CN105080185B - Interpenetrating network type porous polymer with adjustable and controllable surface performance and preparation method of interpenetrating network type porous polymer - Google Patents

Abstract

The invention discloses a porous polymer with controllable interpenetrating network surface properties and a preparation method thereof, which is characterized in that it comprises: a main body made of a porous material, and a layer of silicone rubber and paraffin wax are polymerized on the three-dimensional porous structure of the main body Silicone rubber/paraffin microsphere composite composed of microspheres. The present invention provides a porous polymer with controllable interpenetrating network surface properties and a preparation method thereof, which realizes continuous separation and recovery of oil phases, can significantly improve the efficiency of oil separation and environmental restoration, and has low preparation costs. The process is simple, and the preparation process is green and pollution-free; it has wide application prospects in the field of oil-water two-phase separation.

Description

Porous polymer with adjustable surface properties of interpenetrating network and preparation method thereof

technical field

The invention relates to a porous polymer with adjustable interpenetrating network surface properties and a preparation method thereof, in particular to a porous polymer with adjustable interpenetrating network surface properties for oil/water separation and a preparation method thereof. The invention belongs to the technical field of organic solvent and water two-phase separation.

Background technique

If oily wastewater is not recycled, it will cause waste; if oily wastewater is discharged into rivers, lakes or bays, it will pollute the water body and affect the survival of aquatic organisms; if used for agricultural irrigation, it will block the soil gap and hinder the growth of crops. After the oily wastewater is discharged into water bodies such as rivers, lakes and seas, the oil layer covers the water surface, preventing the oxygen in the air from diffusing into the water. Due to the reduction of dissolved oxygen in the water body, the photosynthesis of algae is limited; it affects the normal growth of aquatic organisms, makes aquatic animals and plants smell oily or toxic, and even makes the water body smelly, destroying the utilization value of water resources. Livestock often contract fatal esophageal disease if they drink oily wastewater. If the farmland is irrigated with oily wastewater, the oil and its derivatives will cover the surface of the soil and plants, block the pores of the soil, prevent air from penetrating, make the fruit smell oily, or prevent the soil from performing normal metabolism and microbial metabolism. cause crop failure or death. In addition, due to the drift and spread of oil spills, beaches and seaside tourist areas will be abandoned, causing great environmental and social harm. But the more important hazard is that oil contains carcinogenic hydrocarbons, which are enriched by fish and shellfish and endanger human health through the food chain.

The most commonly used oil spill remediation techniques today include oil skimmers, coagulation fils, dispersants, bioremediation, and in-situ burning. These technologies only focus on cleaning a large amount of oil on water, and ignore the adverse effects of dispersed oil in water on the environment. Some oil spill repair materials have also appeared at present, but most of the oil spill repair materials are limited to materials with volume and adsorption capacity, which has also become a big problem hindering the practical application of the current oil spill repair materials.

Contents of the invention

The technical problem to be solved by the present invention is to provide a continuous three-dimensional porous structure with a large specific surface area and developed pore structure. The continuous three-dimensional porous structure forms several channels. The channel has strong selectivity and only allows the oil phase to pass through. The continuous and efficient separation of the oil phase substances in the oil-water mixture is realized, and it is no longer limited to the volume and adsorption capacity of the adsorption material itself, and can be used continuously without regeneration. The interpenetrating network-type porous polymer with adjustable surface properties; further , the invention provides a method for preparing a porous polymer with adjustable interpenetrating network surface properties. The method has low preparation cost, simple process, green and pollution-free preparation process, and utilizes the hydrophobicity and lipophilicity of silicone rubber and paraffin microspheres. Using porous materials as carriers and self-developed paraffin microspheres as modifiers, a material capable of continuous oil-water two-phase separation is prepared; further, the present invention provides a preparation method for micron-scale paraffin microspheres, which The paraffin microsphere prepared by the method increases the hydrophobicity of the porous polymer of the present invention, increases the selectivity of the channel to the oil phase substance, and has a good effect of separating oil and water.

In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:

The porous polymer with adjustable surface properties of interpenetrating network is characterized in that: it includes: a main body made of porous material, and a silicone rubber/paraffin wax composed of a layer of silicone rubber and paraffin microspheres is polymerized on the three-dimensional porous structure of the main body. Microsphere complex.

The porous material includes polyurethane sponge.

The material of the silicone rubber includes 107-2000 two-component room temperature vulcanized silicone rubber.

The paraffin microspheres are micron-scale paraffin microspheres.

A method for preparing a porous polymer with adjustable interpenetrating network surface properties, characterized in that it includes the following steps:

S01, cut the main body made of porous material into a suitable size according to actual needs, then put it into an oven, and dry it at 110~120 ^o C for 1~2 hours;

S02, take silicone rubber and paraffin microspheres according to the mass ratio, add curing agent after fully stirring evenly, and then fully stir for 1 ~ 2min to obtain a mixed solution; the mass ratio is silicone rubber: paraffin microspheres = 10 ~ 5: 1;

S03, take out the main body from the oven, put it into the mixed liquid in step S02 to fully absorb it, put it into the oven after the absorption is saturated, and cure it at constant temperature for at least 2 hours to obtain a finished product.

The curing agent is a supporting product of the manufacturer, generally 1/10 of the amount of silicone rubber added.

The preparation method of described paraffin microspheres comprises the following steps:

Step 1: Add water and surfactant into the three-necked flask, put it into a constant temperature water bath at 70-80°C and heat it for 10-15 minutes, and stir it with an electric stirrer for 2-3 minutes; the amount of the surfactant added is 3 to 5 times the mass of the paraffin microspheres;

Step 2: Heat and melt the solid sliced paraffin to form liquid paraffin; slowly add it dropwise to the three-necked flask in step 1 at a rate of 3-5 drops per minute, and keep stirring at constant temperature for 2-2.5 hours to obtain a paraffin wax emulsion ;

Step 3: pour the paraffin wax emulsion into a beaker, and age at room temperature for at least 12 hours; remove the aggregated solids in the upper layer, and dry them naturally at room temperature to obtain paraffin wax microspheres.

The surfactant includes polyethylene glycol octylphenyl ether.

The invention uses polyurethane sponge as the main body, polymerizes silicon rubber film on the surface of the porous structure, and utilizes paraffin microspheres to further enhance the hydrophobicity and lipophilicity of the material.

Paraffin is a section paraffin with a higher melting point of 58-60°C.

The use method of the present invention is: the interpenetrating network type surface performance controllable porous polymer of the present invention is connected in the inlet pipe of the pump, and the porous polymer connected at the inlet of the inlet pipe is directly placed in the oil-water mixture; The hydrophobicity of the porous material enables it to float on the water surface; when the pump is working, the oil phase in the oil-water mixture will pass through the pores of the interpenetrating network-type porous polymer with adjustable surface properties; it is concentrated by the discharge pipe of the pump Drain to the container for storage to enrich the oil phase substances; at the same time, due to the hydrophobicity of the porous material itself, the water in the oil-water mixture is repelled from entering the channel of the porous polymer, so that the water phase remains in the original container; thus realizing the oil phase of the oil-water mixture Separated from the aqueous phase.

The present invention provides a porous polymer with adjustable interpenetrating network surface properties and a preparation method thereof, which utilizes the hydrophobicity and lipophilicity of silicone rubber and paraffin microspheres, uses polyurethane sponge as a porous material, and uses self-developed paraffin microspheres As a modifier, a material capable of continuous oil-water two-phase separation is prepared; the present invention utilizes polyurethane sponge, silicone rubber, paraffin and other cheap raw materials, and the preparation process is simple and pollution-free; the main feature of the material is that the pore structure is developed, forming a continuous The connected three-dimensional porous structure has a large specific surface area and strong adsorption capacity for the oil phase. At the same time, the addition of paraffin microspheres increases the hydrophobicity of the material, and realizes the continuous and efficient separation of the oil phase substances in the oil-water mixture; The connected three-dimensional porous structure forms several channels, which have strong selectivity and only allow the oil phase to pass through. Therefore, compared with conventional oil-water separation materials, the present invention is no longer limited to the volume or adsorption capacity of the adsorption material itself, and can be used continuously for a long time , no need for regeneration treatment, simple operation, easy to use, and can directly and continuously collect oil phase substances, which greatly simplifies the recovery process of oil phase substances; the preparation method of micron-scale paraffin microspheres in the present invention, the paraffin microspheres prepared by this method The ball increases the hydrophobicity of the porous polymer, making the channel selectivity high and further enhancing the effect of separating oil and water. The present invention provides a porous polymer with controllable interpenetrating network surface properties and its preparation method, which realizes the continuous separation and recovery of oil phase, can significantly improve the separation efficiency of oil stains and the efficiency of repairing the environment, and the preparation cost is low. The process is simple, and the preparation process is green and pollution-free; it has broad application prospects in the field of oil-water two-phase separation (for example, oil tanker leakage, etc.).

Description of drawings

Fig. 1 is the enlarged photograph of paraffin microsphere among the present invention;

Fig. 2 is the contact angle of silicone rubber/paraffin microsphere composite to water among the present invention;

Fig. 3 is the scanning electron microscope picture of the porous structure of porous polymer of the present invention;

Fig. 4 is the microscopic scanning electron microscope picture of the porous structure of porous polymer of the present invention;

Fig. 5 is a stress-strain test diagram of a porous polymer with a mass ratio of silicone rubber and paraffin microspheres of the present invention of 10:1.

detailed description

The present invention will be further described below in conjunction with the accompanying drawings.

Example 1:

As shown in Figures 1 to 5, the interpenetrating network-type porous polymer with adjustable surface properties is characterized in that it includes: a main body made of a porous material, and a layer of silicone rubber and paraffin wax are polymerized on the three-dimensional porous structure of the main body Silicone rubber/paraffin microsphere composite composed of microspheres.

The porous material includes polyurethane sponge.

The material of the silicone rubber includes 107-2000 two-component room temperature vulcanized silicone rubber.

The manufacturer of 107-2000 two-component RTV silicone rubber is Jinan Guobang Chemical.

The paraffin microspheres are micron-scale paraffin microspheres.

A method for preparing a porous polymer with adjustable interpenetrating network surface properties, characterized in that it includes the following steps:

S01, cut the main body made of porous material into a suitable size according to actual needs, then put it in an oven, and dry it at 110 ^o C for 1 hour;

S02, take silicone rubber and paraffin microspheres according to the mass ratio, add curing agent after fully stirring evenly, and then fully stir for 1min to obtain a mixed solution; the mass ratio is silicone rubber:paraffin microspheres=10:1;

S03, take out the main body from the oven, put it into the mixed liquid in step S02 to fully absorb it, put it into the oven after the absorption is saturated, and cure it at a constant temperature for 2 hours to obtain a finished product.

Curing agent: silicone rubber = 1:10 weight ratio added.

The preparation method of described paraffin microspheres comprises the following steps:

Step 1: Add water and polyethylene glycol octylphenyl ether into a three-necked flask, then put it into a 70°C constant temperature water bath and heat for 10 minutes, and stir with an electric stirrer for 2 minutes; the polyethylene glycol octylphenyl ether The addition of ether is 3 times the amount of the quality of the paraffin microspheres;

Step 2: heating and melting the solid sliced paraffin to form liquid paraffin; slowly drop it into the three-necked flask in step 1 at a rate of 3 drops per minute, and keep stirring at constant temperature for 2 hours to obtain a paraffin emulsion;

Step 3: Pour the paraffin wax emulsion into a beaker, and age at room temperature for 12 hours; remove the aggregated solids in the upper layer, and dry them naturally at room temperature to obtain paraffin wax microspheres.

Example 2:

As shown in Figures 1 to 5, the interpenetrating network-type porous polymer with adjustable surface properties is characterized in that it includes: a main body made of a porous material, and a layer of silicone rubber and paraffin wax are polymerized on the three-dimensional porous structure of the main body Silicone rubber/paraffin microsphere composite composed of microspheres.

The porous material includes polyurethane sponge.

The material of the silicone rubber includes 107-2000 two-component room temperature vulcanized silicone rubber.

The manufacturer of 107-2000 two-component RTV silicone rubber is Jinan Guobang Chemical.

The paraffin microspheres are micron-scale paraffin microspheres.

A method for preparing a porous polymer with adjustable interpenetrating network surface properties, characterized in that it includes the following steps:

S01, cut the main body made of porous material into a suitable size according to actual needs, then put it in an oven, and dry it at 120 ^o C for 2 hours;

S02, take silicone rubber and paraffin microspheres according to the mass ratio, add curing agent after fully stirring evenly, and then fully stir for 2 minutes to obtain a mixed solution; the mass ratio is silicone rubber:paraffin microspheres=5:1;

S03, take out the main body from the oven, put it into the mixed liquid in step S02 to fully absorb it, put it into the oven after the absorption is saturated, and cure it at constant temperature for at least 2 hours to obtain a finished product.

Curing agent: silicone rubber = 1:10 weight ratio added.

The preparation method of described paraffin microspheres comprises the following steps:

Step 1: Add water and polyethylene glycol octylphenyl ether into a three-necked flask, then put it into a constant temperature water bath at 80°C and heat for 15 minutes, and stir with an electric stirrer for 3 minutes; the polyethylene glycol octylphenyl ether The amount of ether added is 5 times the quality of the paraffin microspheres;

Step 2, heating and melting the solid sliced paraffin to form liquid paraffin; slowly drop it into the three-necked flask in step 1 at a rate of 5 drops per minute, and keep stirring at a constant temperature for 2.5 hours to obtain a paraffin emulsion;

Step 3: pour the paraffin wax emulsion into a beaker, and age at room temperature for at least 12 hours; remove the aggregated solids in the upper layer, and dry them naturally at room temperature to obtain paraffin wax microspheres.

Example 3:

As shown in Figures 1 to 5, the interpenetrating network-type porous polymer with adjustable surface properties is characterized in that it includes: a main body made of a porous material, and a layer of silicone rubber and paraffin wax are polymerized on the three-dimensional porous structure of the main body Silicone rubber/paraffin microsphere composite composed of microspheres.

The porous material includes polyurethane sponge.

The material of the silicone rubber includes 107-2000 two-component room temperature vulcanized silicone rubber.

The manufacturer of 107-2000 two-component RTV silicone rubber is Jinan Guobang Chemical.

The paraffin microspheres are micron-scale paraffin microspheres.

A method for preparing a porous polymer with adjustable interpenetrating network surface properties, characterized in that it includes the following steps:

S01, cut the main body made of porous material into a suitable size according to actual needs, then put it in an oven, and dry it at 115 ^o C for 1.5 hours;

S02, take silicone rubber and paraffin microspheres according to the mass ratio, add curing agent after fully stirring evenly, and then fully stir for 1.5min to obtain a mixed solution; the mass ratio is silicone rubber:paraffin microspheres=8:1;

S03, take out the main body from the oven, put it into the mixed liquid in step S02 to fully absorb it, put it into the oven after the absorption is saturated, and cure it at constant temperature for at least 2 hours to obtain a finished product.

Curing agent: silicone rubber = 1:10 weight ratio added.

The preparation method of described paraffin microspheres comprises the following steps:

Step 1: Add water and surfactant to the three-necked flask, then put it into a 75°C constant temperature water bath and heat for 13 minutes, and stir with an electric stirrer for 2.5 minutes; the amount of the surfactant added is the mass of the paraffin microspheres 4 times the amount;

Step 2, heating and melting the solid sliced paraffin to form liquid paraffin; slowly drop it into the three-necked flask in step 1 at a rate of 4 drops per minute, and keep stirring at a constant temperature for 2.2 hours to obtain a paraffin emulsion;

Step 3: pour the paraffin wax emulsion into a beaker, and age at room temperature for at least 12 hours; remove the aggregated solids in the upper layer, and dry them naturally at room temperature to obtain paraffin wax microspheres.

The surfactant includes polyethylene glycol octylphenyl ether.

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also possible. It should be regarded as the protection scope of the present invention.

Claims (5)

1. The porous polymer with adjustable surface properties of interpenetrating network is characterized in that: it comprises: a main body whose material is a porous material, and a silicone rubber composed of a layer of silicone rubber and paraffin microspheres is polymerized on the three-dimensional porous structure of the main body / paraffin microsphere composite; the material of the silicone rubber includes 107-2000 two-component room temperature vulcanized silicone rubber; the paraffin microspheres are micron-scale paraffin microspheres. 2. The interpenetrating network-type porous polymer with adjustable surface properties according to claim 1, characterized in that: the porous material comprises polyurethane sponge. 3. The preparation method of the interpenetrating network-type porous polymer whose surface properties can be regulated according to any one of claims 1 to 2, characterized in that: comprising the following steps: S01, cut the main body made of porous material into a suitable size according to actual needs, then put it into an oven, and dry it at 110~120 ^o C for 1~2 hours; S02, take silicone rubber and paraffin microspheres according to the mass ratio, add curing agent after fully stirring evenly, and then fully stir for 1 ~ 2min to obtain a mixed solution; the mass ratio is silicone rubber: paraffin microspheres = 10 ~ 5: 1; S03, take out the main body from the oven, put it into the mixed liquid in step S02 to fully absorb it, put it into the oven after the absorption is saturated, and cure it at constant temperature for at least 2 hours to obtain a finished product. 4. The preparation method of the interpenetrating network type surface property controllable porous polymer according to claim 3, characterized in that: the preparation method of the paraffin microspheres comprises the following steps: Step 1: Add water and surfactant into the three-necked flask, put it into a constant temperature water bath at 70-80°C and heat it for 10-15 minutes, and stir it with an electric stirrer for 2-3 minutes; the amount of the surfactant added is 3 to 5 times the mass of the paraffin microspheres; Step 2: Heat and melt the solid sliced paraffin to form liquid paraffin; slowly add it dropwise to the three-necked flask in step 1 at a rate of 3-5 drops per minute, and keep stirring at constant temperature for 2-2.5 hours to obtain a paraffin wax emulsion ; Step 3: pour the paraffin wax emulsion into a beaker, and age at room temperature for at least 12 hours; remove the aggregated solids in the upper layer, and dry them naturally at room temperature to obtain paraffin wax microspheres. 5 . The method for preparing an interpenetrating network-type porous polymer with adjustable surface properties according to claim 4 , wherein the surfactant comprises polyethylene glycol octylphenyl ether. 6 .