WO2018049965A1 - Method for quickly preparing aerogel by using microemulsion as precursor - Google Patents

Method for quickly preparing aerogel by using microemulsion as precursor Download PDF

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WO2018049965A1
WO2018049965A1 PCT/CN2017/098237 CN2017098237W WO2018049965A1 WO 2018049965 A1 WO2018049965 A1 WO 2018049965A1 CN 2017098237 W CN2017098237 W CN 2017098237W WO 2018049965 A1 WO2018049965 A1 WO 2018049965A1
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microemulsion
aerogel
silicate
sodium
fiber
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PCT/CN2017/098237
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French (fr)
Chinese (zh)
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周水林
姜法兴
林芬
熊风
赵科仁
姚献东
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周水林
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Priority to DE112017001567.7T priority Critical patent/DE112017001567T5/en
Publication of WO2018049965A1 publication Critical patent/WO2018049965A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/155—Preparation of hydroorganogels or organogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C01B33/166—Preparation of silica xerogels by acidification of silicate in the presence of an inert organic phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/064—Silica aerogel
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/42—Glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors

Definitions

  • the invention relates to a method for preparing an aerogel and a composite material thereof by using a microemulsion as a precursor, in particular to a rapid preparation of a hydrophobic aerogel and a composite material thereof, which comprises surface hydrophobicization modification in a microemulsion system. method.
  • Silica aerogel is a new type of lightweight porous material composed of nano-sized particles and a mixture of air and dispersion medium.
  • the hole rate is as high as 80-99%, and the typical size of the hole is 1-100 nm. It has the advantages of low thermal conductivity, low acoustic impedance, low refractive index and strong adsorption performance in chemical, thermal, optical, acoustic and electrical fields. It has unique characteristics and has broad application prospects in the general rudder fields of aerospace, military, telecommunications, medical, materials, electronics, metallurgy, and chemical industry.
  • silica aerogel As “a magical material that can change the world.” Because of its enormous application potential, researchers around the world have invested in the development of a variety of silica aerogel preparation methods. Based on the existing patents and literatures, the current silica aerogel production methods are mainly divided into two types: dry pressure drying and supercritical drying. From the types of silicon sources, they are mainly classified into inorganic silicon sources and organic materials. There are two major categories of silicon-like sources; from the surface modification methods, they are mainly divided into two categories: pre-drying modification and post-drying modification. The usual preparation process mainly includes 1. hydrolysis of silicon source, 2. hydrophobization of sol, 3. sol-gel process (composite other materials), 4. gel aging, 5.
  • a typical silicone silicon source preparation process uses ethyl orthosilicate or methyl orthosilicate (and corresponding polymer) as a silicon source, and ethanol or a mixture of ethanol and water as a solvent, acid is added for hydrolysis, and alkali is added.
  • the hydrolyzate is accelerated to a gel, aging is enhanced, and the liquid in the gel is repeatedly replaced with an organic solvent, and then passed through a reactive silane such as trimethylchlorosilane or hexamethyldisilazane or hexamethyldisiloxane.
  • a reactive silane such as trimethylchlorosilane or hexamethyldisilazane or hexamethyldisiloxane.
  • the reagent is subjected to surface hydrophobic treatment of the gel, and then dried by supercritical or normal pressure to obtain a hydrophobized silica aerogel.
  • the raw materials used in such methods are generally expensive and toxic, the process is complicated, the amount of organic solvent is large, and the safety is low, which restricts the large-scale production and application of the process.
  • a typical inorganic silicon source preparation silica aerogel process uses water glass as a silicon source. With the help of ion exchange resin, an acidic silica sol is obtained. A base is added to make the silica sol polycondensed into a gel, and then the gel is removed by washing with water.
  • the electrolyte removes the electrolyte by washing several times; then the hydrogel is repeatedly replaced with an organic solvent to reduce the water content in the gel to a certain value, and passes through trimethylchlorosilane, six
  • a reactive silane reagent such as methyldisilazane or hexamethyldisiloxane is surface-hydrophobized and then subjected to supercritical or atmospheric pressure. Drying gives a hydrophobized silica aerogel.
  • WO 96/22942 (CN1181053A), WO97/17288 (CN1087271C), WO97/48642 (CN1105679C), WO98/23367 (CN1101725C), EP-A-0658513, CN1636871B, CN1241953B, CN101844771A.
  • a typical post-modification method usually based on the above sol-gel-aging-displacement, eliminates the surface modification process of the silane-based modification liquid, and after supercritical drying, is fumigated by a silylation reagent. In a manner, the surface of the aerogel is hydrophobized.
  • the method usually leaves the smell of the heavier silane reagent or its decomposition product.
  • a typical pre-modification method consists of two methods: one is to surface-modify by silanization reagent after gel formation, usually the organic reagent is used in a larger amount and longer time; the other is self-hydrophobic gel process, usually In the preparation process of the sol, a silylating agent such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane or the like is added, and these are under the action of an acidic or basic catalyst.
  • the silylation reagent is hydrolyzed, and the hydrolyzate containing the hydrophobic group interacts with the sol particles produced by the hydrolysis-polycondensation of other silicon sources.
  • hydrophobic group is coupled to the surface of the particle, and then polycondensed into a gel by a basic catalyst, and then The drying process results in a hydrophobic silica aerogel.
  • This kind of method avoids the large-scale use of organic reagents, but before the gel occurs, the surface of the sol particles is coated with a large number of hydrophobic groups, which tends to cause mutual repulsion between the particles, and the gelation process is hindered even if various alkaline catalysts are added.
  • the gelation process is also greatly prolonged than in the absence of hydrophobic groups.
  • the gel time takes more than 4 hours; the gel strength formed is relatively weak, requiring long-term aging or aging, and the patent CN100372765C is required. Aging 24h.
  • Some inventors have tried to avoid pre- or post-modification and solvent replacement processes by adding surfactants, such as the patent CN103204666A, CN103496707A, to obtain a hydrophilic or poorly hydrophobic dry gel with a higher density. , porosity and specific surface area are low.
  • surfactants such as the patent CN103204666A, CN103496707A
  • the preparation of silica aerogels from organic silicon sources is relatively expensive, the amount of organic solvents is large, and the safety is low; inorganic silicon sources are concerned because of low prices, but there are still problems such as cumbersome operation and long production cycle.
  • the self-hydrophobic gel process can shorten the production cycle and avoid the use of a large amount of organic reagents, but the current cost of the raw materials is high, which restricts the application of the process.
  • Patent CN104003406A discloses a method for preparing aerogel powder, which is characterized in that a microemulsion prepared by using a silicon source solution, an oil phase, a surfactant and a co-surfactant is used to prepare a wet gel, which is washed and washed by Chen Hua. , solvent replacement, surface modification treatment, drying at room temperature and normal temperature to obtain hydrophobic silica aerogel powder.
  • the method differs from the above process for preparing an aerogel from an inorganic silicon source in that a microemulsion method is used to prepare a wet gel, and the subsequent process is still a conventional cumbersome treatment method, and the amount of the organic solvent in the washing and replacing process is large, plus the surface. Modified treatment, the whole process is longer. Based on this, the present invention has been proposed.
  • the present invention provides a method for rapidly preparing an aerogel using a microemulsion as a precursor, which is realized by a microemulsion method using a water-soluble inorganic silicon source as a main raw material.
  • the self-hydrophobicization process effectively avoids the inadequacies of the previous self-hydrophobic process, shortens the entire production cycle, avoids complicated replacement and surface modification processes, and obtains a hydrophobic silica aerogel material with good high temperature resistance.
  • a method for rapidly preparing an aerogel using a microemulsion as a precursor comprising the steps of:
  • microemulsion mixing a quantitative water-soluble silicon source with water, adding a certain amount of surfactant and co-surfactant; slowly adding one or more organosilicon compounds and assisting under high-speed stirring by a stirrer Oil phase until a translucent homogeneous microemulsion is obtained;
  • the microemulsion obtained in the step (1) is accelerated over a certain period of time and/or an appropriate amount of an acidic or basic catalyst is added;
  • step (3) aging enhancement process: the gel material formed in step (2) is aged for a certain period of time and/or under heating conditions;
  • the water-soluble silicon source in the step (1) is water glass, an acidic silica sol whose solvent is water, an alkaline silica sol whose solvent is water, lithium methyl silicate, sodium methyl silicate, potassium methyl silicate One or more of lithium silicate, lithium metasilicate, sodium silicate, sodium metasilicate, potassium silicate or potassium metasilicate;
  • the surfactant in the step (1) is sodium dioctyl sulfonate sulfonate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, fatty alcohol polyoxyethylene.
  • the co-surfactant in the step (1) is one of acetone, methyl butanone, methyl isobutyl ketone, ethyl acetate, methanol, ethanol, ethylene glycol, n-propanol or isopropanol or Multiple
  • the organosilicon compound in the step (1) is hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, monomethyldiethoxyhydrosilane, methyl Triethoxysilane, methyltrimethoxysilane, polymethyltriethoxysilane, polymethyltrimethoxysilane, methylhydroxysilicone oil, hydroxyhydrogen silicone oil, methyltrifluoropropyl silicone oil or methyl One or more of vinyl silicone oils;
  • the auxiliary oil phase in the step (1) is one or more of n-hexane, cyclohexane, n-pentane or liquid paraffin.
  • the acidic catalyst in the step (2) is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid or oxalic acid.
  • One or more of the basic catalysts in the step (2) are one or more of ammonia water, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate or potassium carbonate.
  • the microemulsion obtained in the step (1) is added with an appropriate amount of inorganic additives, and after being uniformly mixed, the microemulsion is sprayed or integrally immersed and the fiber is used. The material is compounded, and the microemulsion is transformed into a gel to form a whole with the fiber.
  • the fiber material is one or more of glass fiber, aluminum silicate fiber, mullite fiber, basalt fiber, polyester fiber, polyacrylonitrile fiber, carbon fiber or viscose fiber; Titanium dioxide, iron oxide, ferrous oxide, aluminum oxide, magnesium oxide, zinc oxide, aluminum silicate, magnesium silicate, calcium silicate, zinc silicate, zinc borate, magnesium hydroxide, aluminum hydroxide or iron hydroxide One or more.
  • the aging time in the step (3) is 10 min to 10 h, and the aging temperature is 10 to 75 ° C.
  • a certain amount of an organic solvent is added, and the organic solvent is one or more of methanol, ethanol or acetone.
  • the drying temperature is 50-200 ° C
  • the drying temperature is 30-65 ° C
  • the drying temperature is 220 -250 ° C.
  • the invention has the following advantages: 1.
  • the water-soluble silicon source is the main silicon source, the cost is low, and the production prospect is large; 2.
  • the microemulsion method is used to prepare the precursor, and the hydrophobicization process is completed. It can also form a gel faster, which reduces the influence of the hydrophobizing agent on the gel process;
  • the operation process is simple and fast, avoiding the extensive use of organic reagents, shortening the entire manufacturing process;
  • the method is novel and unique, fully blending the respective characteristics of the microemulsion method and the sol-gel method, breaking the previous gel preparation
  • the single mode of the sol-gel process provides a new idea for the production of hydrophobic silica aerogels;
  • the microemulsion of the method has good wettability and permeability, and has good compatibility with various inorganic additives and fiber materials, and the obtained aerogel material has high mechanical strength and good high temperature resistance.
  • FIG. 1 is a three-dimensional structural view in which an aqueous phase containing an inorganic silicon source and an oil phase containing an organosilicon compound are interdigitated at a microscopic level;
  • Figure 2 is a diagram showing the microstructure of an aerogel produced in the present invention.
  • the gel is prevented from being volatilized by solvent evaporation by adding an effective seal and adding a small amount of ethanol.
  • the gel was dried in a blast oven at 150 ° C for 2 h to obtain a hydrophobic silica aerogel block having a density of about 110 mg/cm 3 , and a microscopic structure such as a scanning electron microscope photograph is shown in FIG. 2 .
  • an inorganic additive-fiber composite gel material was formed; the gel material was aged in ethanol at 60 ° C for 5 h, and the volume of ethanol was 5 times the volume of the gel material; after the aging was completed, the gel material was Put it into the supercritical carbon dioxide extraction kettle, set the pressure to 12Mpa, the temperature is 50 °C, dry for 6h, then keep warm and reduce the pressure, and finally get the hydrophobic, reinforced fiber composite silica aerogel material, the inorganic additive is more evenly dispersed, 25
  • the thermal conductivity of °C is 0.0186W/m*K
  • the thermal conductivity at an average temperature of 500°C is 0.059W/m*K
  • the shrinkage at 24°C is less than 2% at 800°C, which has excellent high-temperature performance.
  • the invention provides a method for preparing a hydrophobic aerogel and a composite material thereof with a microemulsion as a precursor, a low cost and a rapid preparation.
  • Microemulsion is a uniformly transparent, thermodynamically stable dispersion of two mutually incompatible liquids formed spontaneously by surfactants and co-surfactants.
  • the two incompatible continuums are separated into small spaces by surfactant amphiphiles to form a microreactor, the size of which can be controlled in the nanometer range, and the reactants react in the system to form solid phase particles.
  • the microemulsion can precisely control the particle size and stability of the nanomaterial, the process of nucleation, growth, coalescence, agglomeration and the like of the nanoparticles is limited, and the formed nanoparticles are coated with a layer of surfactant, and have certain Condensed structure.
  • the invention forms a uniform and stable microemulsion system by adding a surfactant and a co-surfactant, supplemented by high-speed stirring, a water-soluble silicon source aqueous solution, a water-insoluble organosilicon compound and an auxiliary oil phase, and contains an inorganic silicon source.
  • a surfactant and a co-surfactant supplemented by high-speed stirring
  • a water-soluble silicon source aqueous solution e.g., a water-insoluble organosilicon compound
  • an auxiliary oil phase e.g., a water-soluble silicon source aqueous solution
  • a water-insoluble organosilicon compound e.g., a water-insoluble organosilicon compound
  • an auxiliary oil phase e.g., auxiliary oil phase
  • the surfactant and the co-surfactant form a dynamic boundary between the two phases, after a certain period of time or
  • the inorganic silicon source in the microemulsion system is gradually reduced to a three-dimensional skeleton, and at the same time, the hydroxyl group obtained by hydrolysis or the existing hydroxyl group is condensed with the hydroxyl group on the surface of the skeleton, silicone The compound is coated on the surface of the skeleton. It is also possible to immerse the bulky fibrous felt matrix before the microemulsion loses fluidity and to form a mutually reinforcing composite with the fiber mat.
  • the condensate obtained by the above or the composite material thereof is further aging-enhanced, and a hydrophobic aerogel and a composite material thereof can be obtained after drying under normal pressure; and the water in the pores of the condensate can be replaced by an organic solvent while aging is enhanced. Then, supercritical drying is carried out to obtain a hydrophobic aerogel and a composite thereof.
  • the invention has novel preparation process, low raw material cost and wide application range, and can be used for both normal pressure drying method and supercritical drying process, and the obtained material has excellent thermal insulation performance, high structural strength and small shrinkage rate in long-term use.

Abstract

A method for quickly preparing an aerogel by using a microemulsion as a precursor, comprising: 1. measuring off a specific water-soluble silicon source to prepare a quantitative aqueous solution, adding a specific amount of surfactant and co-surfactant, and fully dissolving; 2. measuring off a specific active organic silicon compound and an auxiliary oil phase, adding into the aqueous solution, and stirring at a high speed for a period to form a semi-transparent, uniform, and stable mixed solution, namely, a microemulsion; and 3. compounding the microemulsion with an inorganic additive and a fiber mat, to form a solidified phase after a period, and carrying out aging and ambient pressure drying or supercritical drying to obtain an aerogel material compounded with fiber mat. The method is novel in preparation process, low in raw material costs, and wide in application range. An ambient pressure drying approach can be used, and a supercritical drying process can also be used. The obtained material has an excellent thermal insulation performance, a high structural strength, and a low shrinkage rate after long-term use.

Description

一种以微乳液为前体快速制备气凝胶的方法Method for rapidly preparing aerogel with microemulsion as precursor 技术领域Technical field
本发明涉及一种以微乳液为前体制备气凝胶及其复合材料的方法，尤其是一种涉及在微乳液体系内完成表面疏水化改性的快速制备疏水气凝胶及其复合材料的方法。The invention relates to a method for preparing an aerogel and a composite material thereof by using a microemulsion as a precursor, in particular to a rapid preparation of a hydrophobic aerogel and a composite material thereof, which comprises surface hydrophobicization modification in a microemulsion system. method.
背景技术Background technique
二氧化硅气凝胶是一种由纳米级微粒相互聚集而成，以空气为分散介质的新型轻质多孔材料。其孔洞率高达80-99％，孔洞的典型尺寸为1-100纳米，具有导热系数低、声阻抗低、折射率低和吸附性能强等优点，在化学、热学、光学、声学、电学等方面表现出独特性质，在航空航天、军工、通讯、医疗、材料、电子、冶金、化工等总舵领域有着广阔的应用前景。2007年英国《***》盛赞二氧化硅气凝胶是“能够改变世界的神奇材料”。正是由于其具有巨大的应用潜力，世界各地的研究者们纷纷投入精力开发了各种各样的二氧化硅气凝胶制备方法。综合已有的专利及文献，目前二氧化硅气凝胶生产方法从干燥方式上主要分为常压干燥和超临界干燥两类；从硅源种类上分，主要分为无机类硅源和有机类硅源两大类；从表面改性方式上主要分为干燥前改性和干燥后改性两大类。通常的制备流程主要包含1.硅源水解、2.溶胶疏水化、3.溶胶-凝胶过程(复合其他材料)、4.凝胶老化、5.凝胶中溶剂置换、6.凝胶表面修饰(疏水化处理)、7.干燥过程(超临界或常压干燥)、8.气凝胶表面修饰(疏水化处理)。以上过程的某些步骤在不同的工艺中可以不是必须的步骤，也有一些制备工艺需要增加更多的中间步骤。典型的有机硅硅源制备工艺采用正硅酸乙酯或正硅酸甲酯(及相应的聚合物)为硅源，以乙醇或乙醇和水的混合液为溶剂，加入酸进行水解，加入碱使水解液加速凝胶，经老化增强，并以有机溶剂多次置换凝胶内的液体，然后通过三甲基氯硅烷或六甲基二硅氮烷、六甲基二硅氧烷等活性硅烷试剂对凝胶进行表面疏水化处理，然后经超临界或常压干燥得到疏水化的二氧化硅气凝胶。此类方法所用原料通常较昂贵，且具有毒性，工艺复杂、有机溶剂用量大、安全性较低，制约了该工艺的规模化生产和应用。如专利CN101671030B，CN101264891B、US5830387、CN100384726C、CN100400153C。典型的无机硅源制备二氧化硅气凝胶工艺采用水玻璃为硅源，在离子交换树脂的帮助下，得到酸性硅溶胶，加入碱使硅溶胶缩聚成凝胶，然后使用水洗涤凝胶去除电解质，或者在形成凝胶后通过多次水洗，去除电解质；然后用有机溶剂对水凝胶进行多次置换，使凝胶内的水含量降低到一定值，并通过三甲基氯硅烷、六甲基二硅氮烷、六甲基二硅氧烷等活性硅烷试剂对凝胶进行表面疏水化处理，然后经超临界或常压 干燥得到疏水化的二氧化硅气凝胶。如专利WO96/22942(CN1181053A)、WO97/17288(CN1087271C)、WO97/48642(CN1105679C)、WO98/23367(CN1101725C)、EP-A-0658513、CN1636871B、CN1241953B、CN101844771A。此类方法操作繁琐、生产周期长，且制备工艺中会产生大量含盐废水。典型的后改性方法，通常是在上述溶胶-凝胶-老化-置换的基础上，省却了硅烷类改性液的表面修饰过程，而在超临界干燥后，通过用硅烷化试剂气态熏蒸的方式，对气凝胶表面进行疏水化处理。如专利：CN1317188C、US6005012，US5738801等，该方法通常会残留较重的硅烷试剂或其分解产物的气味。Silica aerogel is a new type of lightweight porous material composed of nano-sized particles and a mixture of air and dispersion medium. The hole rate is as high as 80-99%, and the typical size of the hole is 1-100 nm. It has the advantages of low thermal conductivity, low acoustic impedance, low refractive index and strong adsorption performance in chemical, thermal, optical, acoustic and electrical fields. It has unique characteristics and has broad application prospects in the general rudder fields of aerospace, military, telecommunications, medical, materials, electronics, metallurgy, and chemical industry. In 2007, the British "Times" praised silica aerogel as "a magical material that can change the world." Because of its enormous application potential, researchers around the world have invested in the development of a variety of silica aerogel preparation methods. Based on the existing patents and literatures, the current silica aerogel production methods are mainly divided into two types: dry pressure drying and supercritical drying. From the types of silicon sources, they are mainly classified into inorganic silicon sources and organic materials. There are two major categories of silicon-like sources; from the surface modification methods, they are mainly divided into two categories: pre-drying modification and post-drying modification. The usual preparation process mainly includes 1. hydrolysis of silicon source, 2. hydrophobization of sol, 3. sol-gel process (composite other materials), 4. gel aging, 5. solvent replacement in gel, 6. gel surface Modification (hydrophobic treatment), 7. Drying process (supercritical or atmospheric drying), 8. Aerogel surface modification (hydrophobic treatment). Some of the steps of the above process may not be necessary steps in different processes, and some preparation processes require more intermediate steps. A typical silicone silicon source preparation process uses ethyl orthosilicate or methyl orthosilicate (and corresponding polymer) as a silicon source, and ethanol or a mixture of ethanol and water as a solvent, acid is added for hydrolysis, and alkali is added. The hydrolyzate is accelerated to a gel, aging is enhanced, and the liquid in the gel is repeatedly replaced with an organic solvent, and then passed through a reactive silane such as trimethylchlorosilane or hexamethyldisilazane or hexamethyldisiloxane. The reagent is subjected to surface hydrophobic treatment of the gel, and then dried by supercritical or normal pressure to obtain a hydrophobized silica aerogel. The raw materials used in such methods are generally expensive and toxic, the process is complicated, the amount of organic solvent is large, and the safety is low, which restricts the large-scale production and application of the process. Such as the patent CN101671030B, CN101264891B, US5830387, CN100384726C, CN100400153C. A typical inorganic silicon source preparation silica aerogel process uses water glass as a silicon source. With the help of ion exchange resin, an acidic silica sol is obtained. A base is added to make the silica sol polycondensed into a gel, and then the gel is removed by washing with water. The electrolyte, or after washing the gel, removes the electrolyte by washing several times; then the hydrogel is repeatedly replaced with an organic solvent to reduce the water content in the gel to a certain value, and passes through trimethylchlorosilane, six A reactive silane reagent such as methyldisilazane or hexamethyldisiloxane is surface-hydrophobized and then subjected to supercritical or atmospheric pressure. Drying gives a hydrophobized silica aerogel. For example, WO 96/22942 (CN1181053A), WO97/17288 (CN1087271C), WO97/48642 (CN1105679C), WO98/23367 (CN1101725C), EP-A-0658513, CN1636871B, CN1241953B, CN101844771A. Such methods are cumbersome to operate, have a long production cycle, and produce a large amount of salty wastewater in the preparation process. A typical post-modification method, usually based on the above sol-gel-aging-displacement, eliminates the surface modification process of the silane-based modification liquid, and after supercritical drying, is fumigated by a silylation reagent. In a manner, the surface of the aerogel is hydrophobized. Such as the patent: CN1317188C, US6005012, US5738801, etc., the method usually leaves the smell of the heavier silane reagent or its decomposition product.
典型的前改性方法，包含两种方式：一是在凝胶形成后通过硅烷化试剂浸泡进行表面修饰，通常有机试剂用量较大，时间较长；另一种即自疏水凝胶工艺，通常是在溶胶的配制过程中，加入硅烷化试剂，如甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲基二乙氧基硅烷等，在酸性或碱性催化剂的作用下，这些硅烷化试剂发生水解，含有疏水基团的水解产物与其他硅源水解-缩聚产生的溶胶粒子相互作用，疏水基团联接到粒子表面，再经碱性催化剂作用下，缩聚成凝胶，然后经干燥过程得到疏水的二氧化硅气凝胶。如专利：CN100372765C、CN100398492C、CN101372337B、WO2005/110919(CN1984843A)、CN101450852A、CN101439958A、CN101973752A、US8663739B2。该类方法避免了有机试剂的大量使用，但在凝胶发生前，溶胶粒子表面大量包裹有疏水基团，往往容易造成粒子间相互排斥，凝胶过程受阻，即使添加各种碱性催化剂，凝胶过程也会比没有疏水基团的情况大大延长，如在专利CN100372765C中，凝胶时间需要4小时以上；形成的凝胶强度相对较弱，需要长时间的陈化或老化，专利CN100372765C中需陈化24h。也有一些发明人试图以添加表面活性剂的方式，避免前改性或后改性及溶剂置换过程，如专利CN103204666A，CN103496707A，得到的是亲水的或者是疏水性差的干凝胶，密度较高，孔隙率和比表面积较低。综上，以有机硅源制备二氧化硅气凝胶成本较高，有机溶剂用量大、安全性较低；无机硅源因价格低廉受到关注，但仍存在操作繁琐、生产周期长等问题。自疏水凝胶工艺可以缩短生产周期并避免大量有机试剂的使用，但目前其原料的成本较高，制约了该工艺的应用。专利CN104003406A公布了一种制备气凝胶粉体的方法，其特征在于：采用硅源溶液、油相、表面活性剂和助表面活性剂制备的微乳液来制备湿凝胶，经陈华、洗涤、溶剂替换、表面改性处理，常压常温干燥后得到疏水性二氧化硅气凝胶粉体。该方法与前述无机硅源制备气凝胶的过程不同之处在于采用微乳液法来制备湿凝胶，后续过程仍是传统的繁琐处理方法，洗涤和替换过程中有机溶剂用量大，加上表面改性处理，整个过程较长。有基于此，提出本发明。 A typical pre-modification method consists of two methods: one is to surface-modify by silanization reagent after gel formation, usually the organic reagent is used in a larger amount and longer time; the other is self-hydrophobic gel process, usually In the preparation process of the sol, a silylating agent such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane or the like is added, and these are under the action of an acidic or basic catalyst. The silylation reagent is hydrolyzed, and the hydrolyzate containing the hydrophobic group interacts with the sol particles produced by the hydrolysis-polycondensation of other silicon sources. The hydrophobic group is coupled to the surface of the particle, and then polycondensed into a gel by a basic catalyst, and then The drying process results in a hydrophobic silica aerogel. Such as patents: CN100372765C, CN100398492C, CN101372337B, WO2005/110919 (CN1984843A), CN101450852A, CN101439958A, CN101973752A, US8663739B2. This kind of method avoids the large-scale use of organic reagents, but before the gel occurs, the surface of the sol particles is coated with a large number of hydrophobic groups, which tends to cause mutual repulsion between the particles, and the gelation process is hindered even if various alkaline catalysts are added. The gelation process is also greatly prolonged than in the absence of hydrophobic groups. For example, in the patent CN100372765C, the gel time takes more than 4 hours; the gel strength formed is relatively weak, requiring long-term aging or aging, and the patent CN100372765C is required. Aging 24h. Some inventors have tried to avoid pre- or post-modification and solvent replacement processes by adding surfactants, such as the patent CN103204666A, CN103496707A, to obtain a hydrophilic or poorly hydrophobic dry gel with a higher density. , porosity and specific surface area are low. In summary, the preparation of silica aerogels from organic silicon sources is relatively expensive, the amount of organic solvents is large, and the safety is low; inorganic silicon sources are concerned because of low prices, but there are still problems such as cumbersome operation and long production cycle. The self-hydrophobic gel process can shorten the production cycle and avoid the use of a large amount of organic reagents, but the current cost of the raw materials is high, which restricts the application of the process. Patent CN104003406A discloses a method for preparing aerogel powder, which is characterized in that a microemulsion prepared by using a silicon source solution, an oil phase, a surfactant and a co-surfactant is used to prepare a wet gel, which is washed and washed by Chen Hua. , solvent replacement, surface modification treatment, drying at room temperature and normal temperature to obtain hydrophobic silica aerogel powder. The method differs from the above process for preparing an aerogel from an inorganic silicon source in that a microemulsion method is used to prepare a wet gel, and the subsequent process is still a conventional cumbersome treatment method, and the amount of the organic solvent in the washing and replacing process is large, plus the surface. Modified treatment, the whole process is longer. Based on this, the present invention has been proposed.
发明内容Summary of the invention
针对现有技术中以上工艺的各自特点和不足，本发明提供了一种以微乳液为前体快速制备气凝胶的方法，该方法以水溶性无机硅源为主要原料，以微乳液法实现其自疏水化过程，有效避免了此前自疏水工艺的不足之处，缩短了整个生产周期，避免了繁杂置换、表面改性过程，得到了耐高温性能良好的疏水二氧化硅气凝胶材料。In view of the respective characteristics and deficiencies of the above processes in the prior art, the present invention provides a method for rapidly preparing an aerogel using a microemulsion as a precursor, which is realized by a microemulsion method using a water-soluble inorganic silicon source as a main raw material. The self-hydrophobicization process effectively avoids the inadequacies of the previous self-hydrophobic process, shortens the entire production cycle, avoids complicated replacement and surface modification processes, and obtains a hydrophobic silica aerogel material with good high temperature resistance.
为达到上述目的，本发明是通过以下技术方案实现的：In order to achieve the above object, the present invention is achieved by the following technical solutions:
一种以微乳液为前体快速制备气凝胶的方法，其特征在于包括以下步骤：A method for rapidly preparing an aerogel using a microemulsion as a precursor, comprising the steps of:
(1)微乳液的配制：将定量的水溶性硅源与水混合，加入定量的表面活性剂及助表面活性剂；在搅拌器高速搅拌下，缓慢加入一种或多种有机硅化合物及辅助油相，直至得到半透明均匀的微乳液；(1) Preparation of microemulsion: mixing a quantitative water-soluble silicon source with water, adding a certain amount of surfactant and co-surfactant; slowly adding one or more organosilicon compounds and assisting under high-speed stirring by a stirrer Oil phase until a translucent homogeneous microemulsion is obtained;
(2)凝胶的制备：将步骤(1)得到的微乳液，通过一定时间，并/或添加适量的酸性或碱性催化剂加速凝胶；(2) Preparation of the gel: the microemulsion obtained in the step (1) is accelerated over a certain period of time and/or an appropriate amount of an acidic or basic catalyst is added;
(3)老化增强过程：将步骤(2)形成的凝胶材料，在一定时间内，并/或在加热条件下进行老化；(3) aging enhancement process: the gel material formed in step (2) is aged for a certain period of time and/or under heating conditions;
(4)超临界或常压干燥：将步骤(3)所得到的凝胶进行超临界或常压干燥，获得疏水的二氧化硅气凝胶。(4) Supercritical or atmospheric drying: The gel obtained in the step (3) is subjected to supercritical or normal pressure drying to obtain a hydrophobic silica aerogel.
所述步骤(1)中的水溶性硅源为水玻璃、溶剂为水的酸性硅溶胶、溶剂为水的碱性硅溶胶、甲基硅酸锂、甲基硅酸钠、甲基硅酸钾、硅酸锂、偏硅酸锂、硅酸钠、偏硅酸钠、硅酸钾或偏硅酸钾中的一种或多种；The water-soluble silicon source in the step (1) is water glass, an acidic silica sol whose solvent is water, an alkaline silica sol whose solvent is water, lithium methyl silicate, sodium methyl silicate, potassium methyl silicate One or more of lithium silicate, lithium metasilicate, sodium silicate, sodium metasilicate, potassium silicate or potassium metasilicate;
所述步骤(1)中的表面活性剂为琥珀酸二辛酯磺酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠、吐温60、吐温80、司盘20或聚乙二醇单油酸酯中的一种或多种；The surfactant in the step (1) is sodium dioctyl sulfonate sulfonate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, fatty alcohol polyoxyethylene. One or more of sodium ether sulfate, Tween 60, Tween 80, Span 20 or polyethylene glycol monooleate;
所述步骤(1)中的助表面活性剂为丙酮、甲基丁酮、甲基异丁酮、乙酸乙酯、甲醇、乙醇、乙二醇、正丙醇或异丙醇中的一种或多种；The co-surfactant in the step (1) is one of acetone, methyl butanone, methyl isobutyl ketone, ethyl acetate, methanol, ethanol, ethylene glycol, n-propanol or isopropanol or Multiple
所述步骤(1)中的有机硅化合物为六甲基二硅氧烷、六甲基二硅氮烷、二甲基二乙氧基硅烷、一甲基二乙氧基一氢硅烷、甲基三乙氧基硅烷、甲基三甲氧基硅烷、聚甲基三乙氧基硅烷、聚甲基三甲氧基硅烷、甲基羟基硅油、羟基含氢硅油、甲基三氟丙基硅油或甲基乙烯基硅油中的一种或多种；The organosilicon compound in the step (1) is hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, monomethyldiethoxyhydrosilane, methyl Triethoxysilane, methyltrimethoxysilane, polymethyltriethoxysilane, polymethyltrimethoxysilane, methylhydroxysilicone oil, hydroxyhydrogen silicone oil, methyltrifluoropropyl silicone oil or methyl One or more of vinyl silicone oils;
所述步骤(1)中的辅助油相为正己烷、环己烷、正戊烷或液体石蜡中的一种或多种。The auxiliary oil phase in the step (1) is one or more of n-hexane, cyclohexane, n-pentane or liquid paraffin.
所述步骤(2)中的酸性催化剂为盐酸、硫酸、硝酸、磷酸、草酸、醋酸或乙二酸中 的一种或多种；所述步骤(2)中的碱性催化剂为氨水、氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂、碳酸钠或碳酸钾中的一种或多种。The acidic catalyst in the step (2) is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid or oxalic acid. One or more of the basic catalysts in the step (2) are one or more of ammonia water, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate or potassium carbonate.
所述步骤(2)中在添加酸性或碱性催化剂之前，将步骤(1)得到的微乳液，加入适量的无机添加剂，混合均匀后，将微乳液通过喷淋渗透或整体浸没的方式与纤维材料复合，微乳液转变为凝胶后与纤维形成一个整体。In the step (2), before adding the acidic or basic catalyst, the microemulsion obtained in the step (1) is added with an appropriate amount of inorganic additives, and after being uniformly mixed, the microemulsion is sprayed or integrally immersed and the fiber is used. The material is compounded, and the microemulsion is transformed into a gel to form a whole with the fiber.
所述的纤维材料为玻璃纤维、硅酸铝纤维、莫来石纤维、玄武岩纤维、聚酯纤维、聚丙烯腈纤维、碳纤维或黏胶纤维中的一种或多种；所述的无机添加剂为二氧化钛、氧化铁、氧化亚铁、氧化铝、氧化镁、氧化锌、硅酸铝、硅酸镁、硅酸钙、硅酸锌、硼酸锌、氢氧化镁、氢氧化铝或氢氧化铁中的一种或多种。The fiber material is one or more of glass fiber, aluminum silicate fiber, mullite fiber, basalt fiber, polyester fiber, polyacrylonitrile fiber, carbon fiber or viscose fiber; Titanium dioxide, iron oxide, ferrous oxide, aluminum oxide, magnesium oxide, zinc oxide, aluminum silicate, magnesium silicate, calcium silicate, zinc silicate, zinc borate, magnesium hydroxide, aluminum hydroxide or iron hydroxide One or more.
所述步骤(3)中的老化时间为10min-10h，老化温度为10-75℃。所述步骤(3)的老化过程中，加入一定量的有机溶剂，所述的有机溶剂为甲醇、乙醇或丙酮中的一种或多种。The aging time in the step (3) is 10 min to 10 h, and the aging temperature is 10 to 75 ° C. In the aging process of the step (3), a certain amount of an organic solvent is added, and the organic solvent is one or more of methanol, ethanol or acetone.
所述步骤(4)中，在常压条件下，干燥温度为50-200℃，在二氧化碳超临界干燥条件下，干燥温度为30-65℃；在乙醇超临界干燥条件下，干燥温度为220-250℃。In the step (4), under normal pressure conditions, the drying temperature is 50-200 ° C, under the supercritical drying condition of carbon dioxide, the drying temperature is 30-65 ° C; under the supercritical drying condition of ethanol, the drying temperature is 220 -250 ° C.
本发明与现有方法相比，具有以下优点：1、以水溶性硅源为主要硅源，成本低廉，具有规模化生产前景；2、采用微乳液法来配制前驱体，既完成疏水化过程，也可较快的形成凝胶，减少了疏水化试剂对凝胶过程的影响；Compared with the prior methods, the invention has the following advantages: 1. The water-soluble silicon source is the main silicon source, the cost is low, and the production prospect is large; 2. The microemulsion method is used to prepare the precursor, and the hydrophobicization process is completed. It can also form a gel faster, which reduces the influence of the hydrophobizing agent on the gel process;
3、操作过程简洁快速，避免了有机试剂的大量使用，缩短了整个制造过程；4、方法新颖独特，充分融合了微乳液法和溶胶-凝胶法的各自特点，打破了以往凝胶制备中溶胶-凝胶过程的单一模式，为疏水二氧化硅气凝胶的生产提供了新的思路；3, the operation process is simple and fast, avoiding the extensive use of organic reagents, shortening the entire manufacturing process; 4, the method is novel and unique, fully blending the respective characteristics of the microemulsion method and the sol-gel method, breaking the previous gel preparation The single mode of the sol-gel process provides a new idea for the production of hydrophobic silica aerogels;
5、该方法所配的微乳液润湿性、渗透性良好，与各种无机添加剂、纤维材料相容性好，得到的气凝胶材料机械强度高，耐高温性能好。5. The microemulsion of the method has good wettability and permeability, and has good compatibility with various inorganic additives and fiber materials, and the obtained aerogel material has high mechanical strength and good high temperature resistance.
附图说明DRAWINGS
图1为含有无机硅源的水相与含有有机硅化合物的油相在微观层面上形成相互交错的三维立体结构图；1 is a three-dimensional structural view in which an aqueous phase containing an inorganic silicon source and an oil phase containing an organosilicon compound are interdigitated at a microscopic level;
图2为本发明制得的气凝胶微观结构图。Figure 2 is a diagram showing the microstructure of an aerogel produced in the present invention.
具体实施方式detailed description
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。The present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited thereto.
1.微乳液法常压干燥制备气凝胶 碱性硅溶胶500ml，高速搅拌的同时，依次加入水650ml，琥珀酸二辛脂磺酸钠30g，丙酮20g，正己烷350g，甲基三乙氧基硅烷150g，高 速搅拌直至得到半透明均匀的微乳液，加入少量的硫酸水溶液，调节pH至8，高速搅拌10min，然后倒入模具，静置40分钟，微乳液转变成半透明蓝白色凝胶；将凝胶置于60℃乙醇中老化1h，老化过程中通过有效的密封及添加少量乙醇，防止凝胶因溶剂挥发碎裂。老化完成后，将凝胶置于150℃鼓风干燥箱内干燥2h，即得到疏水二氧化硅气凝胶块体，密度约为110mg/cm3，微观结构如扫描电镜照片如图2所示。1. Preparation of aerogel by microemulsion method under normal pressure drying 500 ml of alkaline silica sol, while stirring at high speed, 650 ml of water, 30 g of sodium dioctyl sulfonate succinate, 20 g of acetone, 350 g of n-hexane, methyl triethoxylate Silane 150g, high Stir quickly until a semi-transparent homogeneous microemulsion is obtained, add a small amount of aqueous sulfuric acid solution, adjust the pH to 8, stir at high speed for 10 min, then pour into the mold, let stand for 40 minutes, and convert the microemulsion into a translucent blue-white gel; It is aged in ethanol at 60 ° C for 1 h. During the aging process, the gel is prevented from being volatilized by solvent evaporation by adding an effective seal and adding a small amount of ethanol. After the aging was completed, the gel was dried in a blast oven at 150 ° C for 2 h to obtain a hydrophobic silica aerogel block having a density of about 110 mg/cm 3 , and a microscopic structure such as a scanning electron microscope photograph is shown in FIG. 2 .
2.微乳液法制备气凝胶纤维毡-二氧化碳超临界干燥2. Preparation of aerogel fiber mat by microemulsion method - carbon dioxide supercritical drying
水玻璃500ml，高速搅拌的同时，依次加入水800ml，十二烷基硫酸钠36g，乙酸乙酯20g，异丙醇10g，正己烷350g，聚甲基三乙氧基硅烷200g，高速搅拌直至得到半透明均匀的微乳液，加入少量的硫酸水溶液，调节pH至7，高速搅拌10min，待用。取玻璃纤维针刺毡一块，长30cm，宽30cm，厚度10mm，密度80kg/m3，平铺在准备好的模具内，然后将配置好的微乳液均匀的倒入模具，直至纤维毡浸满液体，盖上模具盖板，防止挥发。静置30分钟后，形成玻璃纤维复合的凝胶材料；将凝胶材料置于60℃乙醇中老化5h，乙醇体积为凝胶材料体积的5倍；老化完成后，将凝胶材料放入二氧化碳超临界萃取釜内，设置压力10Mpa，温度40℃，干燥6h后，保温降压，最终得到疏水的、高强度的纤维毡复合二氧化硅气凝胶材料，25℃导热系数为0.0155W/m*K。500 ml of water glass, while stirring at high speed, 800 ml of water, 36 g of sodium lauryl sulfate, 20 g of ethyl acetate, 10 g of isopropyl alcohol, 350 g of n-hexane, and 200 g of polymethyltriethoxysilane were sequentially added, and stirring was carried out at high speed until A translucent homogeneous microemulsion was added with a small amount of aqueous sulfuric acid solution to adjust the pH to 7, and stirred at high speed for 10 min until use. Take a piece of glass fiber needle felt, 30cm long, 30cm wide, 10mm thick, density 80kg/m 3 , tiled in the prepared mold, and then pour the configured microemulsion into the mold evenly until the fiber mat is full. Liquid, cover the mold cover to prevent evaporation. After standing for 30 minutes, a glass fiber composite gel material was formed; the gel material was aged in ethanol at 60 ° C for 5 h, and the volume of ethanol was 5 times the volume of the gel material; after the aging was completed, the gel material was placed in carbon dioxide. In the supercritical extraction autoclave, the pressure is 10Mpa, the temperature is 40°C, and after drying for 6h, the pressure is reduced and the pressure is reduced. Finally, a hydrophobic, high-strength fiber-bonded composite silica aerogel material is obtained, and the thermal conductivity at 25°C is 0.0155W/m. *K.
3.微乳液法制备增强型气凝胶纤维毡-超临界干燥3. Preparation of reinforced aerogel fiber mat by microemulsion method - supercritical drying
水玻璃300ml，甲基硅酸钠200ml，高速搅拌的同时，依次加入水,600ml，十二烷基硫酸钠36g，丙酮20g，异丙醇10g，正己烷300g，聚甲基三乙氧基硅烷200g，甲基羟基硅油50g，高速搅拌直至得到半透明均匀的微乳液，加入少量的硫酸水溶液，调节pH至7，然后加入二氧化钛15g，氢氧化铝12g，氢氧化镁12，氢氧化铁12g，高速搅拌10min，待用。取玻璃纤维与莫来石纤维混合针刺毡一块，长30cm，宽30cm，厚度10mm，密度为100kg/m3，玻璃纤维与莫来石纤维的重量比为7:3，平铺在准备好的模具内，然后将配置好的微乳液均匀的倒入模具，直至纤维毡浸满液体，盖上模具盖板，防止挥发。静置40分钟后，形成无机添加剂--纤维复合的凝胶材料；将凝胶材料置于60℃乙醇中老化5h，乙醇体积为凝胶材料体积的5倍；老化完成后，将凝胶材料放入二氧化碳超临界萃取釜内，设置压力12Mpa，温度50℃，干燥6h后，保温降压，最终得到疏水的、增强型的纤维复合二氧化硅气凝胶材料，无机添加剂分散较均匀，25℃导热系数为0.0186W/m*K，平均温度500℃时的导热系数为0.059W/m*K，800℃下24小时收缩率小于2％，具有优良的高温使用性能。本发明提供了一种以微乳液为前体、低成本、快速制备疏水气凝胶及其复合材料的方法。微乳液是两种互不相溶液体在表面活性剂及助表面活性剂作用下自发形成的均一透 明、热力学稳定的分散体系。两种互不相溶的连续介质被表面活性剂双亲分子分割成微小空间形成微型反应器，其大小可控制在纳米级范围，反应物在体系中反应生成固相粒子。由于微乳液能对纳米材料的粒径和稳定性进行精确控制，限制了纳米粒子的成核、生长、聚结、团聚等过程，从而形成的纳米粒子包裹有一层表面活性剂，并有一定的凝聚态结构。300 ml of water glass, 200 ml of sodium methyl silicate, while stirring at high speed, water, 600 ml, 36 g of sodium lauryl sulfate, 20 g of acetone, 10 g of isopropanol, 300 g of n-hexane, polymethyltriethoxysilane 200g, 50g of methyl hydroxy silicone oil, stir at high speed until a translucent uniform microemulsion is obtained, a small amount of aqueous sulfuric acid solution is added, the pH is adjusted to 7, and then 15g of titanium dioxide, 12g of aluminum hydroxide, 12 parts of magnesium hydroxide, 12g of ferric hydroxide are added. Stir at high speed for 10 min and set aside. Take a mixture of glass fiber and mullite fiber needle felt, length 30cm, width 30cm, thickness 10mm, density 100kg/m 3 , weight ratio of glass fiber to mullite fiber is 7:3, tiled in preparation Inside the mold, the configured microemulsion is evenly poured into the mold until the fiber mat is saturated with liquid, and the mold cover is covered to prevent evaporation. After standing for 40 minutes, an inorganic additive-fiber composite gel material was formed; the gel material was aged in ethanol at 60 ° C for 5 h, and the volume of ethanol was 5 times the volume of the gel material; after the aging was completed, the gel material was Put it into the supercritical carbon dioxide extraction kettle, set the pressure to 12Mpa, the temperature is 50 °C, dry for 6h, then keep warm and reduce the pressure, and finally get the hydrophobic, reinforced fiber composite silica aerogel material, the inorganic additive is more evenly dispersed, 25 The thermal conductivity of °C is 0.0186W/m*K, the thermal conductivity at an average temperature of 500°C is 0.059W/m*K, and the shrinkage at 24°C is less than 2% at 800°C, which has excellent high-temperature performance. The invention provides a method for preparing a hydrophobic aerogel and a composite material thereof with a microemulsion as a precursor, a low cost and a rapid preparation. Microemulsion is a uniformly transparent, thermodynamically stable dispersion of two mutually incompatible liquids formed spontaneously by surfactants and co-surfactants. The two incompatible continuums are separated into small spaces by surfactant amphiphiles to form a microreactor, the size of which can be controlled in the nanometer range, and the reactants react in the system to form solid phase particles. Since the microemulsion can precisely control the particle size and stability of the nanomaterial, the process of nucleation, growth, coalescence, agglomeration and the like of the nanoparticles is limited, and the formed nanoparticles are coated with a layer of surfactant, and have certain Condensed structure.
本发明通过添加表面活性剂及助表面活性剂，辅以高速搅拌，将水溶性硅源的水溶液与不溶于水的有机硅化合物及辅助油相形成均匀稳定的微乳液体系，含有无机硅源的水相与含有有机硅化合物的油相在微观层面上形成相互交错的三维立体结构，如图1所示，表面活性剂与助表面活性剂则在两相之间形成动态边界，经过一定时间或通过调节体系的酸碱度及温度来加速，微乳液体系内的无机硅源逐渐缩合成三维立体骨架，而同时有机硅化合物经水解获得的或已有的羟基与上述骨架表面的羟基相缩合，有机硅化合物得以包覆在骨架表面。也可在微乳液失去流动性之前，浸入蓬松纤维毡基体，与纤维毡复合形成相互增强的复合材料。上述得到的缩合物或其复合材料，经过进一步老化增强，常压干燥后可得疏水的气凝胶及其复合材料；也可在老化增强的同时，辅以有机溶剂替换缩合物孔洞内的水，然后经超临界干燥得到疏水的气凝胶及其复合材料。The invention forms a uniform and stable microemulsion system by adding a surfactant and a co-surfactant, supplemented by high-speed stirring, a water-soluble silicon source aqueous solution, a water-insoluble organosilicon compound and an auxiliary oil phase, and contains an inorganic silicon source. The aqueous phase and the oil phase containing the organosilicon compound form a three-dimensional structure interlaced at a microscopic level. As shown in Figure 1, the surfactant and the co-surfactant form a dynamic boundary between the two phases, after a certain period of time or By adjusting the pH and temperature of the system, the inorganic silicon source in the microemulsion system is gradually reduced to a three-dimensional skeleton, and at the same time, the hydroxyl group obtained by hydrolysis or the existing hydroxyl group is condensed with the hydroxyl group on the surface of the skeleton, silicone The compound is coated on the surface of the skeleton. It is also possible to immerse the bulky fibrous felt matrix before the microemulsion loses fluidity and to form a mutually reinforcing composite with the fiber mat. The condensate obtained by the above or the composite material thereof is further aging-enhanced, and a hydrophobic aerogel and a composite material thereof can be obtained after drying under normal pressure; and the water in the pores of the condensate can be replaced by an organic solvent while aging is enhanced. Then, supercritical drying is carried out to obtain a hydrophobic aerogel and a composite thereof.
本发明制备工艺新颖，原料成本低，适用范围广，既可用常压干燥方法，也可用超临界干燥工艺，得到的材料具有优良的保温隔热性能，结构强度高，长期使用收缩率小。The invention has novel preparation process, low raw material cost and wide application range, and can be used for both normal pressure drying method and supercritical drying process, and the obtained material has excellent thermal insulation performance, high structural strength and small shrinkage rate in long-term use.
上述实施例仅用于解释说明本发明的发明构思，而非对本发明权利保护的限定，凡利用此构思对本发明进行非实质性的改动，均应落入本发明的保护范围。 The above-mentioned embodiments are only used to explain the inventive concept of the present invention, and are not intended to limit the scope of the present invention. Any insubstantial modification of the present invention by this concept should fall within the scope of the present invention.

Claims (8)

  1. 一种以微乳液为前体快速制备气凝胶的方法，其特征在于包括以下步骤：A method for rapidly preparing an aerogel using a microemulsion as a precursor, comprising the steps of:
    (1)微乳液的配制：将定量的水溶性硅源与水混合，加入定量的表面活性剂及助表面活性剂；在搅拌器高速搅拌下，缓慢加入一种或多种有机硅化合物及辅助油相，直至得到半透明均匀的微乳液；(1) Preparation of microemulsion: mixing a quantitative water-soluble silicon source with water, adding a certain amount of surfactant and co-surfactant; slowly adding one or more organosilicon compounds and assisting under high-speed stirring by a stirrer Oil phase until a translucent homogeneous microemulsion is obtained;
    (2)凝胶的制备：将步骤(1)得到的微乳液，通过一定时间，并/或添加适量的酸性或碱性催化剂加速凝胶；(2) Preparation of the gel: the microemulsion obtained in the step (1) is accelerated over a certain period of time and/or an appropriate amount of an acidic or basic catalyst is added;
    (3)老化增强过程：将步骤(2)形成的凝胶材料，在一定时间内，并/或在加热条件下进行老化；(3) aging enhancement process: the gel material formed in step (2) is aged for a certain period of time and/or under heating conditions;
    (4)超临界或常压干燥：将步骤(3)所得到的凝胶进行超临界或常压干燥，获得疏水的二氧化硅气凝胶。(4) Supercritical or atmospheric drying: The gel obtained in the step (3) is subjected to supercritical or normal pressure drying to obtain a hydrophobic silica aerogel.
  2. 如权利要求1所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述步骤(1)中的水溶性硅源为水玻璃、溶剂为水的酸性硅溶胶、溶剂为水的碱性硅溶胶、甲基硅酸锂、甲基硅酸钠、甲基硅酸钾、硅酸锂、偏硅酸锂、硅酸钠、偏硅酸钠、硅酸钾或偏硅酸钾中的一种或多种；The method for rapidly preparing an aerogel using a microemulsion as a precursor according to claim 1, wherein the water-soluble silicon source in the step (1) is water glass, the solvent is water, the acidic silica sol, and the solvent is Alkaline silica sol of water, lithium methyl silicate, sodium methacrylate, potassium methyl silicate, lithium silicate, lithium metasilicate, sodium silicate, sodium metasilicate, potassium silicate or metasilicate One or more of potassium;
    所述步骤(1)中的表面活性剂为琥珀酸二辛酯磺酸钠、十二烷基磺酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、脂肪醇聚氧乙烯醚硫酸钠、吐温60、吐温80、司盘20或聚乙二醇单油酸酯中的一种或多种；The surfactant in the step (1) is sodium dioctyl sulfonate sulfonate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, fatty alcohol polyoxyethylene. One or more of sodium ether sulfate, Tween 60, Tween 80, Span 20 or polyethylene glycol monooleate;
    所述步骤(1)中的助表面活性剂为丙酮、甲基丁酮、甲基异丁酮、乙酸乙酯、甲醇、乙醇、乙二醇、正丙醇或异丙醇中的一种或多种；The co-surfactant in the step (1) is one of acetone, methyl butanone, methyl isobutyl ketone, ethyl acetate, methanol, ethanol, ethylene glycol, n-propanol or isopropanol or Multiple
    所述步骤(1)中的有机硅化合物为六甲基二硅氧烷、六甲基二硅氮烷、二甲基二乙氧基硅烷、一甲基二乙氧基一氢硅烷、甲基三乙氧基硅烷、甲基三甲氧基硅烷、聚甲基三乙氧基硅烷、聚甲基三甲氧基硅烷、甲基羟基硅油、羟基含氢硅油、甲基三氟丙基硅油或甲基乙烯基硅油中的一种或多种；The organosilicon compound in the step (1) is hexamethyldisiloxane, hexamethyldisilazane, dimethyldiethoxysilane, monomethyldiethoxyhydrosilane, methyl Triethoxysilane, methyltrimethoxysilane, polymethyltriethoxysilane, polymethyltrimethoxysilane, methylhydroxysilicone oil, hydroxyhydrogen silicone oil, methyltrifluoropropyl silicone oil or methyl One or more of vinyl silicone oils;
    所述步骤(1)中的辅助油相为正己烷、环己烷、正戊烷或液体石蜡中的一种或多种。The auxiliary oil phase in the step (1) is one or more of n-hexane, cyclohexane, n-pentane or liquid paraffin.
  3. 如权利要求1所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述步骤(2)中的酸性催化剂为盐酸、硫酸、硝酸、磷酸、草酸、醋酸或乙二酸中的一种或多种；所述步骤(2)中的碱性催化剂为氨水、氢氧化钠、氢氧化钾、氢氧化钙、氢氧化锂、碳酸钠或碳酸钾中的一种或多种。The method for rapidly preparing an aerogel using a microemulsion as a precursor according to claim 1, wherein the acidic catalyst in the step (2) is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid or oxalic acid. One or more of the above; the basic catalyst in the step (2) is one or more of ammonia water, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate or potassium carbonate. .
  4. 如权利要求1或3所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述步骤(2)中在添加酸性或碱性催化剂之前，将步骤(1)得到的微乳液，加入适量的无机添加 剂，混合均匀后，将微乳液通过喷淋渗透或整体浸没的方式与纤维材料复合，微乳液转变为凝胶后与纤维形成一个整体。A method for rapidly preparing an aerogel using a microemulsion as a precursor according to claim 1 or 3, wherein in the step (2), the microparticle obtained in the step (1) is added before the addition of the acidic or basic catalyst. Emulsion, add appropriate amount of inorganic addition After the mixture is uniformly mixed, the microemulsion is compounded with the fiber material by spray permeation or integral immersion, and the microemulsion is transformed into a gel and formed into a whole with the fiber.
  5. 如权利要求4所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述的纤维材料为玻璃纤维、硅酸铝纤维、莫来石纤维、玄武岩纤维、聚酯纤维、聚丙烯腈纤维、碳纤维或黏胶纤维中的一种或多种；所述的无机添加剂为二氧化钛、氧化铁、氧化亚铁、氧化铝、氧化镁、氧化锌、硅酸铝、硅酸镁、硅酸钙、硅酸锌、硼酸锌、氢氧化镁、氢氧化铝或氢氧化铁中的一种或多种。The method for rapidly preparing an aerogel using a microemulsion as a precursor according to claim 4, wherein the fiber material is glass fiber, aluminum silicate fiber, mullite fiber, basalt fiber, polyester fiber, One or more of polyacrylonitrile fibers, carbon fibers or viscose fibers; the inorganic additives are titanium dioxide, iron oxide, ferrous oxide, aluminum oxide, magnesium oxide, zinc oxide, aluminum silicate, magnesium silicate, One or more of calcium silicate, zinc silicate, zinc borate, magnesium hydroxide, aluminum hydroxide or iron hydroxide.
  6. 如权利要求1所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述步骤(3)中的老化时间为10min-10h，老化温度为10-75℃。The method for rapidly preparing an aerogel using a microemulsion as a precursor according to claim 1, wherein the aging time in the step (3) is from 10 min to 10 h, and the aging temperature is from 10 to 75 °C.
  7. 如权利要求1或6所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述步骤(3)的老化过程中，加入一定量的有机溶剂，所述的有机溶剂为甲醇、乙醇或丙酮中的一种或多种。The method for rapidly preparing an aerogel by using a microemulsion as a precursor according to claim 1 or 6, wherein in the aging process of the step (3), a certain amount of an organic solvent is added, and the organic solvent is One or more of methanol, ethanol or acetone.
  8. 如权利要求1所述以微乳液为前体快速制备气凝胶的方法，其特征在于：所述步骤(4)中，在常压条件下，干燥温度为50-200℃，在二氧化碳超临界干燥条件下，干燥温度为30-65℃；在乙醇超临界干燥条件下，干燥温度为220-250℃。 The method for rapidly preparing an aerogel using a microemulsion as a precursor according to claim 1, wherein in the step (4), under normal pressure, the drying temperature is 50-200 ° C, and the carbon dioxide supercritical Under dry conditions, the drying temperature is 30-65 ° C; under ethanol supercritical drying conditions, the drying temperature is 220-250 ° C.
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