CN109096527B - Preparation method of super-hydrophobic polymer open-cell material - Google Patents

Preparation method of super-hydrophobic polymer open-cell material Download PDF

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CN109096527B
CN109096527B CN201810728890.6A CN201810728890A CN109096527B CN 109096527 B CN109096527 B CN 109096527B CN 201810728890 A CN201810728890 A CN 201810728890A CN 109096527 B CN109096527 B CN 109096527B
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polymer
super
hydrophobic
open
polymer solution
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CN109096527A (en
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张振秀
邹立
信支援
温时宝
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Jiangsu Da Mao Niu New Material Co.,Ltd.
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention provides a super-hydrophobic polymer open-cell material and a preparation method thereof, which comprises the steps of dissolving polymer raw materials such as PE, PP, PS, PB, PLA, PPC and the like in a proper organic solvent to form a polymer solution, adding the polymer solution or the polymer solution added with reinforcing materials such as sponge, non-woven fabric, cotton cloth and the like into the polymer solution, and carrying out thermally induced phase separation and supercritical drying to obtain the super-hydrophobic and high open-cell polymer material.

Description

Preparation method of super-hydrophobic polymer open-cell material
Technical Field
The invention belongs to the field of high molecular materials, and particularly relates to a simple formula for preparing a super-hydrophobic polymer open-cell material and a preparation method thereof.
Technical Field
A superhydrophobic/superoleophilic material is a special material with a contact angle between a drop of water and its surface higher than 150 deg., and a contact angle of a drop of oil and its surface close to 0 deg.. The super-hydrophobic/super-oleophylic material is characterized in that: the surface of the material has lower surface energy chemical components; the surface of the material has a certain roughness. When the super-hydrophobic/super-oleophilic material is prepared, a rough structure is constructed on the surface of the super-hydrophobic/super-oleophilic material to increase the roughness of the surface, or a substance with low surface energy is used for modifying the surface of the super-hydrophobic/super-oleophilic material. The specific operation methods include the following two methods: (1) firstly, constructing some rough structures on the surface of the material to increase the roughness of the surface of the material, and then modifying the surface of the material by using a substance with low surface energy; (2) firstly, the material surface is modified by using a substance with low surface energy, and then a rough structure is constructed on the surface of the substance with low surface energy, so that the material obtains super-hydrophobic/super-oleophilic performance. The super-hydrophobic open-cell material can realize the separation of oil-water mixture due to the continuous structure of high open cells inside and special surface chemical properties. Compared with the traditional separation material and separation method, the oil-water separation by utilizing the super-hydrophobic characteristic of the material has the advantages of simple preparation process, stable property, convenient operation, good separation effect, high separation efficiency and the like, and the special super-hydrophobic characteristic and the function of oil-water selectivity can be applied to a plurality of fields, such as self-cleaning materials, waterproof coatings and the like.
Aiming at potential application of the super-hydrophobic open-pore material, a process method for preparing the super-hydrophobic open-pore material by using a polymer as a matrix material and a simple thermally induced phase separation method is developed. The super-hydrophobic polymer open-cell material is prepared by dissolving the polymer in a proper solvent and then separating out the polymer in a self-assembly mode in the cooling process through a thermal phase separation method, the preparation method is simple, and the super-hydrophobic polymer open-cell material has wide potential application in the fields of oil-water separation and self-cleaning.
Disclosure of Invention
The invention aims to provide a super-hydrophobic polymer open-cell material and a preparation method thereof, aiming at the defects of the existing super-hydrophobic material preparation method. The invention takes PE, PP, PS, PB, PLA, PPC and the like as raw materials, then the raw materials are dissolved in organic solvents such as proper dimethylbenzene, methylbenzene, acetone, normal hexane, dichloromethane or gasoline, and then the polymer material with super hydrophobicity and high open pore is obtained after thermally induced phase separation or thermally induced phase separation and drying after adding reinforcing materials such as sponge, non-woven fabric, cotton cloth and the like.
In order to achieve the above object, the present invention provides a superhydrophobic polymer open-cell material and a preparation method thereof. The formula is as follows: the concentration of polymer/solvent is 0.01-1 g/ml; wherein the polymer is one or more of PE, PP, PS, PB, PLA and PPC, the solvent is one or more of dimethylbenzene, methylbenzene, acetone, normal hexane, dichloromethane and gasoline, and the preparation method comprises the following specific steps:
(1) preparation of polymer solution: a proper amount of polymer and solvent are put in a closed container, the polymer is dissolved in the solvent under the condition of mechanical stirring at the temperature of 50-180 ℃, the rotating speed of the mechanical stirring is 40-500rpm, and the dissolving time is 2-24h, so that a uniform polymer solution is formed.
(2) And (3) forming the super-hydrophobic polymer: and pouring the polymer solution into a mold, and naturally cooling the polymer solution to room temperature to form gel, or adding the reinforcing material into the polymer solution, and naturally cooling the polymer solution to room temperature to form gel.
(3) Supercritical drying to prepare polymer aerogel: putting the formed polymer gel into a supercritical reaction kettle, and introducing CO2And (3) leading the pressure to reach 7-20Mpa, leading the temperature of the reaction kettle to be 40-70 ℃, then carrying out saturation for 0.5-4h, slowly releasing the pressure, leading the pressure to return to zero after 2-10h, then cooling, and taking out the material after the temperature is reduced to room temperature to obtain the super-hydrophobic polymer aerogel.
Compared with the prior art, the invention has the following excellent effects:
1. the polymer open-cell material has excellent chemical resistance, high porosity and excellent super-hydrophobic property;
2. the polymer open-cell material prepared by the formula and the process has the characteristics of light weight, high strength, no toxicity, environmental protection, no pollution and the like;
3. compared with the existing super-hydrophobic product, the material has the advantages of simple preparation process, low cost, continuous high-opening structure and the like, has the function of oil-water separation, has high flux and can be recycled.
Drawings
FIG. 1 SEM of PP aerogel surface of example 1;
FIG. 2 scanning electron micrograph of PE aerogel @ sponge surface of example 2;
figure 3 oil absorption effect of PE aerogel @ sponge of example 2.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, but the scope of the present invention is not limited by these examples.
Example 1
PP 12g and xylene 100 ml.
Setting the temperature of an oil bath kettle to be 150 ℃, setting the rotating speed of a mechanical stirring rotor to be 300rpm, adding PP and dimethylbenzene into a round-bottom flask according to the proportion, and mechanically stirring for 3 hours under a closed condition to obtain a uniform PP solution. Mixing the solutionPouring into a mould, and naturally cooling to room temperature under a closed condition to form PP gel. Putting PP gel into a supercritical reaction kettle, setting the temperature at 60 ℃, and introducing CO2The pressure is led to reach 7.5Mpa, supercritical drying is carried out for 3h, then pressure is slowly released, the pressure returns to zero after 4h, the temperature is reduced to room temperature, and the super-hydrophobic PP porous material is obtained after being taken out, wherein the density of the super-hydrophobic PP porous material is 0.178g/cm3The porosity reaches 93 percent, the contact angle of the surface can reach 157 degrees, the scanning electron microscope photo is shown in figure 1, and the open-pore material can absorb a plurality of organic solvents such as normal hexane, xylene, silicone oil, gasoline and the like and has good reusability.
Example 2
PE 10g, xylene 100ml, sponge 3 x 3 cm.
Setting the temperature of an oil bath pot to be 130 ℃, setting the rotating speed of a mechanical stirring rotor to be 300rpm, adding PE and dimethylbenzene into a round-bottom flask according to the proportion, and mechanically stirring for 3 hours under a closed condition to obtain a uniform PE solution. And pouring the solution into a mold containing sponge, and naturally cooling to room temperature under a closed condition to form PE @ sponge gel. The PE gel compounded with the sponge is taken out and then put into a supercritical reaction kettle, the temperature is set to be 60 ℃, the pressure is 7Mpa, supercritical drying is carried out for 12h, the PE @ sponge open-cell material with super hydrophobicity/super oil absorption is obtained after the PE gel is taken out, a scanning electron microscope image of the PE @ sponge open-cell material is shown in figure 2, the oil absorption capacity of the composite material is greatly increased, n-hexane (oil red O dyeing) with the weight 5 times of the self weight can be rapidly absorbed within 3s, and the absorption process is shown in figure 3.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention, and all technical solutions obtained by using equivalent substitutions or equivalent transformations fall within the protection scope of the present invention.

Claims (3)

1. A preparation method of a super-hydrophobic polymer open-cell material is characterized by comprising the following preparation steps: (1) taking a polymer as a raw material, wherein the polymer raw material is PE, PP, PS, PB, PLA and PPC, then putting the polymer into an organic solvent, wherein the organic solvent is dimethylbenzene or methylbenzene, the amount of the polymer/solvent is 0.01-1g/mL, heating, stirring, dissolving, wherein the dissolving temperature is 100-180 ℃, and stirring for 1-6 hours to obtain a polymer solution; (2) stopping heating the polymer solution, slowly cooling to form polymer wet gel, or putting the base material into the polymer solution and cooling together to form composite material wet gel of the polymer and the base material; (3) placing the wet gel in a supercritical high-pressure kettle, pressurizing to 7-20Mpa, then heating to 40-80 ℃, after saturation for 0.5-4h, slowly reducing to normal pressure under the condition of heat preservation, then slowly reducing to room temperature, and opening the kettle to obtain the polymer aerogel material, wherein the aerogel material is used as an oil-water separation material and a super-hydrophobic fabric.
2. The method as claimed in claim 1, wherein the base material in the step (2) is sponge, non-woven fabric or cotton cloth.
3. The method for preparing a superhydrophobic polymeric open cell material according to claim 1, wherein the time for depressurizing in step (3) is 2-10 h.
CN201810728890.6A 2018-07-04 2018-07-04 Preparation method of super-hydrophobic polymer open-cell material Active CN109096527B (en)

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CN110158316B (en) * 2019-05-29 2021-02-26 南京大学 Modified polylactic acid non-woven fabric for oil-water separation and preparation method and application thereof
CN114504955B (en) * 2022-03-10 2023-02-28 北京师范大学 Method for preparing polymer porous membrane by low-temperature thermally induced phase separation and product thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030073158A1 (en) * 2001-10-17 2003-04-17 Ma Peter X. Degradable porous materials with high surface areas
CN102886155A (en) * 2012-09-20 2013-01-23 北京航空航天大学 Bionic construction of metal-foam-based oil-water separation material
CN103464003A (en) * 2013-09-24 2013-12-25 清华大学 Method for preparing polypropylene hollow-fiber porous membranes
US9034934B1 (en) * 2011-05-31 2015-05-19 Yosry A. Attia Polythylene aerogels and method of their production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030073158A1 (en) * 2001-10-17 2003-04-17 Ma Peter X. Degradable porous materials with high surface areas
US9034934B1 (en) * 2011-05-31 2015-05-19 Yosry A. Attia Polythylene aerogels and method of their production
CN102886155A (en) * 2012-09-20 2013-01-23 北京航空航天大学 Bionic construction of metal-foam-based oil-water separation material
CN103464003A (en) * 2013-09-24 2013-12-25 清华大学 Method for preparing polypropylene hollow-fiber porous membranes

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