CN108641049B - Preparation method of fluorine-free monomer water-based super-hydrophobic material - Google Patents
Preparation method of fluorine-free monomer water-based super-hydrophobic material Download PDFInfo
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Abstract
The invention relates to a preparation method of a fluorine-free monomer water-based super-hydrophobic material. The method comprises the following steps: 1) surface modification of silicon dioxide; 2) surface grafting reaction of modified silicon dioxide: adding water, modified silicon dioxide and sodium bicarbonate (NaHCO) into a reactor3) And ultrasonically dispersing an emulsifier for 30min, dropwise adding a monomer into a reaction system under the protection of argon, emulsifying for 30min, heating the system to 80 ℃, dropwise adding an initiator solution into the reaction system, mechanically stirring, reacting for 16-24 h, and stopping the reaction to obtain the water-based super-hydrophobic materials with different grafting amounts. The invention can be coated on the surfaces of various common materials, the preparation method is simple, and the obtained super-hydrophobic surface has excellent stability, so the water-based super-hydrophobic material prepared by the invention has good application prospect in many fields.
Description
Technical Field
The technical scheme of the invention relates to the field of organic, inorganic and high polymer materials, in particular to a preparation method of a fluorine-free monomer water-based super-hydrophobic material.
Background
As early as the 20 th century, people find that the micron-scale rough structure on the surface of the lotus leaf is the key of the lotus leaf to have hydrophobicity and self-cleaning function. The 2002 Jianglian research group [ L.Jiang, et al. adv.Mater.,2002,14,1857 ] found that nanostructures were present on the papillae of the microstructure on the lotus leaf surface, and the hierarchical structure of the microstructure and the nanostructure combined is considered to be the root cause of the strong hydrophobicity of the surface. The report by this research group, published in Nature 2004, revealed the secret that a water strider can fly on the water surface [ l.jiang, et al. Nature,2004,432,36 ]. When the contact angle of the surface of the material to water is more than 150 degrees and the rolling angle is less than 10 degrees, the material is called to have super-hydrophobicity. The super-hydrophobic coating with special wetting property has important application in the aspects of anti-icing, anti-corrosion [ Q.Liu, et al.J.electro.chem.Soc.,2016,163:213 ], self-cleaning and oil-water separation [ Y.Chen, et al.appl.Surf.Sci.,2015,335:107 ]. Therefore, the preparation of superhydrophobic materials has received increasing attention in recent years.
Surfaces with superhydrophobic effects generally have two conditions: one is that the surface has certain roughness, namely the micro-nano structure; the other is to modify the low surface energy material on the rough surface. The common methods are as follows: etching, sol-gel, templating, and the like. For example, Huang et al use NaOH solution to etch the surface of aluminum alloy to construct a scaly micro-nano structure, and after the surface is modified with low surface energy substance, the contact angle to water reaches 156 ° [ y.Huang, et al.appl.surf.soc.,2015,356:1012.](ii) a Lee et al used sol-gel method to form SiO with nano-protrusions on the surface of Si-Al alloy2Thin film, and modifying SiO with low surface substances2A superhydrophobic surface was obtained [ j.w.lee, et al.mater.lett.,2016,168:83.](ii) a Zhang et al prepared superhydrophobic paper with contact angle up to 160 ° using soot as template [ j.h.zhang, et al.rsc adv.,2016,6:12862.]. The super-hydrophobic coating which can be prepared in a large scale and at low cost and is convenient to use and has friction resistance is the main development direction of the current super-hydrophobic materials.
Polymer/inorganic composite materials have been widely substituted for conventional materials in various fields due to their unique properties. Among them, the preparation of silica/polymer composites and their application in the field of superhydrophobicity have been the focus of research. However, the currently prepared super-hydrophobic material mainly utilizes an organic solvent such as methanol, ethanol or ethyl acetate to dissolve a Low Surface Energy Material (LSEM), and once the organic solvent is produced in an enlarged manner, huge environmental problems are caused; and the low surface energy materials used at present are mainly fluorine-containing monomers, so that the cost is high. Secondly, the particles of these materials in the prior art only have physical interaction, and the binding force between the particles is poor, so that the nanoparticles are easy to fall off, resulting in poor adhesion of the materials. At present, the binding force among particles is increased mainly by adding a binding agent, but the method has some defects that the addition is too little and the binding force among particles is not increased enough; too much addition can cause phase separation and cover the micro-nano structure on the surface of the material, so that the super-hydrophobic effect cannot be achieved.
Disclosure of Invention
Aiming at the defects of poor durability, difficulty in proper amount preparation of an adhesive and nano particles, high cost, environmental pollution and the like in the prior art, the invention provides a preparation method of a fluorine-free monomer water-based super-hydrophobic material. The invention uses fluorine-containing emulsifier and fluorine-free monomer to carry out emulsion polymerization. The fluorine-containing emulsifier used in the invention can coat the surface of the material to form low surface energy, generate super-hydrophobic effect, avoid high cost caused by using fluorine-containing monomer, and more importantly, homopolymer microspheres and SiO can be generated in the process2The @ polymer forms a hierarchical structure, and a superhydrophobic surface is better constructed.
The technical scheme of the invention is as follows:
a preparation method of a fluorine-free monomer water-based super-hydrophobic material comprises the following steps:
1) the surface modification of the silicon dioxide (the particle size is 10-100 nm) can be carried out by the following method:
dispersing silicon dioxide in ethanol, ultrasonically dispersing for 30min, adding the silicon dioxide into a reactor, adding ammonia water, a silane coupling agent and water, mechanically stirring and reacting for 48h at room temperature, washing a product with ethanol for multiple times after the reaction is finished, centrifugally precipitating, and drying in vacuum to obtain silicon dioxide with double bonds on the surface;
wherein the mass ratio of the materials is silicon dioxide: ethanol: ammonia water: water: silane coupling agent ═ 1 to 100: 1-1000: 1-100: 1-100: 1-100; the mass fraction of the ammonia water is 25-28%;
the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, vinyl tri (b-methoxyethoxy) silane or vinyl triethoxysilane;
2) the surface grafting reaction of the modified silica can be carried out by the following method:
adding water, modified silicon dioxide and sodium bicarbonate (NaHCO) into a reactor3) And ultrasonically dispersing an emulsifier for 30min, dropwise adding a monomer into a reaction system under the protection of argon, emulsifying for 30min, heating the system to 80 ℃, dropwise adding an initiator solution into the reaction system, mechanically stirring, reacting for 16-24 h, and stopping the reaction to obtain the water-based super-hydrophobic materials with different grafting amounts.
The material ratio is modified silicon dioxide by mass ratio: water: monomer (b): emulsifier: initiator solution 0.1-10: 1-100: 1-10: 0.01-1: 1-10; adding 0.10-0.24 g of sodium bicarbonate (NaHCO) into 100mL of water3) (ii) a 0.01-0.30 g of initiator is dissolved in 10mL of water in the initiator solution;
wherein the emulsifier is perfluorobutanesulfonyl fluoride, perfluoroalkyl ether acrylate, potassium perfluorooctyl sulfonate or the perfluoroalkyl initiator is potassium persulfate, ammonium persulfate, cumene hydroperoxide or cumene hydroperoxide; the monomer is one or more of styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate and glycerol methacrylate.
The application of the fluorine-free monomer water-based super-hydrophobic material comprises the following steps:
preparing the aqueous super-hydrophobic material into dispersion liquid with required concentration, spraying the dispersion liquid on the surface of a base material, and drying at the temperature of 135-145 ℃ to form a super-hydrophobic coating;
the mass ratio of the materials is that the water-based super-hydrophobic material: water 1: 10-1000 parts; spraying 25-35 g of the dispersion liquid per square meter of the surface of the substrate.
The substrate material is wood, metal, cement, fabric, plastic or glass.
The invention has the substantive characteristics that:
the super-hydrophobic material prepared at present mainly utilizes an added adhesive to increase the bonding force among particles, the addition amount of the adhesive is difficult to control, the addition amount is too small to achieve the effect, and the addition amount is too large to generate phase separation to influence the hydrophobic effect of the material. In addition, the low surface energy fluorine-containing monomer is mainly used for preparing the super-hydrophobic material at present, the fluorine-containing monomer is more in dosage and expensive in price, and the Low Surface Energy Material (LSEM) is dissolved by using an organic solvent such as methanol, ethanol or ethyl acetate, so that once the organic solvent is produced in an enlarged mode, a huge environmental problem is caused. According to the invention, the fluorine-containing emulsifier and the fluorine-free monomer are utilized to graft the surface of the silicon dioxide particles, the long polymer chains are grafted, the polymer chains begin to move by utilizing the hydrophobic polymer above the glass transition temperature, the chains can be intertwined with each other, and the microspheres of the material are more tightly combined with the microspheres, so that the nano particles are not easy to fall off, the wear resistance of the material is increased, and the defects caused by the use of an adhesive are avoided. And emulsion polymerization is adopted, water is used as a dispersing agent, organic solvent is avoided, the environment is protected, the safety is realized, and the process is simple. And the fluorine-containing emulsifier is less in dosage relative to the fluorine-containing monomer, so that the cost can be greatly saved.
The invention has the beneficial effects that:
(1) the invention can be coated on the surfaces of various common materials, the preparation method of the coating is simple, and the obtained super-hydrophobic surface has excellent stability, so that the water-based super-hydrophobic material prepared by the invention has good application prospect in many fields.
(2) The waterborne super-hydrophobic material has strong applicability, can be coated on the surfaces of wood, metal, internal and external walls of buildings, fabrics, plastics and glass, and has super waterproof and antifouling effects.
(3) The invention uses the fluorine-containing emulsifier and the fluorine-free monomer to prepare the water-based super-hydrophobic material by adopting an emulsion polymerization method, avoids the high cost caused by the fluorine-containing monomer used for preparing the general super-hydrophobic material, greatly reduces the cost and has simple process.
(4) In the using process of the super-hydrophobic material, the dendritic structure greatly contributes to the stability of the coating, the surface of the microsphere is provided with a plurality of long polymer chains, and when the material is above the glass transition temperature, the polymer chains are in a motion state and intertwined with each other, so that the microsphere and the microsphere are combined more tightly, the adhesive force of the super-hydrophobic material is increased, and the problem caused by uneven addition of an adhesive is avoided. The static contact angle of the coating obtained by the invention is more than 150 degrees, and the rolling angle is less than 5 degrees, so that the super-hydrophobic effect is achieved.
(5) The preparation method of the water-based super-hydrophobic material accords with the Cassie-Baxter model recognized at present, the preparation operation of the water-based super-hydrophobic material is simple, the cost is low, expensive equipment and severe process conditions are not needed, complex operation and complex equipment are not needed, the super-hydrophobic material has excellent and stable super-hydrophobic performance, the adhesion of the obtained super-hydrophobic material is good, and the industrial development application prospect is good.
Description of the drawings:
FIG. 1: a preparation flow chart of the aqueous super-hydrophobic material;
FIG. 2: an electron micrograph of the silica of example 1, wherein the upper right inset is a static contact angle test photograph of the coating;
FIG. 3: an electron microscope photo of the modified silica in example 1, wherein the insert at the upper right corner is a static contact angle test photo of the coating, and the maximum static contact angle reaches 66.8 degrees;
FIG. 4: the grafting amount in example 1 is an electron micrograph of the grafted silica, wherein the insert at the upper right corner is a static contact angle test photograph of the coating, and the maximum static contact angle reaches 164.2 degrees;
FIG. 5: an electron microscope photo of the material in example 1 after being heated at 140 degrees is taken, wherein an inset on the upper right is a static contact angle test photo of the coating, and the maximum static contact angle reaches 158.3 degrees;
Detailed Description
The present invention will be further described with reference to the following embodiments and the accompanying drawings;
the silica (particle size of 10 to 100nm) of the present invention is a known product, and can be prepared by a commercially available or known method by one of ordinary skill in the art.
The preparation process is shown in figure 1, firstly, a silane coupling agent is used for modifying the surface of silicon dioxide (the particle size is 10-100 nm) to form silicon dioxide with double bonds on the surface, then, a hydrophobic polymer long chain is grafted on the surface by an emulsion polymerization method, and the dendritic aqueous super-hydrophobic material is prepared.
Example 1:
preparation of the material with a grafting amount of 80%
(1) Modification of silica (particle size of 10 to 100nm)
Dispersing 2g of silicon dioxide in 200ml of ethanol, performing ultrasonic dispersion for 30min, adding 10ml of double distilled water, 2ml of ammonia water (the mass fraction is 25-28%) and 6g of gamma-methacryloxypropyltrimethoxysilane, controlling the stirring speed at 300r/min, reacting for 48h at room temperature, stopping the reaction, washing the product with ethanol for 3 times, and performing vacuum drying to obtain the surface-modified silicon dioxide.
FIG. 2 is an electron scanning electron microscope scanning silica with a FEI Nano SEM 450 electron, and FIG. 3 is an electron microscope image of modified silica. It can be seen from fig. 2 and 3 that the silica before and after modification has no obvious change in morphology, the hydrophobic silane coupling agent is on the modified silica, the change in contact angle data is obvious, and the change from 17.7 ° to 66.8 ° proves the successful occurrence of modification.
(2) Surface grafting reaction of modified silicon dioxide by adopting emulsion polymerization method
Dried 0.4g of modified silica was dispersed in 100ml of double distilled water, and 0.24g of sodium hydrogencarbonate (NaHCO) was added in this order3) 0.04g of perfluoroalkyl ether acrylate, ultrasonically dispersing for 30min, adding the mixture into a reactor, heating the mixture to 80 ℃ in an oil bath, introducing argon, mechanically stirring, adding 2g of methyl methacrylate into a reaction system, emulsifying for 30min, dissolving 0.04g of potassium persulfate in 10mL of water, dropwise adding the dissolved potassium persulfate into the previous reactor after complete dissolution, stirring for 1h, reacting at the constant temperature of 80 ℃ for 16h at the rotation speed of 250r/min, standing the obtained emulsion, and obtaining the aqueous superhydrophobic material with the grafting weight of 80% by using TGA (thermogravimetric analysis);
FIG. 4 is an electron microscope image of the silicon dioxide after being grafted by FEI Nano SEM 450 electron scanning electron microscope, the contact angle is 164.2 degrees, FIG. 5 is an electron microscope image of the material after being heated at 140 ℃, the contact angle is 158.2 degrees, and it can be seen from FIGS. 4 and 5 that the shape of the material after being heated at 140 ℃ is not loose as before being processed, and the materials are more compact. The reason is mainly that when the hydrophobic polymer is heated to a temperature higher than the glass transition temperature, polymer chains start to move, the chains can be mutually entangled, and the microspheres of the material are more tightly bonded. The material is added into water to prepare 2% dispersion liquid, 25g of dispersion liquid is sprayed on the surface of a matrix per square meter, the material is sprayed on Chunzi fabric, after the material is dried at 140 ℃, an abrasion resistance test is carried out on the material by using an abrasion tester, an abrasion resistance curve is tested under the pressure of 250g, the contact angle is still more than 150 degrees after 600 circles, and the super-hydrophobic effect is kept.
Example 2:
preparation of a 60% graft Material
(1) Modification of silica (particle size of 10 to 100nm) in the same manner as in the first step (1)
(2) Emulsion polymerization for surface grafting reaction of modified silicon dioxide
Dried 0.8g of modified silica was dispersed in 100ml of double distilled water, and 0.24g of sodium hydrogencarbonate (NaHCO) was added in this order3) 0.04g of perfluoroalkyl ether acrylate, ultrasonically dispersing for 30min, adding into a reactor, heating to 80 ℃ in an oil bath, introducing argon, mechanically stirring, adding 2g of methyl methacrylate into the reaction system at a stirring speed of 250r/min, emulsifying for 30min, dissolving 0.04g of potassium persulfate into 10ml of water, dropwise adding into the reaction system after completely dissolving, finishing dropping within 1h, reacting at the constant temperature of 80 ℃ for 16h, and standing the obtained emulsion to obtain the water-based super-hydrophobic material with the grafting amount of 60%; the material is added into water to prepare a dispersion liquid with the mass ratio of 2%, 25g of the dispersion liquid is sprayed on the surface of a matrix per square meter, the material is sprayed on Chunzi fabric, after the material is dried at 140 ℃, an abrasion resistance test is carried out on the material by using an abrasion tester, an abrasion resistance curve is tested under the pressure of 250g, the contact angle is still larger than 150 degrees after 800 circles, and the super-hydrophobic effect is kept.
Example 3:
preparation of a Material with a grafting amount of 40%
(1) Modification of silica (particle size of 10 to 100nm) in the same manner as in the first step (1)
(2) Emulsion polymerization for surface grafting reaction of modified silicon dioxide
1.2g of dried modified silica was dispersed in 100ml of double distilled water, and 0.24g of sodium hydrogencarbonate (NaHCO) was added in this order3) 0.02g of perfluoroalkyl ether acrylate, ultrasonic dispersion for 30min, adding into a reactor, heating to 80 ℃ in an oil bath, introducing argon, mechanically stirring, then 2g of methyl methacrylate and emulsion are added into the reaction system for 30min, 0.04g of potassium persulfate is dissolved in 10mL of water, after complete dissolution, the mixture is dripped into the reactor for 1 hour, the stirring speed is 250r/min, the constant temperature reaction is carried out for 16 hours at 80 ℃, the obtained emulsion is kept stand, the water-based super-hydrophobic material with the grafting amount of 40 percent is obtained, the material is added into water to prepare the dispersion liquid with the mass of 2 percent, spraying 25g of the dispersion liquid per square meter of the surface of the substrate, spraying the material on a Chunyan fabric, after being dried at 140 ℃, the coating is subjected to wear resistance test by using a wear meter, and under the pressure of 250g, the wear resistance curve is tested, the contact angle is still more than 150 degrees after 700 circles, and the super-hydrophobic effect is kept.
Example 4:
preparation of the Material with a grafting amount of 20%
(1) Modification of silica (particle size of 10 to 100nm) in the same manner as in the first step (1)
(2) Emulsion polymerization for surface grafting reaction of modified silicon dioxide
Dried 1.6g of modified silica was dispersed in 100ml of double distilled water, and 0.24g of sodium hydrogencarbonate (NaHCO) was added in this order3) 0.02g of perfluoroalkyl ether acrylate, ultrasonically dispersing for 30min, adding the mixture into a reactor, heating the mixture to 80 ℃ in an oil bath, introducing argon, mechanically stirring, adding 2g of methyl methacrylate into a reaction system, dissolving 0.04g of potassium persulfate into 10mL of water for 30min, dropwise adding the dissolved potassium persulfate into the previous reactor after complete dissolution, stirring at the rotation speed of 250r/min, reacting at the constant temperature of 80 ℃ for 16h, and standing the obtained emulsion to obtain the aqueous superhydrophobic material with the grafting amount of 20%; adding the material into water to prepare 2% dispersion, spraying 25g dispersion per square meter of substrate surface, spraying the material on Chunzi cloth, and oven drying at 140 deg.CAnd then, an abrasion resistance test is carried out on the product by using an abrasion tester, under the pressure of 250g, the abrasion resistance curve is tested, the contact angle is still more than 150 degrees after 600 circles, and the super-hydrophobic effect is kept.
Example 5:
preparation of a Material with a grafting amount of 10%
(1) Modification of silica (particle size of 10 to 100nm) in the same manner as in the first step (1)
(2) Emulsion polymerization for surface grafting reaction of modified silicon dioxide
Dried 1.8g of modified silica was dispersed in 100ml of double distilled water, and 0.24g of sodium hydrogencarbonate, (NaHCO) was added in this order3) 0.02g of perfluoroalkyl ether acrylate, ultrasonically dispersing for 30min, adding the mixture into a reactor, heating the mixture in a water bath to 80 ℃, introducing argon, mechanically stirring, adding 2g of methyl methacrylate into a reaction system, emulsifying for 30min, dissolving 0.04g of potassium persulfate in 10mL of water, dropwise adding the dissolved potassium persulfate into the previous reactor after complete dissolution, stirring at the rotation speed of 250r/min, reacting at the constant temperature of 80 ℃ for 24h, and standing the obtained emulsion to obtain the aqueous superhydrophobic material with the grafting amount of 10%; the material is added into water to prepare a dispersion liquid with the mass of 2%, 25g of the dispersion liquid is sprayed on the surface of a substrate per square meter, the material is sprayed on Chunzi fabric, after the material is dried at 140 ℃, a wear resistance test is carried out on the material by using a wear meter, the wear resistance curve is tested under the pressure of 250g, the contact angle is still more than 150 degrees after 500 circles, and the super-hydrophobic effect is kept.
The prepared water-based super-hydrophobic material utilizes the hydrophobic polymer to start moving at the temperature above the glass transition temperature, chains can be intertwined with each other, and microspheres of the material are more tightly combined with the microspheres, so that nano particles are not easy to fall off, the wear resistance of the material is improved, and the defects caused by using an adhesive are avoided; the invention adopts emulsion polymerization method to synthesize, avoids using organic solvent, has little pollution to environment and simple preparation process; in addition, the invention adopts the fluorine-containing emulsifier and the fluorine-free monomer to carry out emulsion polymerization, thereby avoiding the defect of high cost caused by the high expense of the fluorine-containing monomer. (the superhydrophobic material is a surface effect, and after emulsion polymerizationThe emulsifier can be coated on the surface of the microsphere, the fluorine-containing emulsifier used in the invention can be coated on the surface of the material to form low surface energy, so that a super-hydrophobic effect is generated, the high cost caused by using fluorine-containing monomers is avoided, and more importantly, homopolymer microspheres and SiO can be generated in the process2The @ polymer forms a hierarchical structure, and a superhydrophobic surface is better constructed. )
The invention is not the best known technology.
Claims (4)
1. A preparation method of a fluorine-free monomer water-based super-hydrophobic material is characterized by comprising the following steps:
1) the surface modification of the silicon dioxide with the particle size of 10-100 nm adopts the following method:
dispersing silicon dioxide in ethanol, ultrasonically dispersing for 30min, adding the silicon dioxide into a reactor, adding ammonia water, a silane coupling agent and water, mechanically stirring and reacting for 48h at room temperature, washing a product with ethanol for multiple times after the reaction is finished, centrifugally precipitating, and drying in vacuum to obtain silicon dioxide with double bonds on the surface;
wherein the mass ratio of the materials is, silicon dioxide: ethanol: ammonia water: water: silane coupling agent = 1-100: 1-1000: 1-100: 1-100: 1-100;
the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, vinyl tri (beta-methoxyethoxy) silane or vinyl triethoxysilane;
2) the surface grafting reaction of the modified silicon dioxide adopts the following method:
adding water, modified silicon dioxide and sodium bicarbonate (NaHCO) into a reactor3) Dispersing an emulsifier by ultrasonic for 30min, dropwise adding a monomer into a reaction system under the protection of argon, emulsifying for 30min, heating the system to 80 ℃, dropwise adding an initiator solution into the reaction system, mechanically stirring, reacting for 16-24 h, and stopping the reaction to obtain the water-based super-hydrophobic materials with different grafting amounts;
the material mass ratio is that modified silicon dioxide: water: monomer (b): emulsifier: initiator solution = 0.1-10: 1-100:1-10: 0.01-1: 1-10; adding 0.10-0.24 g of sodium bicarbonate (NaHCO) into 100mL of water3) (ii) a 0.03-0.10 g of initiator is dissolved in 10mL of water in the initiator solution;
wherein the emulsifier is perfluoropolyether acrylate; the initiator is potassium persulfate, ammonium persulfate or cumene hydroperoxide; the monomer is one or more of styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate and glycerol methacrylate.
2. The method for preparing the fluorine-free monomer aqueous super-hydrophobic material according to claim 1, wherein the mass fraction of the ammonia water is 25 to 28%.
3. The use of the fluorine-free monomeric aqueous superhydrophobic material prepared by the method of claim 1, comprising the steps of:
preparing the aqueous super-hydrophobic material into dispersion liquid with required concentration, spraying the dispersion liquid on the surface of a base material, and drying at 135-145 ℃ to form a super-hydrophobic coating;
the mass ratio of the materials is that the water-based super-hydrophobic material: water = 1: 10-1000 parts; spraying 25-35 g of the dispersion liquid per square meter of the surface of the substrate.
4. Use according to claim 3, wherein the substrate material is wood, metal, cement, fabric, plastic or glass.
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| CN110951296A (en) * | 2019-11-28 | 2020-04-03 | 江西洪屏抽水蓄能有限公司 | Fluorine-free super-hydrophobic coating on metal surface and preparation method thereof |
| WO2021202269A1 (en) * | 2020-04-03 | 2021-10-07 | Sabic Global Technologies, B.V. | Dense modified silica with silane compounds and methods of making and using same |
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