CN107674231B - Hydrophobic and oleophobic polymer composite microsphere and preparation method thereof - Google Patents
Hydrophobic and oleophobic polymer composite microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention provides a hydrophobic and oleophobic composite microsphere and a preparation method thereof. The invention takes fresh wet thermosetting polymer microspheres obtained by a dispersion polymerization method as mother spheres, and obtains the hydrophobic and oleophobic polymer composite microspheres with the interior of thermosetting polymers and the exterior of water-soluble organic silicon tegument by functionally modifying the surface structure of the thermosetting microspheres with water-soluble organic silicon. The invention solves the problems of poor bonding degree and incapability of meeting the practical application when the hydrophilic surface of the thermosetting microsphere needs to be matched with a base material with hydrophobic and oleophobic surface properties, has simple preparation method, is easy to realize industrialization, and can be widely used in the fields of antifouling, photodiffusion, building materials and the like.
Description
Technical Field
The invention belongs to the field of polymer microspheres, and particularly relates to a hydrophobic and oleophobic polymer composite microsphere and a preparation method thereof.
Background
The monodisperse polymer microsphere with the uniform height and the grain diameter of the polymer microsphere of 100 nanometers to tens of micrometers can be used in the fields of coating, paper surface coating, cosmetics and the like, and can be used in the biomedical fields of drug sustained-release microcapsules, protein separation chromatography and the like after being functionalized.
The thermosetting materials such as melamine resin, phenolic resin, urea resin and the like have the advantages of high use temperature, excellent mechanical property, simple and efficient preparation method, high economy and the like, and have good application potential. The thermosetting polymer microsphere is a polycondensation product, is generally prepared in an aqueous solution by a dispersion polymerization method, and has good dispersibility in water and a polar system due to the existence of a polar molecular structure and a surface active group; however, in practical applications, when the hydrophilic surface of these thermosetting microspheres needs to be matched with a substrate having hydrophobic and oleophobic surface properties, the problem of poor bonding degree occurs, and the practical applications cannot be satisfied.
At present, the construction of hydrophobic and oleophobic surfaces is a technical problem, most of the hydrophobic surfaces are not oleophobic, literature reports mainly focus on the preparation of hydrophobic materials, few reports on the hydrophobic and oleophobic modification of the surfaces exist, and no report on the hydrophobic and oleophobic modification of thermosetting polymer microspheres exists. In addition, the surface hydrophobic and oleophobic modification process route related to the literature is generally high in raw material cost, expensive in used equipment, complex in polymerization process, environmentally-friendly in reactants and not beneficial to industrial application.
Disclosure of Invention
Aiming at the problems of the existing thermosetting microspheres, the invention changes the hydrophilic characteristic of the thermosetting polymer microspheres and provides the hydrophobic and oleophobic composite microspheres and the preparation method thereof, so that the surface of the mother sphere is changed from hydrophilic to hydrophobic and oleophobic, the problem of poor bonding degree of the existing thermosetting polymer microspheres when the existing thermosetting polymer microspheres are matched with a base material with hydrophobic and oleophobic surface properties is solved, and the compatibility between the microspheres and the base material is improved. The method has the advantages of simple process, environmental protection, high efficiency, easy industrial production and good application value.
The specific technical scheme of the invention is as follows:
a preparation method of hydrophobic and oleophobic polymer composite microspheres is characterized by comprising the following steps:
(1) weighing wet thermosetting polymer microspheres as mother spheres, adding deionized water, and performing ultrasonic dispersion to obtain a uniformly dispersed microsphere mixture;
(2) preparing an aqueous solution, and adding water-soluble organic silicon to form a modified solvent;
(3) and (3) adding the uniformly dispersed microsphere mixture obtained in the step (1) into the modified solvent prepared in the step (2), magnetically stirring under a water bath condition, settling, separating and drying.
Further, the mother ball in the step (1) is a fresh wet thermosetting polymer microsphere prepared by a dispersion polymerization method in a water system.
Further, the wet thermosetting polymer microspheres in the step (1) are one or a combination of urea-formaldehyde resin, phenol-formaldehyde resin, melamine resin, dicyandiamide-formaldehyde resin and aniline-formaldehyde resin, the solid content of the wet thermosetting polymer microspheres is 35% -75%, the solid content range can effectively avoid microsphere agglomeration, and the hydrophobic and oleophobic modification after the whole microspheres are redispersed is favorably realized.
Further, the adding amount of the deionized water in the step (1) is 4-35 times of the mass of the wet thermosetting polymer microspheres, so that the wet thermosetting polymer microspheres are fully dispersed and are prevented from agglomerating; the ultrasonic dispersion time is 10-60 minutes, so that the weak agglomeration of the microsphere aggregate in the system can be destroyed to completely realize uniform dispersion, the dispersion effect is ensured in the time range, and the re-agglomeration of the microspheres which are completely dispersed and caused by overlong ultrasonic is avoided.
Further, the concentration of the water-soluble organic silicon in the water solution in the step (2) is 5-12%.
Further, the water-soluble organosilicon in the step (2) comprises one or a combination of sodium methyl silicate and potassium methyl silicate. The methyl sodium silicate and the methyl potassium silicate have excellent water solubility, and meanwhile, the hydrolysate thereof has the excellent low surface energy characteristic of organic silicon and has low price and excellent economic performance; different from the conventional organic silicon such as silane, silanol, halogenated silane and the like, the water-soluble organic silicon solution is alkaline, has moderate reaction activity with the hydroxyl, amino and other groups of the thermosetting resin, can be partially hydrolyzed and can also react with the active groups on the surface of the thermosetting microsphere in the modification process, so as to obtain the microsphere product with hydrophobic and oleophobic surface.
Further, the volume of the modified solvent prepared in the step (2) in the step (3) is 2 to 8 times of the volume of the uniformly dispersed microsphere mixture in the step (1).
Further, the temperature of the water bath in the step (3) is 25-55 ℃, and the magnetic stirring time is 15-50 minutes. The surface modification of the system is that the water-soluble organic silicon is partially hydrolyzed and simultaneously reacts with active groups of the microspheres to realize chemical modification, the rate of the chemical reaction is mainly influenced by temperature, the water bath temperature can ensure the reaction speed, and the water-soluble organic silicon is prevented from being hydrolyzed and polymerized to generate non-microsphere impurities.
The invention also provides a hydrophobic and oleophobic polymer composite microsphere which is characterized in that the interior of the composite microsphere is a thermosetting polymer microsphere, and the exterior of the composite microsphere is a water-soluble organic silicon tegument layer.
Furthermore, the thermosetting polymer microspheres are one or a combination of a plurality of urea-formaldehyde resin, phenolic resin, melamine resin, dicyandiamide-formaldehyde resin and aniline-formaldehyde resin, the water-soluble organic silicon is one or a combination of a plurality of sodium methyl silicate and potassium methyl silicate, and the diameter of the hydrophobic and oleophobic polymer composite microspheres is less than 10 microns.
The beneficial effects obtained by the invention are as follows:
the composite microsphere takes a thermosetting microsphere as a mother sphere, silanol (Si-OH) in a water-soluble organic silicon structure reacts with hydroxyl (-OH) on the surface of the microsphere made of materials such as melamine resin, phenolic resin, urea-formaldehyde resin and the like in a water system to generate stronger mutual bond and even cross-linking action to form chemical bonds such as Si-O-C bond and the like, and the surface hydrophobic and oleophobic composite microsphere with the core-shell structure functionalized modification, which takes the thermosetting microsphere as a core and takes an organic silicon polymer as a shell, is prepared. The surface of the mother ball is changed from hydrophilic to hydrophobic and oleophobic, so that the compatibility with other resins is improved, the performance problem of a material prepared by utilizing microspheres due to microsphere agglomeration in the use process is avoided, and meanwhile, the material is ensured to have higher use temperature, so that the mother ball is used in the fields of antifouling, LED photodiffusion, building materials and the like and has important industrial value. The invention provides a hydrophobic and oleophobic polymer composite microsphere with a thermosetting polymer microsphere inside and an organic silicon coating layer outside, belonging to the original invention.
Drawings
FIG. 1 is an optical microscope photograph of the surface hydrophobic and oleophobic polymer composite microsphere prepared in example 1;
FIG. 2 is a photograph showing the water contact angle test result of the surface hydrophobic and oleophobic polymer composite microsphere prepared in example 1;
FIG. 3 is an infrared spectrum of the surface hydrophobic and oleophobic polymer composite microsphere prepared in example 1, wherein 1 is a pure MF microsphere; 2. sodium methyl silicate modified MF; 3. pure silicone.
Detailed Description
Example 1
(1) Weighing 5g of fresh wet melamine resin (MF) thermosetting polymer microspheres (with the solid content of 55%) prepared by a dispersion polymerization method as mother spheres, adding 100mL of water, and performing ultrasonic dispersion for 30 minutes to obtain a microsphere mixture with uniform dispersion.
(2) Preparing 300mL of aqueous solution, wherein 30mL of sodium methylsilicate constitutes a modified solvent;
(3) and (3) adding the uniformly dispersed microsphere mixture obtained in the step (1) into the modified solvent prepared in the step (2), putting into water bath at 45 ℃, simultaneously performing magnetic stirring for 30 minutes, and performing settling separation and drying to obtain the hydrophobic and oleophobic MF polymer composite microsphere on the surface.
Example 2
(1) 5g of fresh wet phenolic resin thermosetting polymer microspheres (solid content is 75%) prepared by dispersion polymerization are weighed as mother spheres, and 150mL of water is added for ultrasonic dispersion for 30 minutes to obtain a dispersed microsphere mixture.
(2) Preparing 500mL of aqueous solution, wherein 60mL of sodium methylsilicate constitutes a modified solvent;
(3) and (3) adding the wet microspheres obtained in the step (1) into the solution prepared in the step (2), adding water with the temperature of 45 ℃, magnetically stirring for 45 minutes, and drying after settling separation to obtain the phenolic aldehyde polymer composite microspheres with hydrophobic and oleophobic surfaces.
Example 3
(1) 5g of fresh wet urea-formaldehyde resin thermosetting polymer microspheres (with the solid content of 35%) prepared by dispersion polymerization are weighed as mother spheres, and 50mL of water is added for ultrasonic dispersion for 20 minutes to obtain a dispersed microsphere mixture.
(2) Preparing 300mL of aqueous solution, wherein 25mL of potassium methyl silicate forms a modified solvent;
(3) and (3) adding the wet microspheres obtained in the step (1) into the solution prepared in the step (2), putting the solution into water with the temperature of 30 ℃, magnetically stirring the solution for 50 minutes, and drying the solution after settling separation to obtain the urea formaldehyde polymer composite microspheres with the hydrophobic and oleophobic surfaces.
Example 4
(1) 5g of fresh wet MF thermosetting polymer microspheres (solid content 45%) prepared by dispersion polymerization are weighed as mother spheres, and 50mL of water is added for ultrasonic dispersion for 50 minutes to obtain a dispersed microsphere mixture.
(2) Preparing 400mL of aqueous solution, wherein 32mL of methyl potassium silicate forms a modified solvent;
(3) and (3) adding the wet microspheres obtained in the step (1) into the solution prepared in the step (2), placing the solution into water with the temperature of 55 ℃, magnetically stirring the solution for 35 minutes, and drying the solution after settling separation to obtain the MF polymer composite microspheres with hydrophobic and oleophobic surfaces.
Example 5
(1) 5g of fresh wet dicyandiamide-formaldehyde resin thermosetting polymer microspheres (solid content is 60%) prepared by dispersion polymerization are weighed as mother spheres, 80mL of water is added for ultrasonic dispersion for 60 minutes, and a dispersed microsphere mixture is obtained.
(2) Preparing 400mL of aqueous solution, wherein 35mL of sodium methyl silicate forms a modified solvent;
(3) and (3) adding the wet microspheres obtained in the step (1) into the solution prepared in the step (2), placing the solution into water with the temperature of 45 ℃, magnetically stirring the solution for 15 minutes, and drying the solution after settling separation to obtain the dicyandiamide-formaldehyde resin polymer composite microspheres with hydrophobic and oleophobic surfaces.
Example 6
(1) 5g of fresh wet aniline-formaldehyde resin thermosetting polymer microspheres (solid content is 75%) prepared by dispersion polymerization are weighed as mother spheres, 175mL of water is added for ultrasonic dispersion for 30 minutes, and a dispersed microsphere mixture is obtained.
(2) Preparing 350mL of aqueous solution, wherein 60mL of sodium methyl silicate forms a modified solvent;
(3) and (3) adding the wet microspheres obtained in the step (1) into the solution prepared in the step (2), adding water with the temperature of 45 ℃, magnetically stirring for 45 minutes, and drying after settling separation to obtain the phenolic aldehyde polymer composite microspheres with hydrophobic and oleophobic surfaces.
Example 7
(1) Weighing 2g of fresh wet thermosetting polymer microsphere urea-formaldehyde resin prepared by dispersion polymerization and 3g of melamine resin (with the solid content of 35%) as mother spheres, and adding 20mL of water for ultrasonic dispersion for 20 minutes to obtain a dispersed microsphere mixture.
(2) Preparing 160mL of aqueous solution, wherein 8mL of potassium methyl silicate forms a modified solvent;
(3) and (3) adding the wet microspheres obtained in the step (1) into the solution prepared in the step (2), putting the solution into water at 25 ℃, magnetically stirring the solution for 50 minutes, and drying the solution after settling separation to obtain the urea formaldehyde polymer composite microspheres with hydrophobic and oleophobic surfaces.
The contact angle tester JY-82C is used for testing the surface tension condition of the product, and the result shows that the contact angle test result of the composite microsphere prepared by the invention and pure water is 100-150 degrees, and compared with the result that the contact angle data cannot be obtained by the super-hydrophilicity of the raw material mother ball, the hydrophobic property of the microsphere is greatly improved.
The analysis result of the FT-IR spectrogram measured by a Fourier transform infrared spectrometer shows that: the carboxyl on the organic silicon and the hydroxyl and imino on the surface of the MF microsphere are subjected to condensation reaction to form a-Si-O-C-covalent bond, and the experimental result of the invention is fully verified to be correct.
The dispersibility of the microspheres is tested by using a two-phase mixed solution of water and toluene (oil), and the result shows that: the organic silicon modified microspheres are positioned at the interface of an oil layer and a water layer, and the surface of the modified composite microspheres is proved to show hydrophobic and oleophobic properties; adding the obtained hydrophobic and oleophobic composite microsphere on the surface into nonpolar base materials such as PS (polystyrene) and the like to prepare an LED photodiffusion material, and observing the dispersion condition of the microsphere to find that: the modified microsphere has greatly improved dispersibility and excellent light diffusion performance.
Claims (6)
1. A preparation method of hydrophobic and oleophobic polymer composite microspheres is characterized by comprising the following steps: step (1): weighing wet thermosetting polymer microspheres as mother spheres, and adding deionized water for ultrasonic dispersion to obtain a uniformly dispersed microsphere mixture; step (2): preparing an aqueous solution, and adding water-soluble organic silicon to form a modified solvent; and (3): adding the microsphere mixture obtained in the step (1) into the modified solvent prepared in the step (2), magnetically stirring under a water bath condition, settling, separating and drying to obtain the hydrophobic and oleophobic macromolecular composite microsphere, wherein the wet thermosetting macromolecular microsphere is a combination of one or more of urea-formaldehyde resin, phenolic resin, melamine resin, dicyandiamide-formaldehyde resin and aniline-formaldehyde resin, the solid content of the wet thermosetting macromolecular microsphere is 35-75%, the water-soluble organic silicon in the step (2) is a combination of one or more of sodium methyl silicate and potassium methyl silicate, and the mother sphere in the step (1) is a fresh wet thermosetting macromolecular microsphere prepared by a dispersion polymerization method in a water system.
2. The method of claim 1, wherein the deionized water is added in an amount of 4-35 times the mass of the wet thermosetting polymer microspheres in step (1), and the ultrasonic dispersion time is 10-60 minutes.
3. The method according to claim 1, wherein the concentration of the water-soluble silicone in the aqueous solution in the step (2) is 5 to 12%.
4. The method of claim 1, wherein the volume of the modified solvent prepared in step (2) in step (3) is 2-8 times the volume of the uniformly dispersed microsphere mixture in step (1).
5. The method according to claim 1 or 4, wherein the temperature of the water bath in the step (3) is 25-55 ℃ and the magnetic stirring time is 15-50 minutes.
6. The hydrophobic and oleophobic polymer composite microsphere is characterized in that a thermosetting polymer microsphere is arranged inside the composite microsphere, a water-soluble organic silicon coating layer is arranged outside the composite microsphere, the thermosetting polymer microsphere is one or a combination of urea-formaldehyde resin, phenolic resin, melamine resin, dicyandiamide-formaldehyde resin and aniline-formaldehyde resin, the water-soluble organic silicon is one or a combination of sodium methyl silicate and potassium methyl silicate, and the diameter of the hydrophobic and oleophobic polymer composite microsphere is less than 10 micrometers.
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| CN115926239B (en) * | 2022-12-23 | 2024-01-26 | 中国工程物理研究院激光聚变研究中心 | Preparation method of polymer hollow microsphere with inner surface free of impurities |
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| CN102604467A (en) * | 2012-01-13 | 2012-07-25 | 中科院广州化学有限公司 | High-dispersion fluorine-containing nanosphere and epoxy resin super-amphiphobic surface |
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Patent Citations (5)
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| JPH0325515B2 (en) * | 1983-01-28 | 1991-04-08 | I Lighting System | |
| CN101864083A (en) * | 2010-05-22 | 2010-10-20 | 大连交通大学 | Preparation method of methyl polysiloxane/SiO2 composite microsphere |
| CN102432781A (en) * | 2011-11-22 | 2012-05-02 | 中科院广州化学有限公司 | Surface fluorine-containing nanosphere capable of crosslinking as well as preparation method and application thereof |
| CN102585243A (en) * | 2012-01-13 | 2012-07-18 | 中科院广州化学有限公司 | Functional fluorine-containing microsphere and self-cleaning surface built by same |
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