TW315375B - - Google Patents

Description

315375 Α7 Β7 The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printing 5. V. Description of the invention (1) The present invention relates to organic aerogels, more specifically to polyisocyanate-based aerogels and their preparation methods. ~ Polyisocyanate-based rigid foam% polyurethane and polyisofluorourate foam, etc. are well known in the art. They are used as thermal insulation media, for example, in the structure of refrigeration equipment. Foams such as & are generally made by reacting suitable polyisocyanates and polyols in the presence of a blowing agent. The thermal insulation properties of rigid foams depend on many factors, including the size of the air cell of the closed rigid foam and the thermal conductivity of the content of the air cell (that is, the blowing agent used in the foam process). One of the substances used in the production of quality polyurethane and polyisocyanurate foams has been widely used as a blowing agent is a fully halogenated atmosphere-containing fluorocarbon, especially trichlorofluoromethane (CFC-11). The very low heat rate of these blowing agents, especially cpc-u, can produce rigid foams with extremely effective thermal insulation. Recent concerns about the potential of chlorofluorocarbons to deplete odors in the atmosphere have led to an urgent need to develop materials that can be changed to environmentally friendly materials, to replace chlorofluorocarbon blowing agents, and to manufacture them for a variety of uses. Foam of the necessary nature. Such other blowing agents technically claimed include hydrofluorocarbons, argon fluorides and (cyclo) alkanes. Although these materials are more environmentally acceptable than CFCs (their ozone depletion potential (ODP) is small or even zero), the heat retention is slightly worse. — In view of the strong demand for energy consumption and environmental legislation, we explored selected polyisocyanate-based insulation materials. One of these options is an evacuated thermal insulation panel filled with open-cell hard polyurethane foam. Vacuum can eliminate the heat conduction of the gas in the sample and reduce the thermal conductivity of the sample. However, the thermal conductivity of this vacuum insulation panel is due to the gas such as air and water vapor inside the panel. This paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X 297 mm) (please read the note on the back first Please fill in this page again.) 袈.,-* A7 B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of invention (2) It gradually spreads and increases rapidly with the increasing internal pressure over time. Aerogel is known for its super insulation because it excludes any involvement from cypress. These substances are good for the environment because they are full of emptiness. And it is not easy to age. Aerogel is a unique type of open-cell foam with ultra-fine air cell size and low density. #Gel has porosity, and its pore size is lower than the microstructure of the average free channel of air (the pore size is in the common sand range), which is the reason for its abnormal thermal properties. Traditional aerogels are made of inorganic substances (such as silica, alumina or zirconia aerogels) by hydrolysis and condensation of gold fermented salt. Silica gas. Gel has been developed as a super-insulating material such as window glass. Organic aerogels are expected to have lower thermal conductivity, thus providing less heat loss in thermal insulation applications. Recently, organic aerogels have been developed. US Patent Nos. 4997804 and 4873218 illustrate resorcinol-formaldehyde aerogels. U.S. Patent Nos. 5,060,085 and 5,811,163 describe melamine-formaldehyde aerogels and the like. -, Organic aerogels based on polyisocyanate chemistry have never been described before. Therefore, the object of the present invention is to provide an organic aerogel based on polyisocyanate compound and its preparation method. The present invention thus provides a polyisocyanate-based organic aerogel. The term "polyisocyanate-based" used in this article means the aerogel of the present invention can have the following types: polyurethane aerogel, polyurea aerogel * polyisocyanurate aerogel, polyisofluoride Urate / polyurethane aerogel, polyadenylate aerogel, polydicoordinate aerogel, poly || di-adeno aerogel. The aerogel according to the invention has a pore size of less than or equal to 100 nni. Generally, the pore size is in the range of 1 to 100 nm, and more often in the range of 5 to 50 nm. The paper size is applicable to the Chinese National Falcon (CNS) Μ specification (210 X 297 gong) (please read the back side first (Notes to fill out this page) 袈 · Order 315375 A7 _ B7 V. Description of the invention (3) Often in the range of 5 to 25 nm. The pore size can be determined visually by transmission electron microscopy (TEM) or Brunauer-Emmet-Teller nitrogen adsorption (BET) for mercury porosimetry. The quoted pore size value is the average pore diameter measured by the Micromeritics AS # 2000 type 3.0 porosimeter system for root nitrogen liquid adsorption. The average pore diameter is calculated at 4 V / A, where V = cumulative porosity per gram of material and A = specific surface area determined by 5-point BET. The density of the aerogel of the present invention is generally in the range of 1 to 1000 kg / η3, more often in the range of 10 to 800 kg / m3, more often in the range of 20 to 400 kg / n3 or even 30 to 300 kg / m3 or even 90 Up to 200 kg / m3. The density can be determined by weighing and measuring the immersion displacement water capacity, or by weighing and measuring the geometric volume of a sample with a regular shape. The surface area of the pneumatic knee of the present invention is generally in the range of 10 to 1500 m2 / g, more often in the range of 50 to 1200 m2 / g-, more often in the range of 200 to 1000 m2 / g or even 700 to 1000 m2 / g. The surface area can be determined by, for example, BET. The organic polyisocyanate-based aerogel of the present invention can be mixed with a polyisocyanate and an isocyanate trimerization catalyst in an appropriate solvent to keep the mixture in a static state for a long period of time to form a polymerized gel Made of glue. Failed this way-I m In ..... i HI -I--HI In One OJ (please read the precautions on the back and then fill out this page) The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative prints different and more Plus ground. The sexual roots are rooted in the life of the super-gelatinized acid, and the post-condensation ester cyanide internal gas acid is a different agent. The urinary solubility of the cyanide can be different from the static state. It is suitable for this high one. Even more together. Liang and Shu mixed the modified ester amine to maintain the dry alkanoate to protect urine cyanide. The cyanide polymer paper of the Chinese standard (CNS) A4 specification is suitable for the standard of the cyanide polymer paper which is super-coated with multi-enzymes, analysing the polyalkane, and dissolving polyuria. (210X297mm) A7 B7 The Ministry of Economic Affairs Central Standards Bureau employee consumption cooperation du printed five. Invention description [4 '1 1 I Can 0 The aerogel thus obtained is based on polyurethane and / or polyadeny chemistry 0 this 1 1 1 The alternative manufacturing method allows a larger selection of the dissolved m and increases the gelation time and drying conditions. The content of the treatment can be obtained. 1> 1 1 The polyisocyanate used in this manufacturing method of this aerogel is included in the literature Known for reading 1 I for making poly * isocyanurate materials commonly used for aliphatic cycloaliphatic aryl aliphatic and backside 1 I of 1 aromatic polyisocyanate. Particularly important are aromatic polyisocyanates such as methylbenzene Note 1 I and diphenylmethane diisocyanate week Known Purity, Improvement and Crude Formula Matters 1 1 Re I is especially diphenylmethylene diisocyanate (MDI) or its 2, 4 *-lead 2, 2 'and -4, 4'-isomer formula (passive MD I) and technically known as a crude form of this page. A system made or polymerized MDI (multi-methylene multiple benzene polyisocyanate) with isoacid 1 I a mixture of functionalities greater than 2 and so-called MDI variants (MD I has introduced 1 1 urethane adenylate adenyl biuret N carbodiimide m ketimide 1 I amine or isocyanurate residues and other improvers) 〇Use of gaseous solvents (such as In the case of HCFC 22, the polyisocyanate used in this method for making an aerogel 1 I is preferably a so-called isocyanate-terminated prepolymer made from a reactive compound of polyisocyanate and monoisocyanate. 0 This item is prepared 1 | Isocyanate reactive compounds for prepolymers are preferred Produces a product for the reaction of an alkylene oxide such as ethylene oxide and / or propylene oxide with a monoalcohol or glycol. This hydroxyalkane monoalcohol or binary enzyme has ethylene oxide / propylene oxide m level 1 adjusted to gas condensation The hydrophilicity K of the specific solvent used in the gumming method makes isocyanic acid 1 1 the prepolymer at the root end soluble in this solvent 0 If more hydrophobic solvents are used (for example 1 HCFC 22 HFC 134a dioxin salt monofluoromethane liquid C0 a) t 1 1 has 0: 100 and 80: 20 ethylene. The hydrophobicity of oxygen / propylene oxide level 1 I hydroxy burned mono-enzyme or monohydric alcohol accounted for 7- for example 1 1 of Debne gate PLC 1 1 1 1 1 1 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 315375 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs.

Arlamo Bu E. If a hydrophilic solvent (for example, acetone, 2-butanone) is used, a hydrophilic hydroxyalkylated monoalcohol or diol with a level of alkylene oxide / propylene oxide between 20:80 and 80:20 In the special case of using hydrogenated hydrocarbons or CO 2 as a solvent, the polyisocyanate used in the method of the present invention to produce gas 1 " gel is preferably a polyisocyanate and a “substantially fluorinated isocyanate-reactive compound” The so-called isocyanate-terminated prepolymer. The term "substantially fluorinated isocyanate-reactive compound" as used herein means that there is at least one isocyanate-reactive functional group in which the hydrogen atoms bonded to the carbon atoms in the corresponding unfluorinated compound have at least 50¾ Any organic compound replaced by a fluorine atom. The isocyanate-reactive compound suitably fluorinated in the production method of the present invention is of formula (I): * 1 [HY-(CH2) m-(Z ') <, ·] p-A- (Z ).-(CHa) "-XH (I) where n is an integer from 1 to 11; m is 1 to 11; P is 0 or 1; a q is 0 or 1; q 'is 0 or 1; 4 0 0 η I) Υ system oxygen, sulfur, -co-form group, or -C-NR, -S〇2-NR-if-NR-form group, wherein R is hydrogen, CK2 alkyl or gasified alkyl This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) m ^ im fn ^ — · ϋ > — B ^ ln ^ i ml tuf ml—Jt (please read the precautions on the back before filling this page) V. Description of the invention (base; A7 B7 I)

X is oxygen, sulfur, -C-0-form group "or -C-NR so2-hr,-or -NR'- group, wherein alkyl, fluorinated alkyl, hydrogen or-(CHzU-Uh-A -HZ'h.-WHzU-Y-HU type base 11

0 II and Z ’are each independently -C-0-, -C-HR", or -S〇2-HR "formula, wherein ir is hydrogen

Cl-1-12 alkyl gasification alkyl group or-((: Η2) "-Α-[((: Η2) · -Υ-Η] ρ formula group, or -R" '-YH formula group where R " 'Is ^-: ^ alkylene; optionally when P is 0, A is a substantially fluorinated or perfluorinated linear or branched alkyl group containing from 2 to 10 carbon atoms; or when P is 1 It is a linear or branched alkylene group containing from 2 to 10 carbon atoms, which is fluorinated or fully fluorinated. The method of the present invention uses a group of preferably substantially fluorinated isocyanate-reactive compounds having the above formula (I ), Where X and Υ are both oxygen, and A, Z, Z ', n, m, p, q and q' have any of the above meanings, preferably p is 0. The method of the present invention uses particularly good substantially fluorinated The isocyanate-reactive compound is of formula (11): — (i) (ϋ) n ^ 't ^ in mV ^ il ^ i * ^ ϋ n 111 1 OJ (Please read the precautions on the back before filling in this (Page) Ministry of Economic Affairs China National Bureau of Standards and Staff's consumer cooperation du printing (CH2) n-〇H / (II) formula A series of substantially fluorinated or perfluorinated paper containing 2 to 10 carbon atoms with direct bonds or branched paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by Zakusha A7 B7. V. Description of the invention (7) Alkyl group and η is 1 to 11. 'In particular, the compound of formula (II) where η is 1 or 2 can be mentioned, and A is perfluoro C3 :. Zhilian Or branched-chain alkyl such as (perfluoropropyl) methanol, (perfluorobutyl) methyl (perfluoropentyl) methanol, (perfluorohexyl) methanol, (perfluoroheptyl) methanol, (perfluorooctyl) Methanol, (per ^ nonyl) methanol, (perfluoroethyl) ethanol, (perfluoropropyl) ethanol, (perfluorobutyl) ethanol, (perfluoropentyl) ethanol, (perfluorohexyl) ethanol, ( Perfluoroheptyl) ethanol and (perfluorooctyl) ethanol. Another special mention can be made to the compounds of formula (II), where η is 1 or 2, Α is substantially fluorinated linear or branched alkyl Such as 1Η, 1Η, 7Ηdodefluoro-1-heptanol • Tetrafluoropropanol, dodecafluoroheptanol, octafluoropentanol, hexafluorononanol, 1H · 1H-perfluorooctanol, hexafluoropropanol The method of the present invention uses another particularly preferred group of substantially fluorinated isocyanate-reactive compounds of formula (III): «Η. A-SOz-N- (CH2) n-〇H (III) I!

In the Rv formula, A is a substantially fluorinated or perfluorinated linear or branched alkyl group containing from 2 to 10 carbon atoms * η is 1 to 11; and _ R "is hydrogen or (^ -12 alkyl or R "'-〇H where R"' is.-^ Alkylene. Special reference to compounds of formula (III) where η is 1 or 2 and A is perfluoro Ce-8 straight or branched alkyl, R "Is hydrogen or alkyl or R" '-〇H where R "' is Ci-4 alkylene, such as N-ethyl-N-2-hydroxyethyl substituted perfluorooctane sulfonamide, N-methyl- N-2-hydroxyethyl substituted perfluorooctane sulfonamide, N-propyl-N- 2-hydroxyethyl-10- This paper scale is applicable to China National Standard (CNS) A4 specifications (210X297mm) I vm ^ in ti ^^ in ^ i In 1 1 (Please read the precautions on the back before filling in this page) 315375 Λ7 Β7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Instructions (8) Substituting PFOS, 1Γ-2-hydroxyethyl substituted perfluorooctane sulfonamide, N-ethyl-N_2-hydroxymethyl substituted perfluorooctane perfluorooctane-amine, N-methyl-H-2-hydroxymethyl substituted perfluorooctane sulfonamide Amine, N-Propyl-N- 2-hydroxy ^ -perfluorooctane sulfonamide, N-2-hydroxymethyl-perfluorooctane sulfonamide, N-methyl-N-2-hydroxyethanidine Alkylamide and bis-is- 2-Hydroxyethyl substituted perfluorooctane sulfonamide. Substantially fluorinated isocyanate-reactive compounds (etc.) can react with them to form suitable organic polyisocyanates including polyisocyanate compositions for use in the process of the present invention. Polyurethane or urethane-modified polyisocyanurate foam-any known one • Especially aromatic polyisocyanates such as diphenylmethane diisoselection: acid ester into its 2, 4'-, 2, 2'- and 4, 4 · -isomers and their mixtures, the mixture of dibenzyl methane diisocyanate (MDI) and its oligomers is technically called, crude " or polymeric MDI (Dorya Methyl multiple phenyl polyisocyanates) with isocyanate functionality greater than 2, toluene diisocyanate into its 2,4- and 2,6-isomers and mixtures thereof, 1,5-naphthalene diisocyanate and 1,4-Diisocyanatobenzene. Other organic polyisocyanates that may be mentioned include aliphatic diisocyanates such as isophorone diisocyanate, 1,6-diisocyanatohexane and 4,4'-diisocyanate Isocyanato dicyclohexylmethane. The isocyanate terminal prepolymer used in the production method of the present invention can be added by adding a special Substantially fluorinated isocyanate-reactive compound in organic polyisocyanate-or adding a mixture of several different fluorinated isofluorate-reactive compounds in organic polyisocyanate, such as a prepolymer at the isocyanate end It is convenient to make V preparation under the conditions known last week. Adding is suitable for thoroughly mixing the sister parts when the temperature is raised from 50t: to 100t: and continues to mix at the temperature. M. Almost all isocyanate-reactive compounds have been added. With organic polyisocyanate-11- This paper scale is applicable to China National Standard (CNS) Α4 specifications (210 X 297 mm) (please read the precautions on the back before filling out this page) 袈 · Order the Central Bureau of Standards of the Ministry of Economic Affairs Employee consumption cooperatives print A7 B7. V. Description of invention (9) Ester reaction. The substantially fluorinated isocyanate-reactive compound (etc.) is suitably added in the weight ratio range of 0.02 to 30¾, preferably 0.1 to 50¾, based on the weight of the organic polyisocyanate ester. .. In order to improve the stability of the polyisocyanate compound used in the production method of the present invention, it is advantageous to make the allophanate variant of the fluorinated isocyanate terminal prepolymer obtained. This allophanate variant can be prepared by reacting the resulting fluorinated isocyanate terminal prepolymer with the organic polyisocyanate itself in the presence of a suitable catalyst. Another method to improve the stability of the polyisocyanate compound used in the method of the present invention is to use the so-called mixed polymer. It is also possible to use these mixed prepolymer allophanate variants. Examples of such preferred prepolymers include from N-ethyl-N- 2-hydroxyethylated perfluorooctane sulfonamide and N-methyl-N-2-hydroxyethylated perfluorooctane sulfonamide. 1〇: 1 to · »1:10 and preferably a prepolymer derived from a ratio of 5: 5 to 1: 9, from (perfluorohexyl) (ra) ethyl yeast and N-B- or N-A- A prepolymer derived from N-2-hydroxyethyl perfluorooctane sulfonamide in a ratio ranging from 10: 1 to 1:10, preferably about 1: 1. The polyisogas ester component used in the production method of the present invention may contain only one type of the reaction product or may contain different types of the reaction product derived from different substantially fluorinated isocyanate-reactive compounds and / or different polyisocyanates. The amount of polyisocyanate used in the preparation of the aerogel in this method ranges from 0.5 to 30¾ / weight based on the total weight of the reaction mixture, preferably from 2 to 20¾ weight, more preferably from 3 to 10¾ weight. This preparation method uses higher-functionality isocyanate-reactive compounds, including sulfonate-12- This paper scale is applicable to the Chinese National Falcon (CNS) A4 specification (210X 297mm> (Please read the precautions on the back before filling in This page) Binding · Order A7 ΒΊ ___ printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (1Q) Oxygen such as ethylene oxide and / or propylene oxide, with 2 to 8 per molecule • V. Active hydrogen Atomic initiator. The two-reaction reaction product preferably has an average hydroxyl number from 300 to 1000, especially from 700 to -1000 mg KOH / g, and a hydroxyl functionality from 2 to 8, especially from 3 to 6. Suitable initiators include: Polyols such as water / glycerol, ethylene glycol, diethylene glycol, tris (hydroxymethyl) propane, tris (ethyl yeast) amine, pentaerythritol, resorcinol, naphthophenol, rowan sugar fermentation and Sucrose; polyamines such as ethylenediamine, toluenediamine, melamine, 1,2,3-triaminobenzene, 1,3,4-triaminobenzene, diethylenetriamine, tetraethylenepentamine, Pentaethylenehexamine, diaminodiphenylmethane and polymethylene multiple phenyl multi-limb; with amino alcohols such as ethanolamine, diethylpyramine and tris Alcohol amine; a mixture with these initiators. This method uses preferred isocyanate-reactive compounds with higher functionality including hydroxyethylated / hydroxypropylated ethylenediamine. If polyfunctional isocyanate-reactive compounds are present When | M based on the amount of polyisocyanate, its dosage range is from 1 to 60¾, preferably from 5 to 30 L by weight. Polyisocyanate and higher-functionality isocyanate-reactive compounds have an isocyanate index between 100 and 600 When changing, the index reaction is preferably about 400. The trimerization catalyst used in this method includes any isocyanate trimerization catalyst known in the art such as quaternary ammonium hydroxide, alkali metal and alkaline earth metal hydroxide L compounds , Fermented salt and hydroxy acid salt such as potassium acetate and potassium 2-ethylhexanoate, some tertiary amines and non-alkaline auronic acid hydroxy acid salt such as lead acetate, and symmetrical tri-cultivated derivatives. The best catalyst used in this method is the tri-catalyst catalyst Δ 1 ycat 4 1 from A bb 〇11 L ab 〇rat ries and DABCO TMR, TMR-2 and TMR- from A ir Products 4. -13- This paper scale is applicable to China National Standards (CNS) A4 Specifications (210X297 mm.) I 1 I— g * l ^ im HI i, ^ OJ (please read the precautions on the back before filling this page) 315375 Central Standard of the Ministry of Economic Affairs, printed by A7 B7 by the Bureau ’s Employee Consumer Cooperative V. Description of the invention (11) The urethane catalyst used in this production method includes any catalyst known in the art to promote the reaction of urethane and / or urea. I Urethane catalyst includes aliphatic and aromatic tertiary amines such as N, N- Dimethycyclohexylamine is good. Metal compounds, especially tin compounds, such as stannous octoate and dibutyltin dilaurate, alkali gold and so on. Preferred urethane catalysts include < catalyst SFC, catalyst SFB from Inner Gate, and Niax A1 from Union Carbide. It can use any mixture of trimeric catalyst and urethane catalyst. The composition of the catalyst package will depend on the reaction conditions required. Urethane catalyst / trimerization The weight ratio of catalyst varies between 0 and 2: 1. The weight ratio of polyisocyanate / catalyst varies between 5 and 1000. The preferred polyisocyanate / catalyst weight ratio depends on the use of polyisocyanate, the reaction / heating temperature, the solvent used and the additives used (such as polyfunctional polyol, etc.). The rules under Μ should be used as examples (not everything). The polyisocyanate / catalyst weight ratio at a polyisocyanate level of about 2 0¾ based on the weight of the total reaction mixture is preferably higher than 600, preferably between 700 and 800; this ratio is about 15¾ weight based on the polyisocyanate level of the reaction mixture Between 400 and 700, preferably between 500 and 600; when the total reaction mixture base polyisofluorate level is about 10¾ weight, the ratio is between 350 and 550, preferably between 40 0 and __ 5 0 0 At low polyisocyanate levels (about 5% by weight of the total reaction mixture base), the ratio is between 50 and 450, preferably between 100 and 350. If the prepolymer of the polyisocyanate and the isofluorate-refractory compound is used together with the gaseous solvent about 20 vfti: the preferred polyisocyanate / catalyst ratio for polyisocyanates varies between 100 and 400, about 15 wt % Polyisofluoric acid-14- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) I ------- see-- (please read the precautions on the back before filling this page) )

* 1T A7 B7 printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (12) The esters are between 50 and 200, and the ones with approximately 10wt% polyisocyanate are between 10 and 100 (compare Good between 30 and 60). ‘-The solvent used in the preparation method according to the present invention should be a monomeric (unreacted) polyisocyanate M and a polymerized (reacted) polyisocyanate solvent. The ability of ## should be able to form a homogeneous solution of unreacted mixture and dissolve the reaction product or at least prevent the reaction product from flocculating. Solvents have S Hansen solubility parameters between 10 and 35 MPa1 / 2, preferably between 15 and 30 MPa1 / 2, and most preferably between 18 and 26 MPa 1/2. In addition, the critical pressure and critical temperature of the solution should be kept as low as possible to simplify the critical drying step. Suitable solvents for use in the method of the present invention include hydrocarbons, dialkyl ethers, cyclic ethers, ketones, alkyl alkanoates, aliphatic and cycloaliphatic hydrofluorocarbons, hydrofluorocarbons, chlorofluorocarbons, hydrochlorocarbons Halogenated aromatic compounds and gas-containing ethers. Mixtures of these compounds can also be used. Suitable hydrocarbon solvents include low-aliphatic or cyclopentane such as n-pentane, isopentane, cyclopentan, neopentam, sesame and cyclohexane. Suitable dialkyls for use as solvents include compounds having 2 to 6 carbon atoms. As examples of suitable ethers, mention may be made of dimethyl ether, methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, dipropyl ether , Propyl isopropyl ether, diisopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl t-butyl ether, ethyl butyl ether, ethyl isobutyl ether and ethyl t-butyl ether. Suitable cyclic ethers include tetrahydrofuran. * Suitable dialkyl ketones for solvents include acetone and methyl ethyl ether. Suitable alkyl alkanoates that can be used as solvents include methyl formate, methyl acetate, -15- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Order (please read the notes on the back first Please fill in this page for details) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (13) Ethyl formate and ethyl acetate. · Suitable hydrogen hydrocarbons that can be used as solvents include low hydrofluoroalkanes such as difluoromethane, 1,2-difluoroethane, 1,1,1,4, bu 4-hexafluorobutane, pentafluoroethane , 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluorobutane, tetrafluoropropane # and pentafluoropropane. Suitable hydrofluorocarbons that can be used as solvents include atmospheric difluoromethane, 1,1-dichloro-2,2,2-trifluoroethane, 1, budichloro-1-fluoroethane, 1-ambient- 1,1-difluoroethane, chloro-2-fluoroethane and 1,1,1,2-tetrafluoro-2-fluoroethane. Suitable chlorofluorocarbons that can be used as dissolving agents include trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane and tetrafluorodichloroethane. Suitable hydrochlorocarbons that can be used as solvents include Bu and 2-chloropropane and dichloromethane. Suitable halogenated aromatics include mononitrobenzene and dichlorobenzene. * # »Suitable fluorinated ethers that can be used as solvents include bis (trifluoromethyl) ether, trifluoromethyl difluoromethyl ether, methyl fluoromethyl ether. Methyl trifluoromethyl ether, bis (difluoromethyl) ether, fluoromethyl difluoromethyl ether, methyl difluoromethyl ether, bis (fluoromethyl) ether, 2, 2,2-trifluoro Ethyl difluoromethyl ether, pentafluoroethyl trifluoromethyl ether, pentafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,2, 2,2-tetrafluoroethyl fluoromethyl ether, 1,2,2-trifluoroethyl; ^ fluoromethyl ether, 1, difluoroethyl methyl ether, 1,1,1,3,3 , 3-Hexafluoroprop-2-ylfluoromethyl ether. The preferred solvents used in the method of the present invention are dichloromethane, methyl ethyl ketone, tetrahydrofuran, monochlorobenzene, trichlorofluoromethane (CFC 11), chlorodifluoromethane (HCFC 22), 1, 1. Butrifluoro-2-fluoroethane (HFC 134a), -16- This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) Binding J, (please read the precautions on the back before filling in this Page) 315375 A 7 B7 5. Description of the invention (14) 1, dichloro-difluoroethane fHCFC 141b) and mixtures thereof such as HCFC 1 41 b / CFC 11 mixtures, etc.-Another suitable solvent is liquid ib carbon (C〇2). Liquid carbon dioxide can be used at various pressures (63 bar M at 20 ° C) and temperatures. Secondary or supercritical carbon dioxide can also be used as a solvent. The solvent power of sub- or supercritical carbon dioxide can be adjusted by adding appropriate modifiers such as methanol, ethanol, acetone, HCFC 22, dichloromethane or any other solvent as mentioned above. In the case of using liquid carbon dioxide as a solvent, a prepolymer of fluorinated isocyanate ends made of a polyisocyanate and a fluorinated isocyanate-reactive compound such as a fluorinated unit enzyme or glycol is used in the present aerogel preparation method Medium made polyisocyanate proved to be advantageous. Polyisocyanates, catalysts (etc.), solvents and higher-functionality isocyanate-reactive compounds are only mixed by shaking the reactor or slowly agitating the mixture. Or first mix polyisocyanate, solvent, and optionally higher-functionality isoxate reactive compound • Then add catalyst (etc.) (in any order). Several catalysts can also be added after gelation to promote post-curing. 'Mixing can be done at room temperature or at a slightly higher temperature. In the case of low-boiling solvents (boiling points below room temperature) such as HCFC 22, @agent is added to its own vapor pressure or under pressure to contain polyisocyanate, printed by the Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative (please read the back first Please pay attention to this page and then fill out this page) (etc.) In the press with optional higher-functionality isoflurate-reactive compounds. The mixture is then left for a period of time to produce a polymeric gel. The time varies from 1 minute to several weeks depending on the size and density of the system and the target gap a -17- This paper scale is applicable to China National Standard (CNS) A4 specifications (210X297 mm) B7 B7 Ministry of Economic Affairs, Central Bureau of Preservation of staff consumption The cooperative prints Λ and invention description (15). It can be used from about 20TC to about 50t, preferably from 40 to 451C. The temperature of the solvent used in M is about 1Dt at the boiling point M: the temperature is better. In the case of low-boiling solvents such as HCPC 22, the pressure in the closed container is maintained at its saturated vapor pressure or higher, and gelation is performed at a higher temperature (preferably in the range of 30 to 50 °). At these elevated reaction temperatures, DABCO TMR is the preferred catalyst for the trimerization reaction. Although the compound gels within a few hours, it has been found that maturing the gel for a minimum of 24 hours is beneficial to obtain a solid gel that is easy to handle in subsequent processing. Can be included in the heating cycle after the high temperature. The size of the small gas chamber of the obtained gel must be supercritically dried. The large capillary force at the liquid-vapour contact surface causes the gel to shrink or break when it evaporates to remove the solvent. In the case of supercritical drying, the surface tension is not exceeded by the pores, and the dry aerogel maintains the original shape of the gel. The supercritical fg drying package of the aerogel obtained in the present invention contains placing a gel filled with a solvent in a temperature-controlled pressure vessel, and raising the pressure of the vessel to the critical pressure M of the solvent (for example, filled with nitrogen). At that point, the container is heated above the critical temperature of the solvent. After a few hours, slowly release the pressure in the device while maintaining a constant temperature. Remove the aerogel from the container after a cooling period at atmospheric pressure. The foam density is higher than its theoretical value due to shrinkage during the drying step. Before the critical drying step, the gel can be exchanged into an agent more suitable for supercritical drying, such as liquid carbon dioxide, possibly through an intermediate solvent such as acetone or through liquid carbon dioxide containing modifiers. y The stupidity of the aerogel according to the present invention and its preparation method is that this solvent exchange step is not really necessary. According to the known organic and inorganic aerogels of the water-based system, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) -------- Installation ------ Order- ---- (Please read the precautions on the back before filling in this page) A7 B7 printed by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ------ V. Invention Instructions (16) At least two solvent inspection steps are required Only supercritical drying.

—V The aerogel obtained in this way exhibits an open-bubble structure with a maximum bubble size of 100 nmM ° / Possible applications of this aerogel include, but are not limited to, eg in the freezer and structure #insulation, catalyst support, choice Sexual permeable membrane, chemical treatment gas filter in the color analysis package, surveillance detector, lens' solar collector and impedance matching device, etc. Future energy applications include lightweight thermal insulation clothing, refractory building materials, high-resolution sound detectors, autofocus cameras, electronic and magnetic dielectric spacers, sound-absorbing and heat absorbers for packaging high-priced temperature-sensitive products, and Cerenkov detectors Sister parts for internal use, sister parts for high-energy physics, or parts for fusion targets in an inert enclosure. When the aerogel is crushed, it can be used as a filler in the evacuated insulation board. The supercritical drying step can include a carbonization step to produce a carbon aerogel, which is particularly suitable for use in capacitors. The present invention is exemplified by, but not limited to, the T Ben example. Example 1 Weigh a known amount of polymeric MDI (Suprasec DNR from Inner Door) in an open cup. Dichloromethane was then added, and the mixture was stirred until a homogeneous blend (20 wt% Suprasec DNR) was obtained. Polycat 41 catalyst (available from Abbott Laboratories) Polycat 41 (polyisocyanate_ester / catalyst weight ratio 200) was added with a microliter syringe, and the timer was started after stirring for 10 seconds with a spatula. Use the .- Vibrating Needle Thermometer to track the increase in viscosity. Use an immersion thermocouple to track the reaction heat in the center of the solution. The gel time (viscosity V reaches half of its maximum rise) is 73 minutes, and the maximum reaction temperature is 29Ϊ :. The resulting gel was supercritically dried. The gel is transferred in a vial and used at room temperature " 19- This paper is suitable for the Chinese National Standard (CNS) A4 specification (210X2M mm) nn ^^^ 1 ml nn l ^ i {n n > ^ n (Please read the precautions on the back before filling in this page) 'va 315375 A7 B7 V. Description of the invention (17) Printed nitrogen pressurized by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. After reaching 70 bar < force, the temperature of the furnace containing the container rises to a temperature of 250 1C. Following this, the gel was flushed with nitrogen for Γ hours, keeping the pressure and temperature unchanged. Yuan slowly releases the pressure in the container until it reaches the clothing condition, while maintaining a constant temperature. After the cooling period (15 minutes), remove the dried aerogel from the container. # 得 gel transparent, orange-yellow. The density of the resulting gel was 800 kg / m3. The resulting gel was characterized by transmission electron microscopy (TEM) and Brunauer-Emmet-Tel ler * nitrogen adsorption (BET). BET measurement of the aerogel showed a specific area of 15 ra2 / g. TEM photographs indicate a characteristic size of 50 nm (see Figures 1 and 2). Example 2 A known amount of polymeric MDI (Suprasec DNR from Inner Door) was weighed in an open cup. Subsequently, diazomethane was added, and the mixture was stirred to obtain a uniform blend (10 v / t% Suprasec DHR). Use a microliter syringe to add catalyst Polycat 41 (polyisocyanate / catalyst weight ratio 400) from M Abbott Laboratories. The reaction was carried out in a closed cup at room temperature. After about 8 hours, a gel was formed and allowed to stand for about 24 hours. The resulting gel was supercritically dried. Transfer the gel into a pressurized vial and rinse it with liquid CO 2 at room temperature and 90 to 95 bar pressure for 30 minutes. Leave it in liquid CO 2 at 25 to 28 ° C and 95 bar for 30 minutes, and then liquid CO at 30¾ And-Rinse from 90 to 95 bar for another 30 minutes. Increase the temperature to 50C while keeping the pressure constant at 90 to 95 bar. Then the gel was rinsed for 3 hours from critical CO2. Slowly (within 1 hour) release the pressure in the vessel to atmospheric pressure while maintaining the temperature. After the cooling period, remove the dried aerogel from the container. 'Get a white opaque aerogel with a density of 350 kg /) " 3. For aerogels (please read the precautions on the back before filling out this page) The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297mm). The Central Consumers ’Bureau of the Ministry of Economic Affairs of the People ’s Consumer Cooperative A7 B7_____ 2. Description of the invention (18) BET measurement found that the specific area was 2100 m2 / g and the average pore diameter was 18 nm in desorption mode. 0 ~ Tube Example 3 〆〆 An aerogel was prepared according to the route described in Example 2, except that the supercritical drying step contained Dissolve exchange to copper propyl. The solvent was exchanged 5 times within 5 days, and the gel changed from yellow transparent to white opaque. A white opaque aerogel was obtained with a density of 350 kg / m3. The BET measurement of the aerogel revealed a specific area of 380 m2 / g and an average pore size of the desorption horizontal mode 2 0 n m 0 -Tuan Li 4 The reactor contains a known amount of polymerized polyisocyanate (SUPRASEC X2185 from ICI). Add diazomethane to obtain a 3¾ weight polyisocyanate blend in dichloromethane. The catalyst DABC0 * 1 TMR from Air Products was added to achieve a polyisocyanate / catalyst weight ratio of 50. Close the container and stir the mixture with a magnetic stirrer. Place the sealed container in the 451 box. After 1 hour, a solid gel formed. The container was kept on the 9th of the 45 ° calendar. After this heating time, the diazomethane was exchanged with propylene through several addition / removal cycles. After the acetone solution does not contain dichloromethane, the liquid carbon dioxide is rinsed with carbon dioxide at room temperature and a pressure of 90 to 95 bar for 30 minutes. Leave sample 1 exposed to liquid carbon dioxide for 30 minutes, and then continue to flush with liquid carbon dioxide for another 30 minutes. Raise the temperature to 50 ° C while maintaining a pressure of 90 bar and flush with supercritical carbon dioxide for 3 hours. After this rinsing, slowly release to atmospheric pressure and allow the sample to cool. -Obtained white opaque aerogel with a density of 140 to 180 kg / m2, compared with Table-21-This paper scale is applicable to the Chinese National Standard (CNS) A4% # (210X297mm) IIIIIII n Order I IV- (please read Jing first Note on the back and then fill out this page) A7 _ i 'Invention Description (19) Area 900 mz / g: and average pore diameter 7.5 nm printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Example 5 • Weighing polymeric polyisocyanate > SUPRASEC X2185 obtained from Buinmen) in a pressure vessel. Add polyisocyanate / catalyst level 50 DABCO TMR (L # from Air Products) and dichloromethane M to obtain a blend of 32 weight polyisofluorate in dichloromethane. Close the container, stir the mixture, and put it statically in a 40-45 t: box for 7 days, following the 7-day room temperature heating time. ○ Under pressure, exchange diazomethane at 90 bar pressure and 25¾ temperature to liquid carbon dioxide. After this solvent exchange, the temperature was raised to 85 ° while still maintaining a constant pressure. Μ Supercritical carbon dioxide rinses the container after 30 minutes and slowly releases pressure and temperature to the surrounding state. The resulting opaque aerogel has a density of 200 kg / m3, a specific surface area of 800-850 m2 / g and an average pore diameter of 6-8 nm. Figure 3 shows the thermal conductivity (lambda value at 10 ° C λ m MW / πΓ Κ) as a function of pressure (M mbar) after the resulting aerogel is crushed into coarse powder with particle sizes of 100 to 200. The same aerogel was crushed to 1 0 -20 ounces to obtain the particle size to obtain the lambda pressure result shown in Fig. 4 Tube example fi — prepared from SUPRASEC X2185 (available from ICI) and hydroxylated alcohol derived from methanol A prepolymer with an ethylene oxide / propylene oxide content of I5 / 85, a molecular weight of 600, and a hydroxyl value of 9i mg KOH / g. The NC0 value of the resulting prepolymer was 15.8¾. Weigh a known amount of this prepolymer in a pressure vessel equipped with a magnetic stirrer-22- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2IOX297mm) I * n 11. ^ 111 I n ^ IIII I- ^ (Please read the precautions on the back before filling out this page) A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (20). Add a mixture of Polycat 41 (available from 'Ai' Products) and HCFC 22 (0.75 m 1 catalyst / 5 0 HC f C 2 2) to the prepolymer M so far to obtain a solution of the prepolymer in HCFC 22 The polyisocyanate / catalyst ratio is 20. The mixture is vigorously stirred for 20 minutes and allowed to stand at room temperature for 5 days. # After the conversion period, add HCFC 22 to the container to a pressure of 40 bar. Gradually increase the temperature to 1 20 ° C and maintain the maximum Pressure 90 bar. Maintain this condition for 30 minutes and then gradually release the pressure. At the same time, flush the pressure vessel with nitrogen at the specified pressure. Gradually relax the pressure to atmospheric conditions and let the sample cool. The resulting opaque aerogel has a density of 650 kg / in3 and a surface area of 4δ m2 / g Ο Example 7 2 g of hydroxypropylated ethylenediamine and 8 g of SUPRASEC Χ2185 (obtained from Bu Nemen) were mixed with 90 g of dichloromethane. To this mixture was added 0.1 m 1 of catalyst SFC ( (Obtained from Bu Neimen). The reaction mixture was stabbed for 1 minute and then stood at 451. After 20 hours, 0.005 ml of DABCO TMR (from Air Products) was added to increase the post-maturation reaction. A uniform translucent gel was generated, using the previous example 5. Supercritical drying according to the procedure described in 5. The obtained aerogel has a density of 427 kg / πι3 and an average pore diameter of 18.5 nra, The surface area is 266m 2 / g. When Example 8 repeats the experiment described in the previous Example 7, using 1 g of hydroxypropylated ethylenediamine * 0.075 ml of catalyst SFC and 0.025 ml of Polycat 41. A uniform gel was generated at 45 ° C for 8 hours, Allow to mature at room temperature for 2 days. After supercritical drying of the transparent aerogel, the specific surface area is 445 m2 / g, and the density is -23. This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm). Install i · ν (Please read the precautions on the back before filling in this page) Employee Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economy Du Yinpei 315375 A7 B7 V. Description of the invention (21) 398 kg / m3 and pore size 10.¾ nm.

• " V When Example 9 is repeated, Example 8 uses only 0.075 cardiac catalyst SFC as the catalyst. Add 0.025 ml DABCO TMR after 4 hours at 45 ° C. After 1 hour at 45 ° C, the gel is evenly cured.

Alfalfa Example 1CL 0,6 g of propylenediamine, 97 g of dichloromethane and 2.4 g of SUPRASEC X2 185 (from Inner Door) were mixed in a pressure vessel. Add 0.3 ml of catalyst SFC- (obtained from Bu Nemen). Close the container and heat to 45t: 2 hours. Add 0.03 ml of DABCO TMR (available from Air

Products) in the reaction mixture. After 90 minutes, a solid opaque gel was formed. 0 Example 1 1

A Repeat Example 10 with 0.3 g hydroxypropylated ethylenediamine and 2.?, G SUPRASEC X2185. After 24 hours, a solid opaque aerogel formed. Example 12 Make a 10 wU SUPRASEC X2185 methyl ethyl methyl solution. A white gel formed after 24 hours at a polyisocyanate / catalyst ratio of 300 plus DABC0TMR (available from Air Products) °. This gel was subjected to liquid carbon dioxide solvent exchange at 90 bar and room temperature, and then supercritical carbon dioxide was removed. The aerogel obtained had a density of 90 kg / m3 and a specific surface area of 56 m2 / g. This aerogel has a powder structure and an average pore size (measured by BET) of 16.7 nra. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling this page) Binding. Order V. Description of Invention (22) A7 B7 Example of window printing by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1 3 Repeat Example 12 in tetrahydrofuran as the solvent, using Polycat 41 with a polyisocyanate / catalyst ratio of 100. 4 The obtained gas gel has a density of 175 kg / n3 and a specific surface area of 448 m2 / g ° g. Example 1 4 Example 13 was repeated in a single gas benzene as solvent. The reaction was slow and a translucent gel was formed after 4δ hours. The obtained aerogel had a density of 284 kg / m3, a specific surface area of 398 m2 / g and a pore diameter of 10.2 n m. Solute 4g SUPRASEC X2185 in 96g THF. Add 0.8 g Polycat 41 to this mixture. Stir the mixture and leave the static Μ9 * · gel-gel. The solvent for exchanging the sol-gel is liquid CO2, and then it dries to a critical temperature at a temperature of 32¾ K and a pressure above 73 bar. An opaque aerogel was obtained with a density of 70 kg / m3, a specific surface area of 515 m2 / g and an average pore size of 10 n is ° Window Li 1 fi dissolved in 3 s XR159 (from Inner Gate) in 125 g CH2CU. To this mixture was added 3.6 g of SUPRASEC X218 5 '(from Inner Gate), and after stirring the mixture for 5 minutes, it was left at room temperature Ψ statically. A few days later, a translucent sol-gel was formed. Transfer this gel to a pressure vessel where the solvent exchange CH2C12 is liquid carbon dioxide. After complete solvent exchange, the sol-gel is supercritically dried at a temperature of 32 t: M and a pressure of more than 73 bar to form a translucent aerogel. Aerogel-25- This paper scale is applicable to China National Standards (CNS) Α4 specification (210Χ: 297mm) (please read the precautions on the back before filling in this page). ** A7 B7 315375 V. Invention Note p) The density is 350 kg / m3 and the specific surface area is 110 m2 / g. Example 1 7 ~ Add 20 g SUPRASEC X2185 (from the inner door) to the pressure vessel. Close the container after flushing the nitrogen hood, and place 0.04 ml Polycat P41 in the & injection ring of the reactor. Charge 13.6 g (: 〇2 into the reactor under steam pressure while evacuating the injection ring. Stir the mixture for 30 minutes, then leave the reactor at room temperature for 1 day. Add 70 g C〇2 after this heating time Enter the manpower device and raise the temperature to above the supercritical temperature (-32Ό) of C02. Allow the pressure inside the device to gradually increase and remain unchanged for at least 30 minutes. Then pressurize in the constant temperature gradual release device. Let the container cool to room temperature. Obtain a solid opaque microporous material with a density of 280 kg / m3. Alfalfa Example 1 8 • I. · Repeat Example 5 with SUPRASEC X24? 4 (1¾ weight from 3M Fluorad FC10 and 99¾ weight from ICI PLC's SUPRASEC X2185) replaces SUPRASEC X2185. (Pluorad is a trademark of 3M) Produces opaque sol-gel, opaque aerogel after supercritical drying, density 183 kg / m3, specific surface area 802 m2 / g and average pore diameter 9.6 nm ° __ SLM..L9. Repeat Example 5 to replace SUPRASEC X2185 with the reaction product of 1¾ weight of 1H, 1H, 7H-dodecyl-1-heptanol from i3M and 99¾ weight of ^ UPRASEC X2273 from ICI PLC 。Produce opaque sol-gel super-pro Opaque gas condensation after drying -26- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 > < 297mm) Packed with i IIIJ (please read the precautions on the back before filling this page) Printed 315375 ay B7 clumps, invention description (> 4) P with density of 174 kg / m 3, specific surface area of 8 3 6 m 2 / g and average pore diameter of 9. 1 To 0, the picture is the glue of the 1 2 picture. 0 凝 _ 凝气 气 明明 发 发 本 This display shows Η: 1Γ According to the number of small and large numbers, the force of the function of the number is the pressure It is a gel of gel, gel, gas and oxygen for sexual conductivity, heat conduction, and heat. 0 Rough milling. This book shows the display. 3 4 Figures (please read the precautions on the back before filling this page).

, Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 7 2 This paper standard applies to China National Standard (CNS) Α4 specification (210 X 297 mm)

Claims (1)

Chinese Shenyan Patent Application No. 6013: Application 11 ¾ Amendment Scope (year β month) Α8 Β8 C8 DS 3 Supplement to the Central Bureau of Standards of the Ministry of Economy ^ Printed by the Industrial and Consumer Cooperatives VI. Patent Scope 1. A preparation of polyisocyanate is The main method of organic aerogel. The aerogel has a pore size less than or equal to 100 nm, a density in the range of 1 to 1000 kg / m3, and a surface area in the range of 10 to 1500 m2 / g. It includes the following steps: ( a) The organic polyisocyanate is selected from the group consisting of fourth ammonium hydroxide, alkali metal and alkaline earth gold hydroxide, alkoxide and carboxylate, fourth amine, non-alkaline metal carboxylate and tri-growth derivatives The sister isocyanate trimerization catalyst is mixed with hydrocarbons, dialkyl ethers, cyclic ethers, _, alkyl alkanoates, aliphatic and cycloaliphatic hydrocarbons, hydrochlorofluorocarbons, chlorofluorocarbons , Hydrochlorocarbons, halogenated aromatic compounds and fluoroethers in the group of solvents, of which organic polyisocyanate is diphenylmethane diisocyanate or polymethylene polybenzyl polyisocyanate or isocyanate terminal prepolymerization Substance and its dosage Based on 0.5 to 30¾ MW weight of the total reaction mixture, and the polyisocyanate / catalyst weight ratio is between 5 and 1000, (b) The mixture is kept static for 1 minute to several weeks to form a polymerized gel , And (c) supercritically drying the resulting gel. 2. The method according to item 1 of the patent application scope, in which a higher-functionality isocyanate-reactive compound and a urethane catalyst are mixed with other components in step (a). 3. The method according to item 2 of the patent application scope, wherein the higher-functionality isocyanate-reactive compound is the reaction product of an alkylene oxide and an initiator containing 2 to 8 active hydrogen atoms per molecule. This paper scale is applicable to China National Standard (CNS) 84 specifications (210X297mm) (please read the precautions on the back before filling this page) --------------: 袭- ---- ίτ ------ Τ --- 6. The patent application garden 4. According to the method of item 3 of the patent application scope, where the initiator is ethylenediamine ------ϋ n-- ---^ (Please read the precautions on the back before filling in this page) 0 5. Root out the method of applying for patent patent item No. 2 'where the amount of high-functionality isocyanate unitary reactive compound is polyisocyanate Vinegar based varies between 1 and 60% by weight. 6. The method of the first item in the scope of patent application, where the isocyanate trimerization catalyst is a trident derivative. 7. According to the method of item 2 of the patent application scope, where the urethane catalyst is a tertiary amine. _ 8. The method according to item 1 of the patent application scope, in which the solvent is methylene chloride 0 9 · According to the method in item 1 of the patent application scope, in which the solvent is supercritically dried after the exchange of the gel. 10. The method according to item 9 of the patent application scope, in which the solvent hydroxyl is exchanged into liquid carbon dioxide. U · —an organic aerogel based on Μ polyisocyanate, which is prepared according to the method of item 1 of the patent application, has a pore size of less than or equal to 100 nm, and a density in the range of 1 to 1000 kg / m3, And the surface area is in the range of 10 to 15 00 m2 / g. Printed by the Ministry of Economic Affairs Central Bureau of Standards and Industry Cooperative Co., Ltd. 1 2. The aerogel according to item 1 of the patent application scope has a pore size in the range of 5 to 50 nm. 13. The aerogel according to the patent application scope of U.S.A. has a density in the range of 20 to 400 kg / m3. 14. According to the aerogel of the patent application scope item u, its surface area is between 200 and -2-This paper scale is applicable to the Chinese standard (CNS > A4 ^ (210X297 公 親) ---- … Yao Liqing, Yin Ke 5: ί: ί ginseng knows snail scales-315375 1 000 m2 / g. Member of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling in this I) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm). Six, the scope of patent application. Binding V '