrimethoxysilane was added, and the mixture was stirred at 45 ℃ for 8 hours. Adding 2g of sieved peanut shell powder, reacting for 2 hours at the temperature, washing the reactant for three times by using absolute ethyl alcohol, and transferring the peanut shell powder to a 70 ℃ oven for drying to obtain the hydrophobically modified peanut shell powder.

Step two: the modified peanut shell powder comprises the following components in percentage by mass: a polyurethane prepolymer: water 1.5: 10: and 20, respectively weighing 10g of polyurethane prepolymer, 20g of water and 1.5g of modified peanut shell powder in a three-neck flask, stirring and mixing for 50s at room temperature, quickly transferring the reactants into an evaporation dish, foaming and curing for 10min at room temperature, cutting the reactants into cubes of 2 multiplied by 2cm3, respectively ultrasonically cleaning the cubes with distilled water and absolute ethyl alcohol for three times, and finally drying the cubes in a 60 ℃ oven to obtain the polyurethane foam loaded hydrophobic modified peanut shell powder composite material.

When the composite foam adsorption device is used, dichloromethane and water to be adsorbed and separated are mixed in a beaker, then a piece of composite foam is controlled by tweezers and placed at the bottom of the beaker, the composite foam is taken out after adsorption is saturated, the mass of the composite foam before and after adsorption is respectively weighed, and the adsorption capacity is calculated.

And during regeneration, extruding and collecting the adsorbed dichloromethane, placing the composite foam into absolute ethyl alcohol, repeatedly extruding, and replacing residual dichloromethane. And (3) drying the cleaned composite foam in a 60 ℃ drying oven for the next oil-water separation experiment.

Referring to fig. 1, fig. 1 is an infrared spectrum before and after the hydrophobic modification of the peanut shell powder, which shows that hydroxyl groups of the modified peanut shell powder are basically disappeared, and a plurality of peaks of hexadecyl trimethoxy silane appear, indicating that the grafting of the long carbon chain silane on the peanut shell powder is successful.

Referring to fig. 2, fig. 2 is an infrared spectrum of a raw polyurethane foam (PUF) and a modified peanut shell powder/polyurethane prepolymer 1/10 syntactic foam material (PSP-PUF-10), and it can be seen from the infrared spectrum that most of the two materials have the same peak position, but the PSP-PUF-10 has double peaks at 2914 and 2852cm-1, which are symmetric and asymmetric stretching vibration peaks of a long carbon chain-CH 2, indicating that the peanut shell powder is successfully loaded.

Referring to fig. 3, fig. 3 is a scanning electron microscope image of the PUF and the PSP-PUF-10. As can be seen, the surface roughness of the PSP-PUF-10 is significantly improved as compared with that of the PUF, providing a water-repellent rough surface.

Referring to fig. 4, fig. 4 is a graph of water contact angles of PUF and PSP-PUF-10, and the loading of the modified peanut shell powder increases the surface roughness of the polyurethane foam, decreasing the surface energy, resulting in an increase in the water contact angle of the polyurethane foam.

The above are specific embodiments of the present invention, but the structural features of the present invention are not limited thereto, and the present invention can be applied to similar products, and any changes or modifications within the scope of the present invention by those skilled in the art are covered by the claims of the present invention.