EP0946277A2 - Procede pour la fabrication d'aerogels durablement hydrophobes modifies organiquement - Google Patents

Procede pour la fabrication d'aerogels durablement hydrophobes modifies organiquement

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Publication number
EP0946277A2
EP0946277A2 EP97952807A EP97952807A EP0946277A2 EP 0946277 A2 EP0946277 A2 EP 0946277A2 EP 97952807 A EP97952807 A EP 97952807A EP 97952807 A EP97952807 A EP 97952807A EP 0946277 A2 EP0946277 A2 EP 0946277A2
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EP
European Patent Office
Prior art keywords
gel
lyogel
water
organic
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP97952807A
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German (de)
English (en)
Inventor
Fritz Schwertfeger
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Cabot Corp
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Cabot Corp
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Publication date
Application filed by Cabot Corp filed Critical Cabot Corp
Publication of EP0946277A2 publication Critical patent/EP0946277A2/fr
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Classifications

    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing organically modified, permanently hydrophobic aerogels.
  • Aerogels especially those with porosities above 60% and densities below 0.6 g / cm 3 , have an extremely low thermal conductivity and are therefore used as heat insulation materials, as described, for example, in EP-A-0 171 722.
  • Aerogels in the wider sense i.e. in the sense of "gel with air as a dispersing agent" are produced by drying a suitable gel.
  • airgel includes aerogels in the narrower sense, xerogels and cryogels.
  • a dried gel is referred to as an airgel in the narrower sense if the liquid of the gel is removed at temperatures above the critical temperature and starting from pressures above the critical pressure. If, on the other hand, the liquid of the gel is removed subcritically, for example with the formation of a liquid-vapor boundary phase, the resulting gel is often referred to as a xerogel.
  • aerogels in the broad sense, i.e. in the sense of "gel with air as a dispersant”.
  • aerogels can basically be divided into inorganic and organic aerogels.
  • Inorganic aerogels have been known since 1931 (SS Kistler, Nature 1931, 127.741). Since then, aerogels have been made from a wide variety of starting materials.
  • Organic aerogels have also been known for some years. In the literature one finds e.g. organic aerogels based on resorcinol / formaldehyde, melamine / formaldehyde or resorcinol / furfural (RW Pekala, J. Mater. Sei. 1989, 24, 3221, US-A-5,508,341, RD 388047, WO 94/22943 and US Pat. A-5,556,892).
  • Organic aerogels made from polyisocyanates (WO 95/03358) and polyurethanes are also known. As described, for example, in US Pat. No.
  • starting materials such as formaldehyde and resorcinoi are dissolved in water, these are reacted with one another by suitable catalysts, and the water in the pores of the gel formed is exchanged for a suitable organic solvent and then dries supercritically.
  • Inorganic aerogels can be produced in different ways.
  • SiO 2 aerogels can be produced by acid hydrolysis and condensation of tetraethyl orthosilicate in ethanol. This creates a gel that can be dried by supercritical drying while maintaining the structure. Manufacturing processes based on this drying technique are known, for example, from EP-A-0 396 076, WO 92/03378 and WO 95/06617.
  • SiO 2 gels An alternative to the above drying is a method for subcritical drying of SiO 2 gels, in which they are reacted with a chlorine-containing silylating agent before drying.
  • the resulting SiO 2 gel, modified on the surface with methylsilyl groups, can then be dried in air from an organic solvent. This enables aerogels with densities below 0.4 g / cm 3 and porosities above 60% to be achieved.
  • the manufacturing process based on this drying technique is described in detail in WO 94/25149.
  • the gels described above can be mixed with tetraalkoxysiianes and aged in the alcohol-aqueous solution before drying in order to increase the gel network strength, e.g. disclosed in WO 92/20623.
  • the resulting SiO 2 gel, modified on the surface with methylsilyl groups, can then also be air-dried from an organic solvent.
  • the manufacturing process based on this technique is described in detail, for example, in DE-A-43 42 548.
  • very large amounts of hydrogen chloride (HCl) and a large number of by-products are inevitably obtained, which may require very complex and costly cleaning of the silylated SiO 2 gels by washing them repeatedly with a suitable organic solvent.
  • DE-C 195 02 453 describes the use of a chlorine-free silylating agent.
  • a silicate lyogel produced by the above-described processes is placed in front and reacted with a chlorine-free silylating agent.
  • the resulting SiO 2 gel, modified on the surface with methylsilyl groups, can then also be air-dried from an organic solvent.
  • chlorine-free silylating agents solves the problem of HCl formation, but the chlorine-free silylating agents used represent a very high cost factor.
  • WO 95/06617 and German patent application 19541 279.6 disclose processes for the production of silica aerogels with hydrophobic surface groups.
  • the silica aerogels are reacted by reacting a water glass solution with an acid at a pH of 7.5 to 11, largely freeing the silica hydrogel formed from ionic constituents by washing with water or dilute aqueous solutions of inorganic bases, where the pH of the hydrogel is kept in the range from 7.5 to 11, displacement of the aqueous phase contained in the hydrogel by an alcohol and subsequent supercritical drying of the alkogel obtained.
  • German patent application 195 41 279.6 similar to that described in WO 95/06617, silica aerogels are produced and then dried subcritically.
  • step c) introducing a lyogel, b) washing the lyogel presented in step a) with an organic solvent, c) surface-silylating the gel obtained in step b), and d) drying the surface-silylated gel obtained in step c),
  • radicals R are, independently of one another, identical or different, each a hydrogen atom or a non-reactive, organic, linear, branched, cyclic, saturated or unsaturated, aromatic or heteroaromatic radical, preferably C r C 18 alkyl or C 6 -C 14- aryl, particularly preferably C r C 6 alkyl, cyclohexyl or phenyl, in particular methyl or ethyl.
  • a lyogel is understood to mean a gel dispersed in at least one solvent.
  • the solvent can also be water. If the water content in the solvent is at least 50% by weight, this is also referred to as a hydrogel.
  • the network of the lyogel can be present in any organic and / or inorganic basic composition. All systems known to the person skilled in the art from the prior art can be used as the basic organic composition.
  • An inorganic basic composition based on oxidic silicon, tin, aluminum, gallium, indium, titanium and / or zirconium compounds is preferred, particularly preferably based on oxidic silicon, aluminum, titanium - and / or zirconium compounds.
  • a silicate hydrogel is particularly preferred, which may contain proportions of zirconium, aluminum, titanium, vanadium and / or iron compounds, in particular a purely silicate hydrogel.
  • the different components do not necessarily have to be homogeneously distributed and / or form a continuous network. It is also possible for individual components to be wholly or partly in the form of inclusions, individual germs and / or deposits in the network.
  • the disiloxanes used according to the invention have compared to those from the
  • chlorine-containing silylating agents have the advantage that none chlorine-containing by-products arise. In addition, they are easy to separate from aqueous phases because of their insolubility, which enables excess reagents to be recycled. This makes it possible to minimize the silylation times by using concentrations in excess.
  • the lyogels presented in step a) can be prepared by all processes known to the person skilled in the art.
  • silicate lyogels Three preferred embodiments for the production of silicate lyogels are described in more detail below, but without being restricted thereto.
  • a silicate lyogel is introduced in step a), which is obtainable by hydrolysis and condensation of Si alkoxides in an organic solvent with water.
  • a tetraalkoxysilane preferably tetraethoxy or tetramethoxysilane, is used as the Si alkoxide.
  • the organic solvent is preferably an alcohol, particularly preferably ethanol or methanol, to which up to 20% by volume of water can be added.
  • acids and / or bases can be added as catalysts in a one- or two-step step.
  • the lyogel presented in step a) can additionally contain zirconium, aluminum, tin and / or titanium compounds capable of condensation.
  • opacifiers as additives in particular IR opacifiers for reducing the radiation contribution to thermal conductivity, such as e.g. Carbon black, titanium oxides, iron oxides and / or zirconium oxides can be added.
  • the sol can increase the mechanical stability of fibers be added.
  • Inorganic fibers such as glass fibers or mineral fibers, organic fibers such as polyester fibers, aramid fibers, nylon fibers or fibers of vegetable origin, and mixtures thereof can be used as fiber materials.
  • the fibers can also be coated, such as polyester fibers, which are metallized with a metal, such as aluminum.
  • the preparation of the lyogel is generally carried out at a temperature between the freezing point of the solution and 70 ° C.
  • a shaping step such as e.g. Spray forming, extrusion or drop formation can be carried out.
  • the lyogel obtained can also be subjected to aging. This is generally between 20 ° C and the boiling point of the organic solvent. If necessary, it can also be aged under pressure at higher temperatures. The time is generally up to 48 hours, preferably up to 24 hours.
  • a silicate hydrogel is introduced in step a), which is prepared by bringing an aqueous water glass solution to a pH ⁇ 3 with the aid of an acidic ion exchange resin, a mineral acid or a hydrochloric acid solution
  • the resulting silica is polycondensed by adding a base to an SiO 2 gel and, if a mineral acid or a hydrochloric acid solution is used, the gel was washed with water essentially free of electrolytes.
  • the polycondensation to the SiO 2 gel can take place in one step or in several stages.
  • Sodium and / or potassium water glass is preferably used as the water glass.
  • An acidic resin is preferably used as the ion exchange resin, with those containing sulfonic acid groups being particularly suitable. If mineral acids are used, hydrochloric acid and / or sulfuric acid are particularly suitable. If you use hydrochloric acid solutions, there are mainly aluminum salts suitable, in particular aluminum sulfate and / or chloride. NH 4 OH, NaOH, KOH, Al (OH) 3 and / or colloidal silica are generally used as the base.
  • the hydrogel preferably produced from the silicate starting compounds described above can additionally contain zirconium, aluminum, tin and / or titanium compounds capable of condensation.
  • opacifiers as additives in particular IR opacifiers for reducing the radiation contribution to thermal conductivity, such as e.g. Carbon black, titanium oxides, iron oxides and / or zirconium oxides can be added.
  • fibers can be added to the sol to increase the mechanical stability.
  • Inorganic fibers such as e.g. Glass fibers or mineral fibers
  • organic fibers such as e.g. Polyester fibers, aramid fibers, nylon fibers or fibers of plant origin, and mixtures thereof can be used.
  • the fibers can also be coated, e.g. Polyester fibers bonded to a metal, e.g. Aluminum, are metallized.
  • the hydrogel is generally prepared at a temperature between the freezing point and the boiling point of the solution.
  • a shaping step such as e.g. Spray forming, extrusion or drop formation can be carried out.
  • the hydrogel obtained can also be subjected to aging. This aging can take place before and / or after a possible wash with water described above, with which the gel is washed essentially free of electrolytes.
  • Aging generally takes place at a temperature in the range from 20 to 100 ° C., preferably at 40 to 100 ° C. and in particular at 80 to 100 ° C., and to a pH of 4 to 11, preferably 5 to 9, and especially 5 to 8.
  • the time for this is generally up to 48 hours, preferably up to 24 hours and particularly preferably up to 3 hours.
  • a silicate hydrogel is introduced in step a), which is prepared by obtaining an SiO 2 gel from an aqueous water glass solution using at least one organic and / or inorganic acid via the intermediate stage of a silica sol.
  • a 6 to 25% by weight (based on the SiO 2 content) sodium and / or potassium water glass solution is generally used as the water glass solution.
  • a 10 to 25% by weight water glass solution is preferred, and a 10 to 18% by weight water glass solution is particularly preferred.
  • the water glass solution can also contain up to 90% by weight of zirconium, aluminum, tin and / or titanium compounds based on SiO 2 .
  • Acids generally used are 1 to 50% by weight acids, preferably 1 to 10% by weight acids.
  • Preferred acids are sulfuric, phosphoric, hydrofluoric, oxalic and / or hydrochloric acid.
  • Hydrochloric acid is particularly preferred. Mixtures of the corresponding acids can also be used.
  • both solutions should preferably independently of one another a temperature between 0 and 30 ° C, particularly preferably between 5 and 25 ° C and in particular between 10 and Have at 20 ° C.
  • a shaping step can take place at the same time during production, e.g. through spray forming, extrusion or drop formation.
  • the hydrogel obtained can also be subjected to aging. This is generally done at 20 to 100 ° C, preferably at 40 to 100 ° C, in particular at 80 to 100 ° C and a pH of 2.5 to 11, preferably 5 to 8.
  • the time for this is generally up to up to 12 hours, preferably up to 2 hours and particularly preferably up to 30 minutes.
  • the gel produced is preferably washed with water, particularly preferably until the washing water used is free of electrolytes. If aging of the gel is carried out, the washing can be carried out before, during, and / or after aging, in which case the gel is preferably washed during or after aging. Part of the water can be replaced with organic solvents for washing. However, the water content should preferably be so high that the salts in the pores of the hydrogel do not crystallize out.
  • the hydrogel can also be treated with a mineral acid before, during and / or after washing with water getting washed.
  • Preferred mineral acids are also the mineral acids mentioned as preferred for the preparation of the hydrogel.
  • the water glass, the acid and / or the sol can be used as additives, in particular IR opacifiers, to reduce the radiation contribution to thermal conductivity, such as e.g. Carbon black, titanium oxides, iron oxides and / or zirconium oxides can be added.
  • IR opacifiers to reduce the radiation contribution to thermal conductivity, such as e.g. Carbon black, titanium oxides, iron oxides and / or zirconium oxides can be added.
  • fibers can be added to the water glass, the acid and / or the sol to increase the mechanical stability.
  • Inorganic fibers such as e.g. Glass fibers or mineral fibers, organic fibers such as e.g. Polyester fibers, aramid fibers, nylon fibers or fibers of vegetable origin, as well as mixtures thereof can be used.
  • the fibers can also be coated, e.g. Polyester fibers bonded to a metal, e.g. Aluminum, are metallized.
  • step b) the gel obtained from step a) is washed with an organic solvent, preferably until the water content of the gel is ⁇ 5% by weight, particularly preferably ⁇ 2% by weight and in particular ⁇ 1% by weight.
  • organic solvent preferably methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dioxane, pentane, n-hexane, n-heptane and toluene.
  • Acetone, tetrahydrofuran, pentane and n-heptane are particularly preferred as solvents.
  • the water can also first be mixed with a water-miscible solvent, e.g. an alcohol, acetone or THF, and then this is washed out with a hydrocarbon.
  • a water-miscible solvent e.g. an alcohol, acetone or THF
  • Pentane or n-heptane is preferably used as the hydrocarbon.
  • the lyogel obtained in step b) can be subjected to further aging. This generally happens between 20 ° C and the boiling point of the organic solvent. If necessary, it can also be aged under pressure at higher temperatures. The time is generally up to 48 hours, preferably up to 24 hours. After such aging, another solvent exchange to the same or a different solvent may follow. This additional aging step can also be repeated if necessary.
  • step c) the solvent-containing gel is reacted with a disiloxane of the formula I as a silylating agent,
  • radicals R independently of one another, identical or different, each represent a hydrogen atom or a non-reactive, organic, linear, branched, cyclic, saturated or unsaturated, aromatic or heteroaromatic radical, preferably C 1 -C 18 alkyl or C 6 -C 14 Aryl, particularly preferably C Cg-alkyl, cyclohexyl or phenyl, in particular methyl or ethyl.
  • the solvent-containing gel is preferably reacted with a symmetrical disiloxane, a symmetrical disiloxane being understood to mean a disiloxane in which both Si atoms have the same R radicals.
  • Disiloxanes in which all the radicals R are the same are particularly preferably used.
  • hexamethyldisiloxane is used.
  • the reaction is generally carried out at 20 ° C. to the boiling point of the silylating agent, if appropriate in a solvent.
  • Preferred solvents are the solvents described as preferred in step b).
  • Acetone, tetrahydrofuran, pentane and n-heptane are particularly preferred.
  • the silylation is carried out in a solvent, the silylation is generally carried out between 20 ° C. and the boiling point of the solvent.
  • the silylation is carried out in the presence of a catalyst, for example an acid or base. Acids are preferably used as the catalyst. Particularly preferred acids are hydrochloric acid, sulfuric acid, acetic acid and / or phosphoric acid.
  • the silylation is carried out in the presence of catalytic amounts of a silylating agent which forms acids in the presence of water.
  • a silylating agent which forms acids in the presence of water.
  • Chlorosilanes are preferred, particularly preferably trimethylchlorosilane (TMCS).
  • TMCS trimethylchlorosilane
  • a combination of acids or bases and TMCS is also possible.
  • the silylated gel is preferably washed with a protic or aprotic solvent until unreacted silylating agent has essentially been removed (residual content ⁇ 1% by weight).
  • Suitable solvents are those mentioned in step b). Analogously, the solvents mentioned there as preferred are also preferred here.
  • the silylated and optionally washed gel is preferably dried subcritically, preferably at temperatures from -30 to 200 ° C, particularly preferably 0 to 100 ° C, and pressures preferably from 0.001 to 20 bar, particularly preferably 0, 01 to 5 bar, in particular 0.1 to 2 bar, for example by radiation, convection and / or contact drying. Drying is preferably continued until the gel has a residual solvent content of less than 0.1% by weight.
  • the aerogels obtained during drying are permanently hydrophobic.
  • the gel obtained in step c) can also be dried supercritically. Depending on the particular solvent, this requires temperatures higher than 200 ° C and / or higher pressures than 20 bar. This is possible without further ado, but it is associated with increased effort and does not bring any significant advantages.
  • the gel can be subjected to a network reinforcement before the silylation in step c).
  • the gel can be formed after the shaping polycondensation and / or each subsequent process step using techniques known to the person skilled in the art, such as, for example, Grind, be crushed.
  • the aerogels produced by the process according to the invention are used in particular as heat insulation materials.
  • the resulting gel is then aged for a further 3 hours at 85 ° C. and then the water is exchanged for acetone with 3 l of acetone.
  • the acetone-containing gel is then silylated with hexamethyldisiloxane at room temperature for 5 hours (2.5% by weight Hexamethyldisiloxane per gram of wet gel).
  • the gel is dried in air (3 hours at 40 ° C., then 2 hours at 50 ° C. and 12 hours at 150 ° C.).
  • the transparent airgel thus obtained has a density of 0.15 g / cm 3 , a thermal conductivity of 16 mW / mK, a specific BET surface area of 600 m 2 / g and is permanently hydrophobic.
  • the airgel thus obtained has a density of 0.15 g / cm 3 , a thermal conductivity of 17 mW / mK, a BET specific surface area of 580 m 2 / g and is permanently hydrophobic.
  • the hydrogel is prepared as described in Example 2.
  • the hydrogel aged at 85 ° C. for 1 hour, is then washed with 3 l of warm water and the water is exchanged for acetone with 3 l of acetone.
  • the acetone-containing gel with hexamethyldisiloxane (2.5% by weight hexamethyldisiloxane per gram of wet gel) in the presence of 0.1% by weight of trimethylchlorosilane (0.1% by weight of trimethylchlorosilane per gram of wet gel) for 5 hours at room temperature silylated.
  • the gel is dried after washing the gel with 3 liters of acetone in air (3 hours at 40 ° C, then 2 hours at 50 ° C and 12 hours at 150 ° C).
  • the airgel thus obtained has a density of 0.14 g / cm 3 , a thermal conductivity of 16 mW / mK, a BET specific surface area of 590 m 2 / g and is permanently hydrophobic.
  • the hydrogel is prepared as described in Example 2.
  • the hydrogel aged at 85 ° C. for 1 hour, is then washed with 3 l of warm water and the water is exchanged for acetone with 3 l of acetone.
  • the acetone-containing gel is then treated with hexamethyldisiloxane (2.5% by weight hexamethyldisiloxane per gram of wet gel) in the presence of 0.1% by weight of 1N aqueous hydrochloric acid (0.1% by weight of 1N aqueous hydrochloric acid per gram of wet gel). Silylated for 5 hours at room temperature.
  • the gel is dried after washing the gel with 3 l of acetone in air (3 hours at 40 ° C., then 2 hours at 50 ° C. and 12 hours at 150 ° C.).
  • the airgel thus obtained has a density of 0.14 g / cm 3 , a thermal conductivity of 16 mW / mK, a BET specific surface area of 570 m 2 / g and is permanently hydrophobic.
  • the thermal conductivities were measured using a heating wire method (see, for example, O. Nielsson, G. Joschenpöhler, J. subject, J. Fricke, High Temperatures - High Pressures, Vol. 21, 267-274 (1989)).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un procédé pour la fabrication d'aérogels modifiés organiquement, comportant des groupes de surface durablement hydrophobes, dans lequel (a) on prend un lyogel, (b) on lave ce lyogel avec un solvant organique, (c) on silyle en surface le gel obtenu à l'étape (b), et (d) on sèche le gel silylé en surface obtenu à l'étape (c). Ce procédé est caractérisé en ce que l'on utilise, lors de l'étape (c), comme agent de silylation un disiloxane de la formule (I) R3Si-O-SiR3, dans laquelle les restes R, qui sont identiques ou différents, représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou bien un reste aromatique ou hétéroaromatique non réactif, organique, linéaire, ramifié, cyclique, saturé ou insaturé.
EP97952807A 1996-11-26 1997-11-26 Procede pour la fabrication d'aerogels durablement hydrophobes modifies organiquement Withdrawn EP0946277A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19648797A DE19648797A1 (de) 1996-11-26 1996-11-26 Verfahren zur Herstellung von organisch modifizierten, dauerhaft hydrophoben Aerogelen
DE19648797 1996-11-26
PCT/EP1997/006596 WO1998023367A2 (fr) 1996-11-26 1997-11-26 Procede pour la fabrication d'aerogels durablement hydrophobes modifies organiquement

Publications (1)

Publication Number Publication Date
EP0946277A2 true EP0946277A2 (fr) 1999-10-06

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EP97952807A Withdrawn EP0946277A2 (fr) 1996-11-26 1997-11-26 Procede pour la fabrication d'aerogels durablement hydrophobes modifies organiquement

Country Status (7)

Country Link
EP (1) EP0946277A2 (fr)
JP (1) JP2001504757A (fr)
KR (1) KR20000057273A (fr)
CN (1) CN1101725C (fr)
CA (1) CA2274911A1 (fr)
DE (1) DE19648797A1 (fr)
WO (1) WO1998023367A2 (fr)

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WO2008044873A1 (fr) * 2006-10-10 2008-04-17 Korea Institute Of Industrial Technology Procédé de préparation d'un aérogel à hydrophobicité permanente et aérogel à hydrophobicité permanente préparé par ce procédé
CN100463852C (zh) * 2006-12-19 2009-02-25 中国人民解放军国防科学技术大学 一种SiO2气凝胶的高温高压制备方法
KR101434273B1 (ko) * 2007-03-15 2014-08-27 알이엠텍 주식회사 표면개질된 실리카겔의 제조 방법
KR100848856B1 (ko) 2007-03-27 2008-07-29 주식회사 넵 영구적 소수성을 갖는 에어로겔의 제조 방법 및 이로부터제조된 영구적 소수성을 갖는 에어로겔
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KR100896790B1 (ko) * 2007-07-16 2009-05-11 한국과학기술연구원 실리카 에어로젤의 제조방법과 이에 의하여 제조된 실리카에어로젤
KR100924782B1 (ko) * 2007-09-19 2009-11-03 주식회사 넵 영구적인 소수성을 갖는 고투광성 입상형 에어로겔제조방법 및 이로부터 제조된 입상형 에어로겔
EP2408864A1 (fr) * 2009-03-18 2012-01-25 Basf Se Particules de silice modifiée et compositions polymères résistant à la salissure les comprenant
KR100981238B1 (ko) * 2009-07-13 2010-09-10 김영일 소수성 에어로겔의 제조 방법 및 제조장치
CN102198943B (zh) * 2011-04-21 2013-03-13 江苏大学 一种低成本常压干燥制备不同接触角硅基气凝胶的方法
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CN104445238B (zh) * 2014-11-17 2016-07-06 中国地质科学院郑州矿产综合利用研究所 一种改性水玻璃及其制备方法
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CN1101725C (zh) 2003-02-19
WO1998023367A3 (fr) 1998-07-16
CN1241953A (zh) 2000-01-19
KR20000057273A (ko) 2000-09-15
CA2274911A1 (fr) 1998-06-04
DE19648797A1 (de) 1998-05-28
WO1998023367A2 (fr) 1998-06-04
JP2001504757A (ja) 2001-04-10

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