阅读说明：本技术 一种磁性吸油聚烯烃泡沫材料及其制备方法 (Magnetic oil-absorbing polyolefin foam material and preparation method thereof ) 是由 许亮 陶慷 洪江 李瑞龙 焦旗 于 2021-07-29 设计创作，主要内容包括：本发明涉及吸油材料技术领域,具体涉及一种磁性吸油聚烯烃泡沫材料及其制备方法。本发明制备方法主要包括以下步骤：首先将四氧化三铁置于共混机中,加入偶联剂进行共混表面改性；然后将改性好的四氧化三铁加入聚烯烃发泡组合物中共混,在挤出机中经超临界气体发泡,冷却造粒,即得该磁性吸油聚烯烃泡沫材料。本发明制备方法简单,成本低,可工业化生产,所制备的磁性吸油聚烯烃泡沫材料具有良好的亲油疏水和高回弹性能,吸油效果良好,可重复使用,铺覆于海面上,通过磁场作用,不扩散,易回收重复使用,并且回收的吸油泡沫材料通过离心可对油品进行回收。(The invention relates to the technical field of oil absorption materials, in particular to a magnetic oil absorption polyolefin foam material and a preparation method thereof. The preparation method mainly comprises the following steps: firstly, ferroferric oxide is placed in a blender, and a coupling agent is added to carry out blending surface modification; and then adding the modified ferroferric oxide into the polyolefin foaming composition for blending, foaming by supercritical gas in an extruder, cooling and granulating to obtain the magnetic oil-absorbing polyolefin foam material. The preparation method is simple, the cost is low, the industrial production can be realized, the prepared magnetic oil absorption polyolefin foam material has good oleophylic and hydrophobic property and high resilience, the oil absorption effect is good, the magnetic oil absorption polyolefin foam material can be repeatedly used, the magnetic oil absorption polyolefin foam material is paved on the sea surface, does not diffuse under the action of a magnetic field, is easy to recover and reuse, and the recovered oil absorption foam material can recover oil products through centrifugation.)

1. The preparation method of the magnetic oil-absorbing polyolefin foam material is characterized by comprising the following steps of:

s1, placing the dried ferroferric oxide into a blender, adding a coupling agent, stirring and mixing uniformly at normal temperature, and standing to obtain modified ferroferric oxide;

s2, uniformly mixing the modified ferroferric oxide and the polyolefin foaming composition in a blender to obtain a magnetic polyolefin foaming composition;

s3, adding the magnetic polyolefin foaming composition into a bin of a single-screw extruder for extrusion, simultaneously adding supercritical gas into a compression section of the extruder through a gas injection system, extruding and foaming through a die head of the extruder, and then cooling and pelletizing to obtain the magnetic oil-absorbing polyolefin foam material.

2. The preparation method of the magnetic oil-absorbing polyolefin foam material according to claim 1, wherein the weight parts of the following components are as follows: in the step S1, 99-99.5 parts of ferroferric oxide and 0.5-1 part of coupling agent are added; in the step S2, 5-15 parts of modified ferroferric oxide and 85-95 parts of polyolefin foaming composition are used.

3. The method for preparing a magnetic oil-absorbing polyolefin foam material according to claim 1 or 2, wherein in the step S1, the coupling agent comprises any one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, triisostearoylphthalate and diisostearoylphthalate.

4. The method for preparing a magnetic oil-absorbing polyolefin foam material according to claim 1, wherein in the step S2, the polyolefin foaming composition comprises 98.5-99.5% by mass of polyolefin and 0.5-1.5% by mass of nucleating agent.

5. The method for preparing the magnetic oil-absorbing polyolefin foam material as claimed in claim 4, wherein the polyolefin comprises any one or more of PP, PE and POE.

6. The method for preparing a magnetic oil-absorbing polyolefin foam material according to claim 4, wherein the nucleating agent comprises any one or more of calcium carbonate, calcium oxide, mica, talc, nanoclay and kaolin.

7. The method for preparing magnetic oil-absorbing polyolefin foam material according to claim 1, wherein in the step S3, the extrusion process of the single-screw extruder is as follows: the temperature of the front half area of the extruder is 190-220 ℃, the temperature of the rear half area of the extruder is 140-190 ℃, and the rotating speed of the extruder is 9-55 rpm.

8. The method of claim 1, wherein in step S3, the gas flow rate of the gas injection system is controlled to be 3-15L/min.

9. The method for preparing magnetic oil absorbing polyolefin foam material according to claim 1, wherein in step S3, the supercritical gas is supercritical carbon dioxide or supercritical nitrogen.

10. The magnetic oil-absorbing polyolefin foam material prepared by the method of any one of claims 1 to 9, wherein the magnetic oil-absorbing polyolefin foam material has an open cell content of more than 95% and a bulk density of 0.03 to 0.08g/cm³The particle size is 3 to 5 mm.

Technical Field

The invention relates to the technical field of oil absorption materials, in particular to a magnetic oil absorption polyolefin foam material and a preparation method thereof.

Background

With the rapid development of the world economy, the acceleration of the global industrialization process and the rapid increase of the global energy demand, the development of crude oil is more and more intensive, and the demand for petroleum resources and derivatives thereof is continuously increased. Oil leakage occurs frequently, oil-water mixing treatment is not good, and serious damage can be caused to the environment, an ecological system and even human existence. Therefore, effective separation of oil-water mixtures has become a focus of recent research. At present, the method for treating the water body oil drainage mainly comprises several modes of dispersion, combustion and adsorption. Among them, adsorption purification of oil stains is considered to be one of the most economical, rapid and effective methods. The porous materials such as foam, sponge and the like are the preferred adsorption materials for oil-water separation treatment due to the advantages of large specific surface area, high oil absorption rate, easily available raw materials, simple manufacture and the like.

The patent with publication number CN104744819B discloses a foamed polypropylene oil absorption material and a preparation method thereof, the oil absorption material has good oleophylic and hydrophobic properties, and can effectively solve the problems of oil recovery purity and reuse, but the prepared oil absorption material is super-hydrophobic, has good fluidity and dispersibility in water, and is often easy to disperse and difficult to gather and recover when applied to oil-water separation treatment, so that the oil absorption material is difficult to be applied in a large scale in an environment of dynamic water surface treatment oil stain leakage. The invention patent with publication number CN104151600B discloses a preparation method of super-hydrophobic magnetic sponge, which is characterized in that sea urchin-shaped carbon-coated ferroferric oxide particles are attached to the surface of polyurethane sponge in a manner of soaking and utilizing an adhesive, so that the sponge obtains magnetism and hydrophobicity, but in the using process of the super-hydrophobic magnetic sponge prepared by the method, along with the increase of repeated use times, the magnetic layer in the sponge is gradually reduced, and the hydrophobicity is gradually weakened, so that the repeated use rate and the oil-water recovery effect are influenced.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a magnetic oil-absorbing polyolefin foam material and a preparation method thereof. The magnetic oil absorption polyolefin foam material provided by the invention has good oleophylic and hydrophobic properties and high resilience, can be repeatedly used, has excellent oil absorption rate and oil retention rate, can be effectively positioned and collected on a dynamic water surface under the action of an external magnetic field, and can effectively solve the technical problems that the existing oil absorption material is not easy to recover when applied on the dynamic water surface, the oil absorption material has low repeated utilization rate, the oil-water separation effect is poor, the purity of the recovered oil product is low and the like.

In order to solve the technical problems, the invention adopts the technical scheme that:

a preparation method of a magnetic oil-absorbing polyolefin foam material comprises the following steps:

s1, placing the dried ferroferric oxide into a blender, adding a coupling agent, stirring and mixing uniformly at normal temperature, and standing to obtain modified ferroferric oxide;

s2, uniformly mixing the modified ferroferric oxide and the polyolefin foaming composition in a blender to obtain a magnetic polyolefin foaming composition;

s3, adding the magnetic polyolefin foaming composition into a bin of a single-screw extruder for extrusion, simultaneously adding supercritical gas into a compression section of the extruder through a gas injection system, extruding and foaming through a die head of the extruder, and then cooling and pelletizing to obtain the magnetic oil-absorbing polyolefin foam material.

The stirring speed of the blender in the step S1 is 100-350 rpm, the stirring time is 10min, and the standing time is 30 min.

In certain embodiments, the weight parts of: in the step S1, 99-99.5 parts of ferroferric oxide and 0.5-1 part of coupling agent are added; in the step S2, 5-15 parts of modified ferroferric oxide and 85-95 parts of polyolefin foaming composition are used.

In certain embodiments, in step S1, the coupling agent comprises any one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, triisostearoylphthalate, and diisostearoylphthalate.

In certain embodiments, in the step S2, the polyolefin foaming composition consists of 98.5 to 99.5% by mass of polyolefin and 0.5 to 1.5% by mass of nucleating agent.

In certain embodiments, the polyolefin comprises any one or more of PP, PE, and POE.

The PP is one or more of HMSPP, copolymerized PP and homopolymerized PP.

In certain embodiments, the nucleating agent comprises any one or more of calcium carbonate, calcium oxide, mica, talc, nanoclay, and kaolin clay.

In certain embodiments, in step S3, the extrusion process of the single screw extruder is: the temperature of the front half area of the extruder is 190-220 ℃, the temperature of the rear half area of the extruder is 140-190 ℃, and the rotating speed of the extruder is 9-55 rpm.

In some embodiments, in the step S3, the gas flow rate of the gas injection system is controlled to be 3-15L/min.

In certain embodiments, in step S3, the supercritical gas is supercritical carbon dioxide or supercritical nitrogen.

The particle size of the ferroferric oxide is less than 300nm, the melt index of polyolefin is 0.5-6 g/10min, and the particle size of a nucleating agent is not more than 0.01 mm.

The invention also provides the magnetic oil-absorbing polyolefin foam material prepared by the method, wherein the magnetic oil-absorbing polyolefin foam material has the aperture ratio of more than 95 percent and the bulk density of 0.03-0.08 g/cm³The particle diameter was 3 mm.

Compared with the existing oil absorption material, the magnetic oil absorption polyolefin foam material and the preparation method thereof provided by the invention have the following beneficial effects:

(1) the magnetic oil absorption polyolefin foam material provided by the invention has good oleophylic hydrophobicity and excellent resilience, can be repeatedly used, and has high oil absorption rate and excellent oil retention performance. The polyolefin foam material is paved on a dynamic water surface, can quickly adsorb oil substances in an oil-water mixture, is not easy to diffuse under the action of an external magnetic field, is convenient to effectively position and collect, and can recycle oil products through centrifugation.

(2) According to the invention, nano-grade ferroferric oxide is adopted, and has a higher specific surface area and a stronger aggregation tendency, so that the coupling agent and hydroxyl on the surface of the ferroferric oxide are subjected to coupling reaction to modify the surface of the ferroferric oxide, the surface energy of ferroferric oxide nano particles is reduced, the interaction between the particles is reduced, the agglomeration of the ferroferric oxide nano particles is avoided, the interface action between the ferroferric oxide and a polymer can be enhanced, and the dispersion effect of the ferroferric oxide in the polymer is improved. And then blending the surface-modified ferroferric oxide with the polyolefin foaming composition for supercritical gas foaming, so that the bonding strength between the ferroferric oxide and the polyolefin foam can be remarkably improved, and the magnetic oil-absorbing polyolefin foam material is ensured to have good magnetism and hydrophobic stability.

(3) In the preparation process of the oil-absorbing foam, the supercritical gas is injected into the compression section of the extruder, so that the environment is not polluted, the nucleation number of microcellular foaming in the polyolefin foam material can be obviously increased, the cell size is reduced, and the oil-absorbing rate and the oil retention performance of the oil-absorbing foam finished product are improved.

Detailed Description

The present invention will be described in further detail with reference to the following detailed description, which should be understood that the following examples are only illustrative of the preferred embodiments of the present invention, show and describe the basic principles, main features and advantages of the present invention, and are only illustrative and explanatory of the present invention, but not restrictive thereof.

Example 1

The preparation method of the magnetic oil-absorbing polyolefin foam material provided by the embodiment comprises the following specific steps:

s1, putting 99 parts of dried ferroferric oxide (the particle size is 200nm) into a blender, adding 1 part of coupling agent KH-550 (gamma-aminopropyltriethoxysilane), mixing and stirring at the stirring speed of 350rpm for 10min at normal temperature, and then standing for 30min to obtain modified ferroferric oxide;

s2, mixing 5 parts of the modified ferroferric oxide and 95 parts of the polyolefin foaming composition uniformly in a blender to obtain a magnetic polyolefin foaming composition, wherein the polyolefin foaming composition consists of 99 parts of homopolymerized PP (with the melt index of 1g/10min) and 1 part of nucleating agent talcum powder (with the particle size of 10 mu m);

s3, adding the magnetic polyolefin foaming composition into a storage bin of a single-screw extruder, setting the temperature of the first half area of the extruder to be 200 ℃, the temperature of the second half area of the extruder to be 150 ℃, the rotating speed of the extruder to be 35rpm, extruding, simultaneously adding supercritical carbon dioxide gas into a compression section of the extruder through a gas injection system, controlling the gas flow to be 5L/min, extruding, foaming through a die head of the extruder, cooling and granulating to obtain the magnetic oil-absorbing polyolefin foam material.

Example 2

The preparation method of the magnetic oil-absorbing polyolefin foam material provided by the embodiment comprises the following specific steps:

s1, putting 99.5 parts of dried ferroferric oxide (the particle size is 30nm) into a blender, adding 0.5 part of coupling agent KH-560 (gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane), mixing and stirring at the stirring speed of 100rpm for 10min at normal temperature, and then standing for 30min to obtain modified ferroferric oxide;

s2, blending 15 parts of the modified ferroferric oxide and 85 parts of the polyolefin foaming composition uniformly in a blender to obtain a magnetic polyolefin foaming composition, wherein the polyolefin foaming composition consists of 75 parts of homopolymerized PP (with the melt index of 3g/10min), 24 parts of HMSPP (with the melt index of 3g/10min) and 1 part of nucleating agent nanoclay (with the particle size of 8 microns);

s3, adding the magnetic polyolefin foaming composition into a storage bin of a single-screw extruder, setting the temperature of the first half area of the extruder to be 220 ℃, the temperature of the second half area of the extruder to be 150 ℃, the rotating speed of the extruder to be 45rpm, extruding, simultaneously adding supercritical carbon dioxide gas into a compression section of the extruder through a gas injection system, controlling the gas flow to be 8L/min, extruding, foaming through a die head of the extruder, cooling and granulating to obtain the magnetic oil-absorbing polyolefin foam material.

Example 3

The preparation method of the magnetic oil-absorbing polyolefin foam material provided by the embodiment comprises the following specific steps:

s1, putting 99 parts of dried ferroferric oxide (the particle size is 100nm) into a blender, adding 1 part of a coupling agent KR-210 (diisostearoyl titanate glycol), mixing and stirring at the normal temperature at the stirring speed of 220rpm for 10min, and then standing for 30min to obtain modified ferroferric oxide;

s2, blending 10 parts of the modified ferroferric oxide and 90 parts of the polyolefin foaming composition uniformly in a blender to obtain the magnetic polyolefin foaming composition, wherein the polyolefin foaming composition consists of 70 parts of homopolymerized PP (with the melt index of 5g/10min), 29.5 parts of POE (with the melt index of 3g/10min) and 0.5 part of nucleating agent calcium carbonate (with the particle size of 5 mu m);

s3, adding the magnetic polyolefin foaming composition into a storage bin of a single-screw extruder, setting the temperature of the first half area of the extruder to be 200 ℃, the temperature of the second half area of the extruder to be 150 ℃, and the rotating speed of the extruder to be 35rpm, extruding, simultaneously adding supercritical carbon dioxide gas into a compression section of the extruder through a gas injection system, controlling the gas flow to be 15L/min, extruding, foaming through a die head of the extruder, cooling and granulating to obtain the magnetic oil-absorbing polyolefin foam material.

Comparative example

Adding 99 parts of homopolymerized PP (with the melt index of 3.6g/10min) and 1 part of nucleating agent talcum powder (with the grain diameter of 10 mu m) into a mixer to be uniformly mixed; and then adding the mixture into a bin of a single-screw extruder, setting the temperature of the first half area of the extruder to be 200 ℃, the temperature of the second half area of the extruder to be 150 ℃, and the rotating speed of the extruder to be 35rpm, extruding, simultaneously adding supercritical carbon dioxide gas into a compression section of the extruder through a gas injection system, controlling the gas flow to be 5L/min, foaming through a die head of the extruder, cooling and granulating to obtain the polyolefin foam material.

After the polyolefin foam materials prepared in the embodiments 1-3 and the comparative example are saturated and adsorb diesel oil, the polyolefin foam materials are placed into extrusion equipment for deoiling, the operations of oil absorption and deoiling are repeated, and the oil absorption rate of the materials after being repeatedly used for 5 times is tested; carrying out an opening rate test according to the standard ISO 4590-2016; the samples were tested for bulk density according to standard GB/T6343-2009; the contact angle of the sample was measured by a contact angle meter.

TABLE 1 Performance test results of polyolefin foams in examples 1-3 and comparative examples

The preparation method has simple process and low manufacturing cost, and can be used for industrial production, and compared with the conventional polyolefin foam material, the prepared magnetic oil absorption polyolefin foam material has good hydrophobic oleophylic property and magnetism, can be moved under the action of a magnetic field, is convenient to recover, can be repeatedly used for many times, and keeps higher oil absorption rate.

Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.