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TWI845247B - High temperature resistance materials covered aerogel insulation composite material and preparation method thereof - Google Patents

High temperature resistance materials covered aerogel insulation composite material and preparation method thereof Download PDF

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TWI845247B
TWI845247B TW112113082A TW112113082A TWI845247B TW I845247 B TWI845247 B TW I845247B TW 112113082 A TW112113082 A TW 112113082A TW 112113082 A TW112113082 A TW 112113082A TW I845247 B TWI845247 B TW I845247B
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aerogel
temperature resistant
fiber
temperature
organic
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TW202440753A (en
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陳建宏
江承書
柯雅淇
羅吉浤
許文延
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台灣氣凝膠科技材料開發股份有限公司
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Abstract

The present invention discloses a high-temperature resistant materials covered aerogel composite with low dielectric, high heat insulation and high fire resistance characteristics and preparation method thereof. The method comprises steps of: (1) mixed hydrolysis, (2) condensation and dispersion, (3) structural molding, (4) atmospheric drying, (5) outer layer covering, (6) curing molding and (7) surface treatment. In this technology, a trace amount of water dispersible high-temperature adhesive is added to the dispersion condensation aerogel sol and injected into the fiber-containing preformed structure, and dried at high temperature and atmospheric to prepare aerogel preformed materials. And then, preformed materials coated with a high-temperature resistance wrapping materials is cured to prepare aerogel composites with low dielectric, high heat insulation and high fire resistance properties. The high-temperature resistance outer layer of this technology contains single-layer, multi-layer or multi-layer stacking with aerogels and wrapping materials, so that the product can be applied in fire prevention, energy saving and carbon reduction, especially application in the cleanroom or the thermal runaway safety protection of lithium battery module of electric vehicle.

Description

耐高溫材料包覆氣凝膠隔熱複合材及其製備方法High temperature resistant material coated aerogel thermal insulation composite material and preparation method thereof

本發明係有關於一種耐高溫材料包覆氣凝膠,尤其關於一種兼具無粉塵、高隔熱、高防火及低介電的氣凝膠複合材料,及其製備方法。The present invention relates to a high temperature resistant material coated aerogel, and more particularly to an aerogel composite material with the characteristics of no dust, high heat insulation, high fire resistance and low dielectric constant, and a preparation method thereof.

眾所皆知地,氣凝膠是一種具立體網狀結構的多孔隙材料,孔隙率高於80%(甚至可高於95%),並具有低密度(約0.005至0.2g/cm 3)、高比表面積(500至2000m 2/g)、低熱導率(k=15至40mW/mk)及低介電性質(D k=1.3至2.0)、低介電損耗(D f<0.003以下)等特性,使得氣凝膠或其複合材料成為高隔熱、高防火、及低介電等優異特性。由於氣凝膠或其複合材料因具有大量孔隙率與極低密度,因此在高隔熱、高防火、低訊號傳輸阻力、及高耐電衝擊等應用方面具有相當高的價值性,因此在未來各類產業如高溫防火、高耗能生產設備或傳送管路的節能減碳應用上有其戰略地位。雖然目前一般有機發泡材料在常溫或120度以下環境擁有不錯的隔熱效果,但這些有機發泡材料製備過程已經造成環境的污染,並且產品應用在溫度高於120度以上環境,將會快速裂解而喪失其隔熱效果,在120度或更高溫環境,有機發泡材料將有其應用的侷限。另外,一般無機纖維隔熱產品可應用在高溫隔熱,但其對於長時間熱源的阻隔性質並不優越,因此,未來針對節能減碳應用上就必須以更優異的氣凝膠或其相關複合材料取代傳統的有機發泡材料或無機纖維隔熱產品,因而能提升隔熱效率及提升能源利用率,以提高節能減碳效果並降低產品製程碳排。另外,未來5G或6G等快速傳輸的資料傳輸設備或電動自駕車訊號高速傳輸等高頻應用上也亟需具備低介電常數(D k<2.5)、低介電損耗(D f<0.003) 及高耐電衝擊等介電材料。由基礎材料理論得知,材料內部多孔性會明顯降低熱能及電子電洞的傳輸,因此材料結構孔隙率越高,其介電性質就越好。緣此,次微米級奈米等級多孔性二氧化矽氣凝膠材料除了能防止熱逸散,也可應用在5G或6G等快速傳輸的資料傳輸設備。因多孔性二氧化矽氣凝膠明顯降低介電常數以及介電損耗,在訊號傳輸端以及接受端應用也可增加訊號傳輸效率及降低訊號損失。在未來自動駕駛車輛或航天器具也有其應用價值。然而,氣凝膠材料擁有以上優異的隔熱及介電效果,但材料內部分子間僅具有微弱的凡得瓦爾作用力,因此導致氣凝膠相關產品極容易造成粉塵脫落,因此,氣凝膠相關產品至目前還不適合應用於無塵室等嚴苛的環境中。對此,本發明團隊期望針對氣凝膠相關產品應用於無塵室製程節能減碳材料及電動車高速傳輸或鋰電池熱失控等高溫阻隔材料進行開發,期望有效解決氣凝膠奈米粉塵擴散或粉塵掉落等造成危害的防制是目前亟需努力的目標。目前,國際已公開專利所揭露的各種氣凝膠材料外加包覆技術中,尚無法完全抑制奈米氣凝膠粉塵外洩的疑慮,尤其在200度高溫以上,目前所揭露之技術使用的有機系列包覆材料(例如:聚丙烯、聚酯、聚醯亞胺及氟聚合物等薄膜)長時間在高溫環境中受熱,相關有機薄膜也將逐漸老化與劣化下,終將會造成氣凝膠粉塵外洩或粉塵掉落等嚴重現象,這些現象對於無塵室或是電動車鋰電池高溫阻隔材料而言,依然是一個重要且須解決的問題。 As is known to all, aerogel is a porous material with a three-dimensional network structure, with a porosity higher than 80% (even higher than 95%), and has low density (about 0.005 to 0.2g/ cm3 ), high specific surface area (500 to 2000m2 /g), low thermal conductivity (k=15 to 40mW/mk), low dielectric properties ( Dk = 1.3 to 2.0), low dielectric loss ( Df <0.003), etc., making aerogel or its composite materials have excellent properties such as high thermal insulation, high fire resistance, and low dielectric properties. Aerogel or its composite materials have a large amount of porosity and extremely low density, so they have a very high value in applications such as high thermal insulation, high fire resistance, low signal transmission resistance, and high electrical shock resistance. Therefore, they have a strategic position in various industries in the future, such as high-temperature fire protection, high-energy-consuming production equipment or transmission pipelines for energy saving and carbon reduction. Although the general organic foam materials currently have a good thermal insulation effect at room temperature or below 120 degrees, the preparation process of these organic foam materials has caused environmental pollution, and the products will quickly decompose and lose their thermal insulation effect when used in an environment with a temperature above 120 degrees. In an environment with a temperature of 120 degrees or higher, organic foam materials will have their application limitations. In addition, general inorganic fiber insulation products can be used for high-temperature insulation, but their barrier properties for long-term heat sources are not superior. Therefore, in the future, for energy-saving and carbon-reduction applications, it is necessary to replace traditional organic foam materials or inorganic fiber insulation products with more excellent aerogels or related composite materials, thereby improving insulation efficiency and energy utilization, thereby improving energy-saving and carbon-reduction effects and reducing product process carbon emissions. In addition, in the future, high-frequency applications such as 5G or 6G data transmission equipment with fast transmission or high-speed transmission of electric self-driving car signals also urgently need dielectric materials with low dielectric constant (D k <2.5), low dielectric loss (D f <0.003) and high electrical shock resistance. According to basic material theory, the internal porosity of a material will significantly reduce the transmission of heat energy and electron holes. Therefore, the higher the porosity of the material structure, the better its dielectric properties. Therefore, in addition to preventing thermal runaway, sub-micron-nano-grade porous silica aerogel materials can also be used in fast-transmission data transmission equipment such as 5G or 6G. Because porous silica aerogel significantly reduces dielectric constant and dielectric loss, its application at the signal transmission end and the receiving end can also increase signal transmission efficiency and reduce signal loss. It also has application value in future autonomous vehicles or aerospace equipment. However, although aerogel materials have the above excellent thermal insulation and dielectric effects, there is only a weak van der Waals force between molecules inside the material, which makes aerogel-related products very easy to cause dust to fall off. Therefore, aerogel-related products are not suitable for use in harsh environments such as clean rooms. In this regard, the invention team hopes to develop aerogel-related products for use in clean room process energy-saving and carbon-reducing materials and high-temperature barrier materials such as electric vehicle high-speed transmission or lithium battery thermal runaway. It is hoped that the prevention of hazards caused by aerogel nano-dust diffusion or dust falling is an urgent goal. At present, the various aerogel material coating technologies disclosed in international patents have not been able to completely suppress the concern of nano aerogel dust leakage, especially at temperatures above 200 degrees. The organic series coating materials (such as polypropylene, polyester, polyimide and fluoropolymer films) used in the currently disclosed technologies are heated in a high temperature environment for a long time, and the relevant organic films will gradually age and deteriorate, which will eventually cause serious phenomena such as aerogel dust leakage or dust falling. These phenomena are still an important problem that needs to be solved for clean rooms or high-temperature barrier materials for electric vehicle lithium batteries.

傳統氣凝膠的製備方法為溶膠凝膠合成法,主要先由烷氧化矽類(alkoxysilane)、正矽酸甲酯或水玻璃等前驅物與大量有機混合溶劑進行混合後,再加入酸觸媒以進行水解反應(hydrolysis)。待水解反應一定時間後,再添加鹼觸媒,以進行縮合反應(condensation),而縮合反應過程中會逐漸形成溶膠,溶膠內的分子繼續進行反應鍵結,逐漸形成半固態的高分子凝膠。接著,再經一段時間熟化(aging),使凝膠形成結構穩定的立體網狀結構。最後,再利用正丁醇、正己醇、正己烷或環己烷等疏水性溶劑進行溶劑置換,再以超臨界乾燥技術將氣凝膠結構中的溶劑萃取乾燥。傳統的製程技術除了需消耗大量且昂貴的有機溶劑及超臨界設備外,另外還須利用疏水性溶劑進行長時間的溶劑置換,因此製備氣凝膠的成本高昂且耗時。The traditional method for preparing aerogels is the sol-gel synthesis method, which mainly involves mixing precursors such as alkoxysilane, methyl orthosilicate or water glass with a large amount of organic mixed solvents, and then adding an acid catalyst to carry out a hydrolysis reaction. After the hydrolysis reaction has been going on for a certain period of time, an alkaline catalyst is added to carry out a condensation reaction. During the condensation reaction, a sol is gradually formed, and the molecules in the sol continue to react and bond, gradually forming a semi-solid polymer gel. Then, after a period of aging, the gel forms a stable three-dimensional network structure. Finally, a hydrophobic solvent such as n-butanol, n-hexanol, n-hexane or cyclohexane is used for solvent replacement, and then the solvent in the aerogel structure is extracted and dried using supercritical drying technology. In addition to consuming a large amount of expensive organic solvents and supercritical equipment, traditional process technology also requires a long time of solvent replacement using hydrophobic solvents, so the preparation of aerogels is costly and time-consuming.

另一方面,疏水性氣凝膠的製備方法同樣採用溶膠凝膠合成法,主要先由如甲基三甲氧基矽烷(methyltrimethoxysilane,MTMS)或甲基三乙氧基矽烷(methyltriethoxysilane,MTES)等甲基烷氧化矽類前驅物與有機溶劑進行混合後,再加入鹼觸媒,以進行水解反應。待水解反應一定時間後進行縮合反應,而縮合反應過程中會逐漸形成溶膠,溶膠內的分子繼續進行反應鍵結,逐漸形成半固態的高分子凝膠。再經過一段時間熟化後(aging),再利用異丙醇、丙酮、正己烷或環己烷等溶劑進行溶劑置換二到三天,使疏水性凝膠形成結構穩定立體網狀結構。最後,以常壓乾燥技術將氣凝膠結構中的溶劑乾燥,以獲得多孔性乾燥的氣凝膠塊材。疏水性氣凝膠的製程也須耗費大量昂貴的有機溶劑,並須進行長時間以醇類或烷類進行溶劑置換,因此製備費時且成本高昂。On the other hand, the preparation method of hydrophobic aerogel also adopts the sol-gel synthesis method, which mainly involves mixing methyl alkoxy silicon precursors such as methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES) with an organic solvent, and then adding an alkaline catalyst to perform a hydrolysis reaction. After the hydrolysis reaction has been carried out for a certain period of time, a condensation reaction is carried out, and a sol is gradually formed during the condensation reaction. The molecules in the sol continue to react and bond, gradually forming a semi-solid polymer gel. After a period of aging, the hydrophobic gel is subjected to solvent replacement for two to three days using solvents such as isopropyl alcohol, acetone, n-hexane or cyclohexane, so that the hydrophobic gel forms a stable three-dimensional network structure. Finally, the solvent in the aerogel structure is dried using atmospheric pressure drying technology to obtain a porous dry aerogel block. The process of hydrophobic aerogel also consumes a large amount of expensive organic solvents and requires a long period of solvent replacement with alcohols or alkanes, so the preparation is time-consuming and costly.

由於上述之氣凝膠製備方法所採用的製程技術均須利用大量疏水性溶劑;如烷類等有機溶劑,進行二至三天的多次溶劑置換,再以超臨界乾燥技術或常壓高溫乾燥技術以避免氣凝膠結構在常壓乾燥過程,受水分子的表面張力影響而收縮或龜裂。「超臨界乾燥」意指水與有機溶劑於高溫及高壓下呈超臨界狀態,使有機溶劑與水同時具備氣-液混合性質,於超臨界狀態下使溶劑直接汽化而乾燥。因此,可以在超臨界條件下移除網狀結構中的剩餘溶劑而不致使濕膠收縮。然而,在相關製程中利用多次疏水性溶劑置換技術以及超臨界乾燥技術相當耗時且成本昂貴,不利於氣凝膠量產及未來應用時的競爭能力。上述疏水改質為利用常溫常壓多梯次溶劑置換技術,但此種改質技術須進行超過24小時,製程所須時間過久而不符成本效益。Since the process technology used in the above-mentioned aerogel preparation method requires the use of a large amount of hydrophobic solvents; such as alkanes and other organic solvents, multiple solvent replacements are carried out for two to three days, and then supercritical drying technology or atmospheric pressure and high temperature drying technology is used to prevent the aerogel structure from shrinking or cracking due to the surface tension of water molecules during the atmospheric pressure drying process. "Supercritical drying" means that water and organic solvents are in a supercritical state under high temperature and high pressure, so that the organic solvent and water have gas-liquid mixing properties at the same time, and the solvent is directly vaporized and dried in the supercritical state. Therefore, the residual solvent in the network structure can be removed under supercritical conditions without causing the wet gel to shrink. However, the use of multiple hydrophobic solvent replacement technology and supercritical drying technology in the relevant process is very time-consuming and costly, which is not conducive to the mass production of aerogels and their competitiveness in future applications. The above hydrophobic modification uses multi-stage solvent replacement technology at room temperature and pressure, but this modification technology must be carried out for more than 24 hours, and the process takes too long and is not cost-effective.

中國發明公開號CN 113873697A及中華民國發明公開號 I750717技術所述之「隔熱件及加熱組件」,其發明提供一隔熱件及加熱組件。一種隔熱件包含一隔熱材料以及一第一包覆隔熱料,並沿一第一車縫位置車縫第一包覆層,以密封隔熱材料。上述隔熱件可防止隔熱材料所產生的粉塵飛散。同時還提供一種包含上述隔熱件之加熱組件。但因氣凝膠粉塵粒徑極小,利用矽膠、銅質烷類潤滑油、非皂基合成潤滑油、鋰基耐壓油脂、矽系油脂以及二硫化鉬類黃油其中之一包覆層包覆氣凝膠材料,再利用車縫線車縫包覆層,雖然可以降低氣凝膠粉塵逸散,但依然無法有效完全抑制次微米及以下氣凝膠粉塵的洩漏而造成無塵室內部污染。The invention of "heat insulation and heating assembly" described in the invention publication number CN 113873697A of China and the invention publication number I750717 of the Republic of China provides a heat insulation and heating assembly. A heat insulation comprises a heat insulation material and a first coating heat insulation material, and the first coating layer is sewn along a first sewing position to seal the heat insulation material. The heat insulation can prevent dust generated by the heat insulation material from scattering. A heating assembly comprising the heat insulation is also provided. However, since the particle size of aerogel dust is extremely small, using a coating layer of silicone, copper alkane lubricant, non-soap synthetic lubricant, lithium-based pressure grease, silicone grease, and molybdenum disulfide butter to coat the aerogel material and then sewing the coating layer with sewing threads can reduce the emission of aerogel dust, but it still cannot effectively and completely suppress the leakage of sub-micron and below aerogel dust and cause internal pollution of the clean room.

中華民國發明公開號TW 201542457所述之「可撓性複合物氣凝膠及製造方法」,主要涉及一種親水性氣凝膠的直接分散製備方法。其方法以本發明係關於可撓性複合物有機氣凝膠,其包含:紡織強化物,於該紡織強化物中放置一有機氣凝膠。該有機氣凝膠係以至少有一部分是由多羥基苯與甲醛產生的樹脂為基礎,該有機氣凝膠係含有至少一種水溶性陽離子聚電解質的聚合有機凝膠,或該有機氣凝膠係多孔碳單塊形態的該凝膠之熱分解物,其包含該至少一種水溶性陽離子聚電解質之熱解作用產物。The "Flexible composite aerogel and manufacturing method" described in the Republic of China Invention Publication No. TW 201542457 mainly relates to a direct dispersion preparation method of a hydrophilic aerogel. The method is related to a flexible composite organic aerogel, which includes: a textile reinforcement, and an organic aerogel is placed in the textile reinforcement. The organic aerogel is based on a resin at least partly produced from polyhydroxybenzene and formaldehyde, the organic aerogel is a polymerized organic gel containing at least one water-soluble cationic polyelectrolyte, or the organic aerogel is a thermal decomposition product of the gel in the form of a porous carbon monolith, which contains the thermal decomposition product of the at least one water-soluble cationic polyelectrolyte.

中華民國發明公開號TW I655094技術所述之「氣凝膠複合物及製備該氣凝膠複合物之方法」,主要涉及一種氣凝膠複合物。該氣凝膠複合物係包含至少一層具有上表面及下表面之基底層,該基底層係包含增強氣凝膠組成物且該氣凝膠組成物係包含增強材料及單塊氣凝膠框架;第一覆面層,其係包含黏附至該基底層之上表面的第一覆面材料;以及第二覆面層,其係包含黏附至該基底層之下表面的第二覆面材料。該基底層之該單塊氣凝膠框架的至少一部分係延伸進入該第一覆面層及該第二覆面層兩者之一部分。該第一覆面材料及該第二覆面材料可各自包含彈性纖維如氨綸、尼龍、萊卡、彈力纖維、或其組合,或主要由彈性纖維組成。但因所製備之氣凝膠包覆材為包含彈性纖維或柔軟高分子片膜,且所使用黏膠材料也為丙烯酸酯、胺基甲酸乙酯、熱熔黏著劑等有機黏著劑,雖然相關柔軟性產品對氣凝膠有不錯的包護性。The "Aerogel composite and method for preparing the aerogel composite" described in the invention publication number TW I655094 of the Republic of China mainly relates to an aerogel composite. The aerogel composite comprises at least one base layer having an upper surface and a lower surface, the base layer comprising a reinforced aerogel composition and the aerogel composition comprising a reinforcing material and a single aerogel frame; a first covering layer comprising a first covering material adhered to the upper surface of the base layer; and a second covering layer comprising a second covering material adhered to the lower surface of the base layer. At least a portion of the single aerogel frame of the base layer extends into a portion of both the first covering layer and the second covering layer. The first covering material and the second covering material may each include elastic fibers such as spandex, nylon, lycra, elastic fibers, or a combination thereof, or may be mainly composed of elastic fibers. However, since the prepared aerogel covering material includes elastic fibers or soft polymer films, and the adhesive material used is also an organic adhesive such as acrylate, urethane, hot melt adhesive, etc., although the relevant soft products have good protection for aerogel.

中華民國發明公開號TW I663062技術所述之「氣凝膠複合體及其製備方法」,其係涉及一種濕潤包括無機纖維及有機纖維中之至少一的一纖維材料;以一捲取結構將該經濕潤的纖維材料與一隔片或一平面形式積層該經濕潤之纖維材料與該隔片;將該纖維材料填進一容器內;藉將一前驅物注入該容器內及膠凝該前驅物同時於真空下去除殘餘氣泡而製備一凝膠-纖維複合物;自該容器取出該氣凝膠-纖維複合物及去除該隔片;利用溶劑取代及有機表面改性該凝膠-纖維複合物,隨後以大氣壓乾燥或超臨界乾燥將該有機表面改性的凝膠-纖維複合物乾燥。The invention of the Republic of China, Publication No. TW I663062, describes an "aerogel composite and its preparation method", which relates to a fiber material comprising at least one of an inorganic fiber and an organic fiber being wetted; the fiber material being wetted and a spacer being layered on a plane in a roll-up structure; the fiber material being filled into a container; and a front drive being provided to the container. The invention relates to a method for preparing a gel-fiber composite by injecting a precursor into the container and gelling the precursor while removing residual bubbles under vacuum; taking out the aerogel-fiber composite from the container and removing the separator; substituting and organically surface modifying the gel-fiber composite by solvent, and then drying the organically surface-modified gel-fiber composite by atmospheric pressure drying or supercritical drying.

中華民國發明公開號TW I743082技術所述之「包含強化氣凝膠複合材料之積層體」,其係涉及一氣凝膠複合材料。該氣凝膠複合材料包含具有一頂部表面和一底部表面的至少一基底層,該基底層包含一強化氣凝膠組成物和一單塊強化氣凝膠框架,該組成物包含一強化材料、一第一面層,其包含接附至該基底層的該頂部表面的一第一面材料、以及一第二面層,其包含接附至該基底層的該底部表面的一第二面材料。該基底層的單塊氣凝膠框架的至少一部分皆延伸至該第一面層和該第二面層兩者的至少一部分。該第一面材料和該第二面材料基本上各自由氟聚合物材料所組成。The "laminated body including a reinforced aerogel composite material" described in the invention publication number TW I743082 of the Republic of China relates to an aerogel composite material. The aerogel composite material includes at least one base layer having a top surface and a bottom surface, the base layer includes a reinforced aerogel composition and a single reinforced aerogel frame, the composition includes a reinforcing material, a first surface layer including a first surface material attached to the top surface of the base layer, and a second surface layer including a second surface material attached to the bottom surface of the base layer. At least a portion of the single aerogel frame of the base layer extends to at least a portion of both the first surface layer and the second surface layer. The first side material and the second side material are each substantially composed of a fluoropolymer material.

中華民國發明公開號TW I765609技術所述之「一種氣凝膠氈的製造方法」,其係涉及一種氣凝膠氈製造方法,其先將氣凝膠漿料注入玻璃纖維氈中,再用浸泡液在玻璃纖維氈表面形成一層封閉塗層,避免氣凝膠氈在儲運和使用過程中出現掉粉的現象。因此,可保證氣凝膠氈中的氣凝膠量不減少,進而不影響氣凝膠氈的保溫性能。其中,其表面封閉塗層為丙烯酸類乳液、滑石粉、VAE乳液和及水性固化劑混合物。The "A method for manufacturing aerogel felt" described in the invention publication number TW I765609 of the Republic of China relates to a method for manufacturing aerogel felt, wherein aerogel slurry is first injected into glass fiber felt, and then a soaking liquid is used to form a closed coating on the surface of the glass fiber felt to prevent the aerogel felt from falling off during storage, transportation and use. Therefore, it can be ensured that the amount of aerogel in the aerogel felt does not decrease, thereby not affecting the thermal insulation performance of the aerogel felt. Among them, the surface closed coating is a mixture of acrylic emulsion, talcum powder, VAE emulsion and water-based curing agent.

本團隊在中華民國發明公開號TW I535658技術所述之「非織物/氣凝膠複合防火/隔熱材及其製備方法」,其係經由一水解步驟及一縮合步驟製備出一氣凝膠,然後在成型步驟時取前述氣凝膠加入一非織物中,使前述氣凝膠充分穿插在該非織物中,並經一乾燥程序,以形成一非織物/氣凝膠複防火/隔熱材,利用將氣凝膠充分穿插在該非織物中係透過含浸加工方式或連續滾壓方式實現;該乾燥程序之條件為常溫常壓下進行無水氣凝膠乾燥,或利用攝氏30度至80度間進行有機溶液快速汽化乾燥。Our team has a patent number TW in the Republic of China. The "non-woven/aerogel composite fireproof/heat-insulating material and its preparation method" described in the I535658 technology is to prepare an aerogel through a hydrolysis step and a condensation step, and then take the aforementioned aerogel and add it to a non-woven fabric during the molding step, so that the aforementioned aerogel is fully interspersed in the non-woven fabric, and undergo a drying process to form a non-woven/aerogel composite fireproof/heat-insulating material. The aerogel is fully interspersed in the non-woven fabric through an impregnation processing method or a continuous rolling method; the conditions of the drying process are to dry the water-free aerogel at room temperature and pressure, or to use the rapid vaporization drying of the organic solution between 30 degrees Celsius and 80 degrees Celsius.

本團隊在中華民國發明公開號TW I643888技術所述之「氣凝膠/複合非織物防火隔熱材之製備方法」,其係經過一混合步驟、一水解步驟及一縮合步驟,以形成一未凝膠化之矽膠-矽氣凝膠-矽烷偶合劑氣凝膠溶液之縮合溶液,然後在成型步驟時採含浸、噴塗、淋噴、或溶液連續壓吸該未凝膠化的矽膠-矽氣凝膠-矽烷偶合劑氣凝膠溶液之縮合溶液至一回收複合非織物毯或一般非織物毯,使該矽膠-矽氣凝膠-矽烷偶合劑氣凝膠凝膠化並穿插在該非織物毯中,並經一乾燥程序,以形成一氣凝膠/複合非織物防火隔熱材,其中,該乾燥程序之條件為常溫常壓下進行氣凝膠乾燥,或利用攝氏30度至80度間進行有機溶液快速汽化乾燥程序,該非織物係利用聚乙烯(PE)、聚丙烯(PP)、聚酯(Polyester)、聚醯胺(Polyamine)、玻璃纖維(glass fiber)、陶瓷纖維(ceramic fibers)、碳纖維(carbon fiber)其中之一或其組合所製成一比較不掉粉塵之氣凝膠複合材料。The "Preparation Method of Aerogel/Composite Nonwoven Fireproof and Heat-Insulating Material" described in the invention publication number TW I643888 of the Republic of China by our team is a process of forming a condensation solution of an ungelled silicone-silicone aerogel-silane coupling agent aerogel solution through a mixing step, a hydrolysis step, and a condensation step. Then, in a molding step, the condensation solution of the ungelled silicone-silicone aerogel-silane coupling agent aerogel solution is impregnated, sprayed, showered, or continuously pressure-absorbed by a solution to a recycled composite nonwoven blanket or a general nonwoven blanket, so that the silicone-silicone aerogel solution is formed. Aerogel-silane coupling agent aerogel is gelled and interspersed in the non-woven blanket, and undergoes a drying process to form an aerogel/composite non-woven fireproof and heat-insulating material, wherein the drying process is performed under normal temperature and pressure, or a rapid vaporization drying process of an organic solution is performed at 30 degrees Celsius to 80 degrees Celsius. The non-woven fabric is made of one or a combination of polyethylene (PE), polypropylene (PP), polyester (Polyester), polyamide (Polyamine), glass fiber (glass fiber), ceramic fiber (ceramic fibers), and carbon fiber (carbon fiber) to form an aerogel composite material that is relatively dust-free.

上述發明專利雖皆係關於氣凝膠複合纖維毯或隔熱材的製造技術,但不管是採用直接製備法,或利用不同有機漿料浸泡法,或利用有機膠材黏結法,以及本團隊先前技術利用軟性矽膠共混合法,其依然存在氣凝膠微細粉塵容易自氣凝膠纖維複合毯中掉落的缺點。當氣凝膠複合纖維毯上容易掉粉時,氣凝膠耐高溫的效果及隔熱性能會逐漸下降,尤其是在180度以上高溫。以上發明專利中所使用有機質氣凝膠、有機包覆材料、有機改質劑或有機膠著劑在180~200度製程條件下會快速老化並裂解,因此產生包覆效果下降下使大量有機微粒或氣凝膠粉塵的洩漏。Although the above invention patents are all about the manufacturing technology of aerogel composite fiber blanket or thermal insulation material, no matter whether it is a direct preparation method, a soaking method using different organic slurries, or a bonding method using organic adhesives, or the previous technology of our team using a soft silicone blending method, it still has the disadvantage that aerogel fine dust is easy to fall from the aerogel fiber composite blanket. When the aerogel composite fiber blanket is easy to fall, the high temperature resistance and thermal insulation performance of the aerogel will gradually decrease, especially at high temperatures above 180 degrees. The organic aerogel, organic coating material, organic modifier or organic adhesive used in the above invention patent will age and decompose rapidly under the process conditions of 180-200 degrees, thereby causing the coating effect to decrease and causing a large amount of organic particles or aerogel dust to leak.

以上有機材料的高溫老化與裂解並導致氣凝膠粉塵外洩,將會造成無塵室或電動汽車內部等高科技產業應用上的污染,此為氣凝膠隔熱材料最大的缺點。會有嚴重的氣凝膠或其複合材料粉塵外洩的主要原因是內部氣凝膠分子間僅具有微弱的作用力縮合聚集形成三次元網狀的多孔洞結構,因此矽基氣凝膠或有機-無機複合材料在高溫應用過程中均極容易產生奈米至微米級的氣凝膠粉塵,這些氣凝膠粉塵一直造成氣凝膠無法快速應用在高科技產業的主要困擾。尤其在高科技產業的精密製程主要是在無塵室內部,因此氣凝膠粉塵對於高科技產業或無塵室污染一直是導致高隔熱氣凝膠省能材料無法應用在高科技產業產線的主要疑慮或主要的問題點。The high-temperature aging and cracking of the above organic materials will lead to the leakage of aerogel dust, which will cause pollution in high-tech industry applications such as clean rooms or the interior of electric vehicles. This is the biggest disadvantage of aerogel thermal insulation materials. The main reason for the serious leakage of aerogel or its composite dust is that the internal aerogel molecules have only weak forces to condense and aggregate to form a three-dimensional network of porous structures. Therefore, silicon-based aerogels or organic-inorganic composites are very easy to produce nano- to micron-sized aerogel dust during high-temperature applications. These aerogel dusts have always been the main problem that aerogels cannot be quickly applied in high-tech industries. Especially in the high-tech industry, the precision manufacturing process is mainly carried out in the clean room. Therefore, the pollution of aerogel dust to the high-tech industry or clean room has always been the main concern or main problem that prevents the application of high-insulation aerogel energy-saving materials in the production lines of the high-tech industry.

針對上述氣凝膠粉塵導致應用上的若干缺失,本發明人萌生改良之構思,並深入進行改善研發與創作,經長時間努力,終有本發明產生。本發明之主要目的即在提供一種高強度、可加工性、高防火、高隔熱性能且具抗靜電之無機材料包覆矽基氣凝膠複合材料之製造方法。In view of the above-mentioned shortcomings of aerogel dust in application, the inventors of the present invention came up with the idea of improvement and carried out in-depth research and development and creation. After a long period of hard work, the present invention was finally produced. The main purpose of the present invention is to provide a method for manufacturing an inorganic material-coated silicon-based aerogel composite material with high strength, processability, high fire resistance, high heat insulation and anti-static properties.

爰此,為改善目前利用聚酯或聚醯亞胺有機薄膜包覆氣凝膠產品在長時間應用過程中容易因老化或裂解導致氣凝膠粉塵洩漏的缺點。本發明技術之目的為提供一兼具高強度、高防火、高隔熱、低介電且避免粉塵洩漏之類纖維強化塑膠(like-fiber reinforced plastic, LFRP)無機包覆矽基氣凝膠複合材料,本技術產品具有高強度、高硬度、高隔熱及高防火等性質,可應用於無塵室高溫製程以及電動車鋰電池模組熱失控的安全防護。本發明技術之另一目的為提供一改善氣凝膠複合材料製備技術,該奈米級至次微米級濕凝膠顆粒懸浮分散溶液中添加一極微量水可分散之耐高溫膠材以製備出兼具高隔熱效率、高防火機能以及不掉粉塵的氣凝膠結構複合材料。Therefore, in order to improve the disadvantage that the current polyester or polyimide organic film coated aerogel products are prone to aging or cracking during long-term application, resulting in aerogel dust leakage. The purpose of the present invention is to provide a fiber-reinforced plastic (LFRP) inorganic coated silicon-based aerogel composite material that has high strength, high fire resistance, high thermal insulation, low dielectric and avoids dust leakage. The product of this technology has the properties of high strength, high hardness, high thermal insulation and high fire resistance, and can be applied to clean room high-temperature processes and safety protection of electric vehicle lithium battery modules from thermal runaway. Another purpose of the present invention is to provide an improved aerogel composite material preparation technology, wherein a very small amount of water-dispersible high-temperature resistant adhesive is added to a suspension dispersion solution of nano-scale to sub-micron-scale wet gel particles to prepare an aerogel structural composite material with high thermal insulation efficiency, high fireproof function and no dust.

爰此,本發明之另一主要目的在氣凝膠產品外層二側分別提供一高隔熱及一高導熱或提供一低介電及一高導電特性表層,以適用於無塵室高溫管路外部覆蓋絕熱層或具絕熱層機具平台,以降低管線內或機具平台介面熱流失以提高節能減碳功效,並利用導電技術提供高溫管路覆蓋絕熱層平台外部導電以降低摩擦靜電的產生。本發明之再另一主要目的則在提供一種複合結構之外部高防火、內部高隔熱,且適用於電動車鋰電池模組的熱逸散阻絕,以避免電動車鋰電池模組的熱失控(thermal runaway),以增加電動車安全性。Therefore, another main purpose of the present invention is to provide a high thermal insulation and a high thermal conductivity or a low dielectric and a high conductive surface on both sides of the outer layer of the aerogel product, so as to be suitable for covering the insulation layer on the outside of the high-temperature pipeline in the clean room or the machine platform with the insulation layer, so as to reduce the heat loss in the pipeline or the machine platform interface to improve the energy saving and carbon reduction effect, and use the conductive technology to provide the high-temperature pipeline covering the insulation layer platform with external conductivity to reduce the generation of friction static electricity. Another main purpose of the present invention is to provide a composite structure with high external fire protection and high internal thermal insulation, and suitable for thermal runaway of electric vehicle lithium battery modules to prevent thermal runaway of electric vehicle lithium battery modules and increase the safety of electric vehicles.

在本技術中首先在氣凝膠製備過程中以懸浮分散技術將縮合溶液分散在大量分散溶液中,隨後加入微量的耐高溫膠著材料分散均勻,再將此懸浮分散溶液注入於預成型的纖維毯中,並經由凝膠成型及常壓乾燥後,可製備低熱傳導係數與高防火的氣凝膠纖維預成型複合結構材;隨後進一步利用含耐高溫樹脂之纖維布、或耐高溫非有機薄膜等進行預成型氣凝膠結構材表層包覆,並隨後進行高溫固化,使含耐高溫樹脂之纖維布或耐高溫非有機薄膜與膠材交聯固化,以此可製備出表層為高強度高緻密性的類纖維強化塑膠(LFRP)包覆高隔熱且高防火氣凝膠毯之產品,以此組合之產品將兼具有不掉粉塵、高隔熱效率、高防火及低介電或抗靜電的包覆氣凝膠複合材料。In this technology, the condensed solution is first dispersed in a large amount of dispersed solution by suspension dispersion technology during the preparation of aerogel, and then a small amount of high-temperature resistant adhesive material is added to disperse it evenly. Then, the suspended dispersed solution is injected into the preformed fiber blanket, and after gel molding and atmospheric pressure drying, aerogel fiber preformed composite structural materials with low thermal conductivity and high fire resistance can be prepared; then, fiber cloth containing high-temperature resistant resin or high-temperature resistant non-organic thin film is further used to prepare the aerogel fiber preformed composite structural materials. The surface of the preformed aerogel structure is coated with a film, and then high-temperature curing is performed to crosslink and cure the fiber cloth containing high-temperature resistant resin or high-temperature resistant non-organic film with the rubber material. In this way, a product with a high-strength and high-density fiber-reinforced plastic (LFRP) surface coated with a high-insulation and high-fireproof aerogel blanket can be prepared. The combined product will have the characteristics of dust-free, high thermal insulation efficiency, high fire resistance and low dielectric or anti-static coated aerogel composite materials.

本發明關於一種耐高溫材料包覆氣凝膠,尤其關於一種兼具無粉塵、高隔熱、高防火及低介電的氣凝膠複合材料,其中,本發明之實施樣態包含:(1) 混合水解步驟:於一乙醇水溶液中加入一矽氧烷前軀體攪拌混合形成一混合溶液,其中,該矽氧烷前軀體包括一矽氧烷化合物及一不同烷基鏈長取代的疏水性矽氧烷化合物或其組合,隨後將一酸觸媒加入該混合溶液中以進行水解反應;(2)縮合分散步驟:於該混合溶液中加入一大量分散水溶液進行快速攪拌,使該縮合溶液懸浮分散在水溶液中,該分散溶液包括一鹼觸媒,以進行縮合反應形成一懸浮分散次微米級縮合溶液,隨後可在懸浮分散次微米級縮合溶液體系中添加微量水可分散之耐高溫膠材;(3)結構成型步驟:將懸浮分散溶膠溶液注入一預成型模型中,促使該分散溶膠溶液進一步縮合形成一類固態氣凝膠濕膠之預成型模型結構。另外,也可將該懸浮分散溶膠溶液注入一含纖維材料模型中,促使該懸浮分散溶膠溶液在一含纖維材料預成型模型中進一步縮合而形成一含纖維材料之類固態氣凝膠濕膠預成型複合結構,並以微量水可分散之耐高溫膠材包覆在氣凝膠結構表面;(4) 常壓乾燥步驟:利用高溫烘箱結合微波技術,利用高溫烘箱提供一常壓及一高溫乾燥氣流,促使該類固態氣凝膠成型結構中溶劑快速汽化,另外利用水分子轉動頻率之微波技術,促使氣凝膠成型結構內部水分子快速旋轉而破壞水分子的氫鍵,使乾燥過程中抑制水分子的介面張力所導致氣凝膠結構收縮破裂的行為,結合以上技術可快速獲得一多孔結構且兼具低熱傳與低介電之預成型氣凝膠材料; (5) 外層包覆步驟:準備一耐300度以上高溫膠材溶液,將該膠材溶液含浸或噴塗在一耐高溫纖維布或無機模板表面,隨後進一步利用含浸膠材溶液之耐高溫纖維布或非有機膜板進行之氣凝膠預成型材料多層包覆; (6)固化成型步驟:將該含耐高溫膠材之耐高溫纖維布/非有機膜板多層包覆的氣凝膠預成型材料在一高溫固化環境下使樹脂固化成型,以獲得兼具高強度、高緻密性且不掉粉塵的類纖維強化塑膠包覆氣凝膠複合材料。由以上製程技術所製備之外層為一具高強度、高模量且高緻密性的類纖維強化塑膠(like-fiber reinforced plastic, LFRP)包覆層,內層為一具高隔熱、低介電的含微量耐高溫膠材氣凝膠結構複合材料,以此組合之產品將兼具有不掉粉塵以及高隔熱效率的氣凝膠複合結構材料;及(7) 表面處理步驟:將該高強度高緻密性LFRP包覆高隔熱氣凝膠毯利用高壓噴氣、噴砂、水砂輪或乾砂輪等拋光以及表面塗油等表面處理技術進行FRP包覆層表面處理,以此製程組合之氣凝膠複合結構材料將兼具高強度、高耐熱、不掉粉塵以及高隔熱效率。The present invention relates to a high temperature resistant material coated aerogel, and more particularly to an aerogel composite material having the characteristics of being dust-free, highly heat-insulating, highly fire-resistant and having low dielectric properties. The implementation of the present invention comprises: (1) a mixing and hydrolysis step: adding a siloxane precursor to an ethanol aqueous solution and stirring and mixing to form a mixed solution, wherein the siloxane precursor comprises a siloxane compound and a hydrophobic siloxane compound substituted with different alkyl chain lengths or a combination thereof, and then adding an acid catalyst to the mixed solution to perform a hydrolysis reaction; (2) a condensation and dispersion step: adding a large amount of dispersed aqueous solution to the mixed solution and rapidly stirring the condensation solution. The liquid is suspended and dispersed in an aqueous solution, and the dispersed solution includes an alkaline catalyst to perform a condensation reaction to form a suspended dispersed sub-micron condensation solution. A small amount of water-dispersible high-temperature resistant adhesive material can then be added to the suspended dispersed sub-micron condensation solution system; (3) a structure forming step: injecting the suspended dispersed sol solution into a pre-molded model to promote the dispersed sol solution to further condense to form a pre-molded model structure of a solid aerogel wet gel. In addition, the suspended dispersed sol solution can also be injected into a fiber-containing material model to cause the suspended dispersed sol solution to further condense in a fiber-containing material preform model to form a fiber-containing material-like solid aerogel wet-gel preform composite structure, and a high-temperature resistant glue material that can be dispersed in a trace amount of water is coated on the surface of the aerogel structure; (4) Normal pressure drying step: using a high temperature oven combined with microwave technology, using a high temperature oven to provide a normal pressure and a high temperature dry airflow, prompting the rapid vaporization of the solvent in the solid aerogel molding structure, and using microwave technology with the rotation frequency of water molecules to prompt the water molecules inside the aerogel molding structure to rotate rapidly and destroy the hydrogen bonds of the water molecules, so that the interface tension of the water molecules during the drying process is suppressed, causing the aerogel structure to shrink and rupture. Combining the above technologies can quickly obtain a porous structure and a preformed aerogel material with both low heat transfer and low dielectric properties; (5) Outer layer coating step: prepare a high temperature resistant rubber solution of more than 300 degrees, impregnate or spray the rubber solution on a high temperature resistant fiber cloth or inorganic template surface, and then further coat the aerogel preformed material with multiple layers of high temperature resistant fiber cloth or non-organic membrane board impregnated with the rubber solution; (6) Curing and molding step: cure the aerogel preformed material with multiple layers of high temperature resistant fiber cloth/non-organic membrane board containing high temperature resistant rubber in a high temperature curing environment to obtain a fiber-reinforced plastic-coated aerogel composite material with high strength, high density and no dust. The outer layer prepared by the above process technology is a high-strength, high-modulus and high-density fiber-reinforced plastic (LFRP) coating layer, and the inner layer is a high-insulation, low-dielectric, high-temperature-resistant aerogel structural composite material containing a trace amount of high-temperature-resistant plastic. The product with this combination will have the characteristics of aerogel composite structural material that is dust-free and has high thermal insulation efficiency; and (7) Surface treatment step: The high-strength, high-density LFRP-coated high-insulation aerogel blanket is treated with surface treatment techniques such as high-pressure air spraying, sandblasting, water-grinding wheel or dry-grinding wheel polishing, and surface oiling. The aerogel composite structural material with this process combination will have high strength, high heat resistance, no dust and high insulation efficiency.

進一步地,在 (1) 混合水解步驟中,該矽氧烷化合物包含四甲氧基矽烷(Tetramethoxysilane, TMOS)、四乙氧基矽烷(Tetraethoxysilane, TEOS)或其組合;該疏水性改質矽氧烷化合物包含甲基三甲氧基矽烷(Methyltrimethoxysilane,MTMS)、丙基三甲氧基矽烷(Propyltrimethoxysilane,PTMS)、己基三甲氧基矽烷(Hexyltrimethoxysilane,HTMS)、辛基三甲氧基矽烷(Octyltrimethoxysilane,OTMS)、六甲基二矽氮烷(Hexamethyldisilane,HMDS)等不同烷基鏈長取代的疏水性矽氧烷之一或其組合,其中,在整體混合溶液中,該矽氧烷化合物與該疏水性改質矽氧烷化合物之含量莫耳比介於0:100 mol%至95:5 mol%,添加該疏水改質矽氧烷化合物其目的在於降低氣凝膠結構於乾燥過程產生的龜裂現象;另一方面,添加該矽氧烷化合物其目的則在於提供調控氣凝膠結構內部微細結構及增加結構中之孔洞結構及孔隙率,以降低熱傳導性質或提高隔熱性質。Furthermore, in the mixed hydrolysis step (1), the siloxane compound comprises tetramethoxysilane (TMOS), tetraethoxysilane (TMOS), TEOS) or a combination thereof; the hydrophobic modified siloxane compound comprises one or a combination of hydrophobic siloxanes substituted with different alkyl chain lengths such as methyltrimethoxysilane (MTMS), propyltrimethoxysilane (PTMS), hexyltrimethoxysilane (HTMS), octyltrimethoxysilane (OTMS), hexamethyldisilane (HMDS), etc., wherein in the overall mixed solution, the molar ratio of the siloxane compound to the hydrophobic modified siloxane compound is between 0:100 mol% and 95:5 mol%, the purpose of adding the hydrophobic modified siloxane compound is to reduce the cracking phenomenon of the aerogel structure during the drying process; on the other hand, the purpose of adding the siloxane compound is to provide regulation of the internal microstructure of the aerogel structure and increase the pore structure and porosity in the structure to reduce thermal conductivity or improve thermal insulation.

進一步地,在 (1) 混合水解步驟中,當該酸觸媒於該混合溶液中的含量比越高,水解速率越快,但含大量酸離子在電場作用下將會產生離子導電性質,因此將會明顯提高氣凝膠結構的介電常數以及介電損耗;相對地,酸觸媒的含量比越低,整體水解速率越慢,因此本發明通過降低酸觸媒含量伴隨增加製程溫度來提高微量酸離子的水解速率,因此可明顯降低整體所添加的酸根離子以及縮合之鹼基離子的含量;另一方面,矽氧烷化合物及疏水化矽氧烷化合物在水解過程會產生大量的醇類分子,是以在水解過程中以去離子水取代氨水及烷類等有機溶劑,藉此降低氨水及烷類等有機溶劑添加,除了減少氨水等有機溶劑對氣凝膠的介電性質影響之外,更可降低製程中有機溶劑處理的危害及環境污染,亦可降低整體氣凝膠的製備成本。Furthermore, in the mixed hydrolysis step (1), when the content ratio of the acid catalyst in the mixed solution is higher, the hydrolysis rate is faster, but a large amount of acid ions will produce ionic conductivity under the action of the electric field, thereby significantly increasing the dielectric constant and dielectric loss of the aerogel structure; in contrast, the lower the content ratio of the acid catalyst, the slower the overall hydrolysis rate. Therefore, the present invention increases the hydrolysis rate of trace acid ions by reducing the acid catalyst content and increasing the process temperature, thereby significantly reducing the overall amount of acid radicals added. ions and condensed alkali ions; on the other hand, siloxane compounds and hydrophobic siloxane compounds will produce a large amount of alcohol molecules during the hydrolysis process. Therefore, deionized water is used to replace ammonia water and organic solvents such as alkanes during the hydrolysis process to reduce the addition of ammonia water and organic solvents such as alkanes. In addition to reducing the impact of ammonia water and organic solvents on the dielectric properties of aerogels, it can also reduce the hazards and environmental pollution of organic solvent treatment in the process, and can also reduce the overall preparation cost of aerogels.

進一步地,在 (1) 混合水解步驟中,在整體混合溶液中,該溶劑含量越高,在後續乾燥的濕膠顆粒內孔隙率越高;相對地,在整體混合溶液中,該溶劑含量越低,在後續乾燥的濕膠顆粒內孔隙率越低。該溶劑包含乙醇、回收乙醇水溶液、回收甲醇水溶液、回收水、去離子水、過濾水、蒸餾水或其組合。Furthermore, in the (1) mixed hydrolysis step, the higher the content of the solvent in the whole mixed solution, the higher the porosity of the wet gel particles in the subsequent drying; conversely, the lower the content of the solvent in the whole mixed solution, the lower the porosity of the wet gel particles in the subsequent drying. The solvent comprises ethanol, a recovered ethanol aqueous solution, a recovered methanol aqueous solution, recovered water, deionized water, filtered water, distilled water or a combination thereof.

進一步地,在 (2) 縮合分散過程中,在含微量鹼觸媒之大量含乙醇分散水溶液的添加下,該水解溶液中矽氧烷分子或疏水性矽氧烷分子的混合溶液在乳化機或均質機快速攪拌下,使該水解的矽氧烷分子或疏水性矽氧烷分子在大量分散水溶液的稀釋攪拌下,將會形成奈米級至次微米級的圓形分子懸浮油滴分散在大量分散水溶液中。利用此步驟的主要目的之一,為加速使該水解的矽氧烷分子或疏水性矽氧烷分子在大量分散水溶液的稀釋攪拌下,將會形成奈米級至次微米級的圓形分子懸浮油滴以增加反應接觸面積,使其加速縮合反應速率以便快速老化形成奈米級至次微米級濕凝膠顆粒;利用此步驟另一目的,為所形成的奈米級至次微米級濕凝膠顆粒在後續乾燥過程中,也因明顯提升其比表面積因而乾燥速率也會提升。Furthermore, in the (2) condensation dispersion process, a large amount of ethanol-containing aqueous dispersion solution containing a trace amount of alkaline catalyst is added, and the mixed solution of the siloxane molecules or hydrophobic siloxane molecules in the hydrolyzed solution is rapidly stirred in an emulsifier or homogenizer, so that the hydrolyzed siloxane molecules or hydrophobic siloxane molecules will form nano-scale to sub-micron-scale round molecular suspended oil droplets dispersed in the large amount of aqueous dispersion solution under the dilution and stirring of the large amount of aqueous dispersion solution. One of the main purposes of using this step is to accelerate the hydrolyzed siloxane molecules or hydrophobic siloxane molecules to form nano-scale to sub-micron-scale circular molecular suspended oil droplets under the dilution and stirring of a large amount of dispersed aqueous solution to increase the reaction contact area, thereby accelerating the condensation reaction rate so as to quickly age and form nano-scale to sub-micron-scale wet gel particles; another purpose of using this step is that the drying rate of the formed nano-scale to sub-micron-scale wet gel particles will also be increased in the subsequent drying process because of the significantly increased specific surface area.

更進一步地,在上述 (2) 縮合分散過程中,本發明在該奈米級至次微米級濕凝膠顆粒與分散水中也可添加一極微量水可溶解分散的耐高溫膠材,利用該水可溶解分散耐高溫膠材在後續乾燥中披覆在該奈米級至次微米級濕凝膠顆粒表面,並以此披覆膠材作為濕凝膠顆粒結構的穩固劑,因此在本製備方法中產品較不會龜裂,因此可不添加大量疏水性甲苯、正己烷等有機溶劑,並且在製備中也可不添加界面活性劑等助劑,可免去多次疏水性有機溶劑的置換步驟。Furthermore, in the above-mentioned (2) condensation and dispersion process, the present invention can also add a very small amount of water-soluble and dispersible high-temperature resistant rubber material to the nano-scale to sub-micron-scale wet gel particles and the dispersion water, and use the water-soluble and dispersible high-temperature resistant rubber material to coat the surface of the nano-scale to sub-micron-scale wet gel particles in the subsequent drying, and use this coated rubber material as a stabilizer for the wet gel particle structure. Therefore, in this preparation method, the product is less likely to crack, so it is not necessary to add a large amount of hydrophobic organic solvents such as toluene and n-hexane, and it is also not necessary to add additives such as surfactants in the preparation, and multiple replacement steps of the hydrophobic organic solvent can be avoided.

進一步地,在 (3) 結構成型步驟中包含預成型及成型步驟:在預成型步驟中將該形成奈米級至次微米級的已水解矽氧烷分子及疏水性矽氧烷分子混合懸浮分散溶液注入一預成型模具中,使該奈米級至次微米級濕凝膠顆粒進一步縮合聚集形成預成型結構的凝膠結構,如各種尺寸的管狀、板狀或特定外觀型態預成型凝膠結構;本技術中利用該奈米至次微米級的濕凝膠顆粒相互聚集而形成三次元的濕膠顆粒網狀結構,利用該凝膠化使之奈米級至次微米級的氣凝膠濕凝膠縮合聚集形成成型模具的結構,且利用微量水可分散之耐高溫膠材包覆在氣凝膠結構表面以形成有機-無機複合結構;在另一實施例中,也可將該未進行縮合反應的縮合懸浮分散溶膠溶液注入一含纖維材料預成型模具中,使該奈米級至次微米級的已水解濕凝膠顆粒進入預成型模具中,並進一步在纖維結構之間縮合聚集形成三次元的濕膠顆粒網狀結構,利用凝膠化在此預成型模具中促使該矽基濕膠顆粒與纖維材料相互結合,隨後在該預成型模型中進一步縮合而形成一含纖維材料之類固態氣凝膠濕膠的成型結構,且利用微量水可分散之耐高溫膠材包覆在氣凝膠結構表面以形成有機-無機複合結構。Furthermore, in (3) The structural forming step includes a preforming and a forming step: in the preforming step, the hydrolyzed siloxane molecules and hydrophobic siloxane molecules of nanometer to sub-micrometer scale are mixed and suspended in a dispersed solution and injected into a preforming mold, so that the nanometer to sub-micrometer scale wet gel particles are further condensed and aggregated to form a gel structure of a preforming structure, such as a tubular, plate-shaped or preformed gel structure of a specific appearance of various sizes; in the present technology, the nanometer to sub-micrometer scale wet gel particles are aggregated to form a three-dimensional wet gel particle network structure, and the gelation is used to make the nanometer to sub-micrometer scale aerogel wet gel condense and aggregate to form the structure of the forming mold, and the high-temperature resistant adhesive material that can be dispersed by a small amount of water is used to cover the aerogel. In another embodiment, the condensed suspension dispersed sol solution that has not undergone condensation reaction can also be injected into a preformed mold containing fiber material, so that the hydrolyzed wet gel particles of nanometer to sub-micrometer scale enter the preformed mold and further condense and aggregate between the fiber structure to form a three-dimensional wet gel. The particle network structure utilizes gelation to promote the mutual combination of the silicon-based wet gel particles and the fiber material in the pre-forming mold, and then further condenses in the pre-forming model to form a solid aerogel wet gel molding structure containing a fiber material, and a high-temperature resistant glue material that can be dispersed by a small amount of water is coated on the surface of the aerogel structure to form an organic-inorganic composite structure.

更進一步地,在上述 (3) 結構成型步驟中,也可利用含浸技術、壓吸技術、高壓注入、高壓噴淋、高壓噴霧或真空吸附等技術,將該水解矽氧烷分子及疏水性矽氧烷分子分散溶液注入一含纖維結構中,以進行含纖維氣凝膠薄板複合加工。Furthermore, in the above-mentioned (3) structure forming step, the hydrolyzed silicone molecules and the hydrophobic silicone molecules dispersed solution can also be injected into a fiber-containing structure by using impregnation technology, pressure suction technology, high-pressure injection, high-pressure spraying, high-pressure misting or vacuum adsorption technology to perform fiber-containing aerogel sheet composite processing.

更進一步地,在上述 (3) 結構成型步驟中,該耐300度以上高溫膠材包含無機膠或熱固性樹脂之一或其組合,具體而言,例如、水玻璃、無機矽樹脂、氧化銅-磷酸膠、矽酸鹽膠、磷酸-矽酸鹽膠、硫酸鹽膠、氧化鎂-二氧化矽-硼砂無機膠、環氧樹脂、聚醯亞胺、聚醚醯亞胺、聚苯醚、聚苯硫醚、聚醚酮液晶高分子、聚四氟乙烯、聚三聚氰胺、聚酚醛、聚三聚氰胺-甲醛、聚醯胺、聚醯胺酯、矽膠等各類有機或無機膠材之一或其組合。Furthermore, in the above (3) structure forming step, the high temperature resistant adhesive material of 300 degrees or above comprises one or a combination of inorganic adhesives or thermosetting resins, specifically, for example, water glass, inorganic silicone resin, copper oxide-phosphate adhesive, silicate adhesive, phosphoric acid-silicate adhesive, sulfate adhesive, magnesium oxide-silicon dioxide-borax inorganic adhesive, epoxy resin, polyimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyetherketone liquid crystal polymer, polytetrafluoroethylene, polymelamine, polyphenolic acid, polymelamine-formaldehyde, polyamide, polyamide, silicone and other types of organic or inorganic adhesive materials or a combination thereof.

更進一步地,在上述 (3) 結構成型步驟中,本發明所指耐高溫纖維包括金屬纖維、無機纖維、液晶纖維、有機纖維;具體而言,例如微米至奈米尺度之各類金屬纖維或金屬棒、玻璃纖維、碳纖維、石英纖維、陶瓷纖維、岩棉纖維、Kevlar聚醯胺纖維、Nomex聚醯胺纖維、尼龍纖維、聚酯纖維、生物可分解無機纖維或生物可分解有機纖維所製備之各類多孔隙散棉、蓆、紙、毯、繩、厚板等或其組合。Furthermore, in the above-mentioned (3) structure forming step, the high temperature resistant fiber referred to in the present invention includes metal fiber, inorganic fiber, liquid crystal fiber, organic fiber; specifically, for example, various types of metal fibers or metal rods of micron to nanometer scale, glass fiber, carbon fiber, quartz fiber, ceramic fiber, rock wool fiber, Kevlar polyamide fiber, Nomex polyamide fiber, nylon fiber, polyester fiber, various types of porous loose cotton, mats, paper, blankets, ropes, thick plates, etc. or combinations thereof prepared from biodegradable inorganic fibers or biodegradable organic fibers.

進一步,在 (4) 常壓乾燥步驟包含:(4-1)溶劑共沸汽化步驟:將該類固態氣凝膠之預成型結構放置於結合高溫設備及微波設備中,利用高溫烘箱、UV光或IR等熱源提供一該混合溶劑共沸溫度的高溫氣流,並結合水分子轉動頻率之微波頻率,促使氣凝膠成型結構內部水分子隨微波頻率快速旋轉而破壞氣凝膠結構中水分子的氫鍵鍵結,以加速產品的乾燥速率。結合以上技術可使氣凝膠結構內部的水分子以及醇類分子快速乾燥,並抑制水分子的介面張力所導致氣凝膠結構收縮破裂的行為,一般該類固態氣凝膠成型結構中大量的混合溶劑快速共沸汽化溫度為60~90℃之間;(4-2)溶劑回收:在該共沸溫度環境下,將汽化蒸氣引導至一熱交換回收設備;在該熱交換回收設備中促使含水酒精冷凝並回收,該回收目的為以降低成本以及降低對環境的污染;及(4-3)突沸步驟:調整該乾燥氣凝膠之預成型結構之乾燥設備溫度至此混合劑的突沸溫度以上高溫,並結合微波頻率快速旋轉以破壞氣凝膠結構中水分子的氫鍵鍵結,並快速提供溶劑分子摩擦熱,使該接近乾燥的氣凝膠內部所剩餘的混合溶劑產生快速突沸而形成一正壓力,利用此氣凝膠結構內部的正壓力抑制氣凝膠在乾燥過程中所產生的收縮行為;另外,也可利用氣凝膠結構內部的正壓力,促使氣凝膠結構膨脹過程中產生大量奈米級至次微米級的微細孔洞,以提高氣凝膠產品的孔洞率及隔熱性質,該突沸溫度為110~180℃。Furthermore, the (4) atmospheric pressure drying step includes: (4-1) solvent azeotropic vaporization step: placing the preformed structure of the solid aerogel in a high temperature device and a microwave device, using a high temperature oven, UV light or IR and other heat sources to provide a high temperature gas flow at the azeotropic temperature of the mixed solvent, and combining the microwave frequency with the rotation frequency of water molecules to promote the water molecules inside the aerogel forming structure to rotate rapidly with the microwave frequency, thereby destroying the hydrogen bonds of the water molecules in the aerogel structure, thereby accelerating the drying rate of the product. The above technologies can be combined to quickly dry the water molecules and alcohol molecules inside the aerogel structure, and inhibit the interface tension of the water molecules that causes the aerogel structure to shrink and rupture. Generally, the rapid azeotropic vaporization temperature of a large amount of mixed solvents in such solid aerogel molding structures is between 60 and 90°C; (4-2) Solvent recovery: In the azeotropic temperature environment, the vaporized steam is guided to a heat exchange recovery device; in the heat exchange recovery device, the water-containing alcohol is condensed and recovered. The purpose of the recovery is to reduce costs and reduce environmental pollution; and (4-3) Boiling step: Adjust the temperature of the drying equipment of the preformed structure of the dried aerogel The temperature is raised to a high temperature above the sudden boiling temperature of the mixture, and combined with the rapid rotation of the microwave frequency to destroy the hydrogen bonds of the water molecules in the aerogel structure, and quickly provide friction heat to the solvent molecules, so that the remaining mixed solvent inside the nearly dry aerogel produces a rapid sudden boiling to form a positive pressure. The positive pressure inside the aerogel structure is used to inhibit the shrinkage of the aerogel during the drying process; in addition, the positive pressure inside the aerogel structure can also be used to promote the generation of a large number of nano-scale to sub-micron-scale microscopic pores during the expansion process of the aerogel structure, so as to improve the porosity and thermal insulation properties of the aerogel product. The sudden boiling temperature is 110~180℃.

進一步地,在 (5) 外層包覆步驟中:準備一耐300度以上高溫膠材溶液,包含有機、無機樹脂或其組合,將該耐高溫膠材溶液含浸或噴塗在一耐高溫纖維布、耐高溫非有機薄膜、或耐高溫非有機薄板上,使該耐高溫膠材溶液均勻噴塗在該耐高溫纖維布、該耐高溫非有機薄膜或耐高溫非有機薄板表面,隨後進一步利用此含耐高溫膠材之耐高溫材料等產品進行氣凝膠預成型結構材表面包覆或披覆。Furthermore, in the (5) outer layer coating step: a high temperature resistant adhesive solution of 300 degrees or above is prepared, comprising an organic, inorganic resin or a combination thereof, and the high temperature resistant adhesive solution is impregnated or sprayed on a high temperature resistant fiber cloth, a high temperature resistant non-organic film, or a high temperature resistant non-organic sheet, so that the high temperature resistant adhesive solution is evenly sprayed on the surface of the high temperature resistant fiber cloth, the high temperature resistant non-organic film or the high temperature resistant non-organic sheet, and then the high temperature resistant material containing the high temperature resistant adhesive is further used to coat or cover the surface of the aerogel preformed structural material.

進一步地,在上述 (5) 外層包覆步驟中,該耐高溫非有機薄膜、耐高溫非有機薄板或耐高溫纖維之一或其組合,其中有關耐高溫非有機薄膜、耐高溫非有機薄板包含金屬、無機及有機-無機複合等耐高溫薄膜、薄板。進一步,其中金屬膜板包含鋁、不鏽鋼、銅等金屬材料所製備的薄膜或其組合;無機膜板包含雲母薄片、石墨薄片、石墨烯薄片、玻璃薄片及各類陶瓷薄片、金屬氧化物、金屬氮矽化合物及金屬碳矽化合物所製備成薄片、薄板或其組合;有機-無機複合薄膜包含如鋁、不鏽鋼、銅、雲母片、石墨、石墨烯、玻璃、陶瓷、金屬氧化物、金屬氮矽化合物及金屬碳矽化合物與各類有機膠或各類無機膠所複合製造的耐高溫有機-無機複合薄膜、薄板或無機-無機複合薄膜、薄板等組合。更進一步,其中耐高溫纖維包含如石英纖維、玻璃纖維、陶瓷纖維、碳纖維;有機纖維如尼龍纖維、聚酯纖維、聚氟纖維;液晶纖維如Kevlar聚醯胺纖維、Nomex聚醯胺纖維;及各類纖維素、生物可分解無機或有機纖維等複合所製備之各類多孔隙散棉、蓆、紙、毯、繩、厚板之一或其組合。Furthermore, in the above-mentioned (5) outer layer coating step, the high-temperature resistant non-organic film, high-temperature resistant non-organic sheet or high-temperature resistant fiber is one or a combination thereof, wherein the high-temperature resistant non-organic film and high-temperature resistant non-organic sheet include metal, inorganic and organic-inorganic composite high-temperature resistant films and sheets. Furthermore, the metal membrane plate includes a film or a combination thereof made of metal materials such as aluminum, stainless steel, and copper; the inorganic membrane plate includes a thin film, a thin plate or a combination thereof made of mica flakes, graphite flakes, graphene flakes, glass flakes and various ceramic flakes, metal oxides, metal nitrogen silicon compounds and metal carbon silicon compounds; the organic-inorganic composite film includes a high-temperature resistant organic-inorganic composite film, a thin plate or a combination of inorganic-inorganic composite films, thin plates, etc., which are composited with aluminum, stainless steel, copper, mica flakes, graphite, graphene, glass, ceramics, metal oxides, metal nitrogen silicon compounds and metal carbon silicon compounds and various organic glues or various inorganic glues. Furthermore, the high temperature resistant fiber includes quartz fiber, glass fiber, ceramic fiber, carbon fiber; organic fiber such as nylon fiber, polyester fiber, polyfluorinated fiber; liquid crystal fiber such as Kevlar polyamide fiber, Nomex polyamide fiber; and various porous loose cotton, mats, paper, blankets, ropes, thick boards prepared from various types of cellulose, biodegradable inorganic or organic fibers, or one or a combination thereof.

更進一步地,在上述 (5) 外層包覆步驟中,該耐高溫膠材溶液包含無機膠、熱塑性或熱固性有機樹脂之一或其組合,具體而言,耐高溫無機膠例如水玻璃膠、無機矽樹脂膠、氧化銅-磷酸膠、矽酸鹽膠、磷酸-矽酸鹽膠、硫酸鹽膠、氧化鎂-二氧化矽-硼砂無機膠等或其組合;耐高溫熱固性有機膠例如環氧樹脂、聚醯亞胺樹脂、聚醚醯亞胺樹脂、聚苯醚樹脂、聚苯硫醚樹脂、聚醚酮液晶高分子樹脂、聚四氟乙烯樹脂、聚三聚氰胺樹脂、聚酚醛樹脂、聚三聚氰胺-甲醛樹脂、聚醯胺膠、聚醯胺酯膠、聚丙烯酸樹脂膠、矽膠等或其組合。Furthermore, in the above-mentioned (5) outer layer coating step, the high temperature resistant adhesive solution comprises an inorganic adhesive, a thermoplastic or thermosetting organic resin, or a combination thereof. Specifically, the high temperature resistant inorganic adhesive is, for example, water glass adhesive, inorganic silicone resin adhesive, cupric oxide-phosphate adhesive, silicate adhesive, phosphoric acid-silicate adhesive, sulfate adhesive, magnesium oxide-silicon dioxide-borax inorganic adhesive, or a combination thereof; Thermosetting organic adhesives include epoxy resins, polyimide resins, polyetherimide resins, polyphenylene ether resins, polyphenylene sulfide resins, polyetherketone liquid crystal polymer resins, polytetrafluoroethylene resins, polymelamine resins, polyphenolic resins, polymelamine-formaldehyde resins, polyamide adhesives, polyamide ester adhesives, polyacrylic resin adhesives, silicone adhesives, etc., or combinations thereof.

進一步地,以外層包覆步驟整體而言,該耐高溫膠材溶液的固含量濃度介於10.0 ~ 75.0wt%;將該噴塗或塗布膠材溶液之該纖維布、該耐高溫非有機薄膜、或該耐高溫非有機薄板進行多層包覆的氣凝膠預成型複合材料。其中,耐高溫膠材溶液的濃度越低,膠材溶液滲入纖維布內部溶液效率越佳且加工越容易,但所製備的含浸膠材溶液之纖維布多層包覆的氣凝膠成型複合材料的緻密性越差,結構中孔洞含量越高,因此越容易產生氣凝膠粉塵洩漏;相對地,耐高溫膠材溶液的濃度越高,膠材溶液披覆在纖維布表面含量越高,所製備的含浸膠材溶液之纖維布多層包覆的氣凝膠成型複合材料的強度越高、緻密性越佳且越不易產生氣凝膠粉塵洩漏,但加工越困難且膜厚較不易控制。是以,利用所含浸膠材溶液的濃度可以控制含浸膠材溶液之纖維布多層包覆的氣凝膠成型複合材料的成型加工及不掉粉塵性質,最佳化的膠材溶液濃度介於30~50.0wt%。Furthermore, in terms of the outer layer coating step as a whole, the solid content concentration of the high-temperature resistant rubber solution is between 10.0 and 75.0wt%; the fiber cloth, the high-temperature resistant non-organic film, or the high-temperature resistant non-organic sheet coated with the sprayed or applied rubber solution is multi-layered to form an aerogel preformed composite material. Among them, the lower the concentration of the high-temperature resistant rubber solution, the better the efficiency of the rubber solution penetrating into the internal solution of the fiber cloth and the easier the processing, but the poorer the density of the prepared aerogel molding composite material coated with multiple layers of fiber cloth impregnated with the rubber solution, the higher the pore content in the structure, and therefore the easier it is to produce aerogel dust leakage; relatively, the higher the concentration of the high-temperature resistant rubber solution, the higher the content of the rubber solution coated on the surface of the fiber cloth, the higher the strength of the prepared aerogel molding composite material coated with multiple layers of fiber cloth impregnated with the rubber solution, the better the density and the less likely it is to produce aerogel dust leakage, but the more difficult it is to process and the film thickness is more difficult to control. Therefore, the concentration of the impregnated rubber solution can be used to control the molding process and dust-free properties of the aerogel molding composite material with multiple layers of fiber cloth impregnated with the rubber solution, and the optimized concentration of the rubber solution is between 30 and 50.0wt%.

進一步地,在(6) 固化成型步驟中包含(6-1)溶劑乾燥及(6-2)交聯固化,在溶劑乾燥步驟將該含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板表面進行多層包覆的氣凝膠預成型複合材料放置在含浸膠材溶液的溶劑沸點溫度下,促使該膠材溶液的溶劑汽化以降低成型缺陷或氣泡孔洞的形成,如果該膠材為常溫固化樹脂,則在溶劑乾燥期間伴隨樹脂的固化,稱之為常溫乾燥固化步驟,而形成一高強度、高緻密性、且不掉粉塵之類纖維強化塑膠(like-fiber reinforced plastic, LFRP)無機包覆矽基氣凝膠複合材料。Furthermore, the (6) curing and molding step includes (6-1) solvent drying and (6-2) crosslinking curing. In the solvent drying step, the aerogel preformed composite material containing the impregnated or coated rubber material solution and coated with multiple layers on a fiber cloth or a high-temperature resistant film/high-temperature resistant sheet is placed at the boiling point temperature of the solvent impregnated with the rubber material solution to promote the vaporization of the solvent in the rubber material solution to reduce the formation of molding defects or air bubbles and cavities. If the rubber material is a room-temperature curing resin, the resin is cured during the solvent drying period, which is called a room-temperature drying and curing step, thereby forming a high-strength, high-density, and dust-free like-fiber reinforced plastic (LFRPE, LFRP) inorganic coated silicon-based aerogel composite.

進一步地,在此提供一高強度、高防火、高隔熱、具抗靜電且避免粉塵洩漏之類纖維強化塑膠(like-fiber reinforced plastic, LFRP)無機包覆矽基氣凝膠複合材料,相關產品具有高強度、高硬度以及高防火等性質,可應用於無塵室高溫製程以及電動車鋰電池模組熱逸散的安全防護。本發明之目的為提供一改善氣凝膠複合材料製備技術,以製備出兼具高隔熱效率、高防火機能以及不掉粉塵的無機包覆氣凝膠結構複合材;本發明之另一目的為提供一改善傳統有機膜包覆矽基氣凝膠或有機-無機複合氣凝膠在高溫應用上老化或裂解的缺點; 另一方面,本發明則提供一種適用於無塵室高溫管路外部覆蓋絕熱層或具絕熱層機具平台,以降低管線內或機具平台介面熱流失,進而提高節能減碳功效。Furthermore, a high-strength, high-fireproof, high-heat-insulating, anti-static and dust-leakage-resistant like-fiber reinforced plastic (LFRP) inorganic-coated silicon-based aerogel composite material is provided herein. The related product has the properties of high strength, high hardness and high fireproofing, and can be applied to clean-room high-temperature processes and safety protection of thermal runaway of electric vehicle lithium battery modules. The purpose of the present invention is to provide an improved aerogel composite material preparation technology to prepare an inorganic coated aerogel structural composite material with high thermal insulation efficiency, high fireproof function and no dust. Another purpose of the present invention is to provide a method to improve the shortcomings of aging or cracking of traditional organic film coated silicon-based aerogels or organic-inorganic composite aerogels in high temperature applications. On the other hand, the present invention provides a heat-insulating layer suitable for covering the outside of high-temperature pipelines in clean rooms or a machine platform with a heat-insulating layer to reduce heat loss in the pipeline or at the interface of the machine platform, thereby improving energy saving and carbon reduction effects.

在上述 (6-1)溶劑乾燥步驟中,具高耐熱性、高強度且兼具不掉粉塵的含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板表面的有機溶劑伴隨著汽化,使該膠材溶液逐漸乾燥,此處溶劑乾燥溫度隨該膠材溶液的混合溶劑沸點而定;在一些實施例中,溶劑為乙醇,其溶劑乾燥溫度為60~75℃;在另一些實施例中,溶劑為丁酮,其溶劑乾燥溫度為80~90℃;在另一些實施例中,溶劑為水,其水溶劑乾燥溫度為80~102℃;基於降低該乾燥溶劑的危害性,將該溶劑汽化經由一回收裝置進行溶劑回收以減少工作環境中汽化溶劑的含量,一以降低危害。In the above-mentioned (6-1) solvent drying step, the organic solvent impregnated or coated with the rubber solution having high heat resistance, high strength and no dust on the surface of a fiber cloth or a high temperature resistant film/high temperature resistant sheet is vaporized, so that the rubber solution is gradually dried. The solvent drying temperature here depends on the boiling point of the mixed solvent of the rubber solution. In some embodiments, the solvent is ethanol, and the solvent drying temperature is In some embodiments, the solvent is butanone, and the solvent drying temperature is 80-90°C; in some other embodiments, the solvent is water, and the water solvent drying temperature is 80-102°C; based on reducing the hazard of the drying solvent, the solvent is vaporized and recovered through a recovery device to reduce the content of the vaporized solvent in the working environment, so as to reduce the hazard.

在另一實施例,在 (6-1)溶劑乾燥步驟中,含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板內部的有機溶劑伴隨著汽化,在該膠材溶液逐漸乾燥,該含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板即可獲得具高耐熱性、高強度且兼具不掉粉塵的含浸膠材溶液之纖維布或耐高溫薄膜/耐高溫薄板包覆氣凝膠複合材料。In another embodiment, in the solvent drying step (6-1), the organic solvent impregnated or coated with the rubber solution in a fiber cloth or a high-temperature resistant film/high-temperature resistant thin plate is vaporized, and the rubber solution is gradually dried to obtain a fiber cloth or a high-temperature resistant film/high-temperature resistant thin plate impregnated with the rubber solution, which has high heat resistance, high strength and is dust-resistant and coated with an aerogel composite.

進一步地,在 (6-2)交聯固化步驟中,將該含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板多層包覆的氣凝膠預成型複合材料在一特定交聯固化溫度下,使無機膠或熱固性高分子鏈之間以及無機膠或熱固性分子與氣凝膠分子之間進行交聯反應,並結合固化。如水玻璃膠、無機矽樹脂膠等無機膠以及熱固性高分子為環氧樹脂(epoxy),該交聯固化溫度約為120~200℃,在一些實施例中,最佳交聯固化溫度為150~180℃或185~190℃;另一方面,如氧化銅-磷酸膠、矽酸鹽膠、磷酸-矽酸鹽膠等無機膠以及熱固性高分子為聚醯亞胺(polyimide),該交聯固化溫度約為120~325℃一系列交聯固化溫度,在一些實施例中,最高交聯固化溫度為320~325℃。在該(6-2)交聯固化步驟中,於特定的交聯溫度下,該含浸或塗布有機或無機樹脂溶液在一纖維布或耐高溫薄膜/耐高溫薄板分子間相互交聯反應,使其形成一高隔熱性、高防火、高強度且不掉粉塵之含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板多層包覆的氣凝膠成型複合材料。Furthermore, in the cross-linking and curing step (6-2), the impregnated or coated rubber solution is placed in an aerogel preformed composite material coated with multiple layers of fiber cloth or high-temperature resistant film/high-temperature resistant sheet at a specific cross-linking and curing temperature to allow cross-linking reactions to occur between inorganic rubber or thermosetting polymer chains and between inorganic rubber or thermosetting molecules and aerogel molecules, and to bond and cure. For inorganic glues such as water glass glue and inorganic silicone glue, and thermosetting polymers such as epoxy, the crosslinking curing temperature is about 120-200°C. In some embodiments, the optimal crosslinking curing temperature is 150-180°C or 185-190°C. On the other hand, for inorganic glues such as copper oxide-phosphate glue, silicate glue, phosphoric acid-silicate glue, and thermosetting polymers such as polyimide, the crosslinking curing temperature is about 120-325°C. In some embodiments, the highest crosslinking curing temperature is 320-325°C. In the (6-2) crosslinking and curing step, at a specific crosslinking temperature, the organic or inorganic resin solution impregnated or coated on a fiber cloth or a high-temperature resistant film/high-temperature resistant sheet undergoes a crosslinking reaction between the molecules, thereby forming an aerogel molding composite material having high thermal insulation, high fire resistance, high strength and no dust, in which the impregnated or coated rubber solution is coated on a fiber cloth or a high-temperature resistant film/high-temperature resistant sheet in multiple layers.

進一步地,在(7) 表面處理步驟中,將該高強度、低熱傳、低介電、高防火的耐高溫薄膜包覆氣凝膠和材料利用拋光、噴氣及表面噴塗氣凝膠防火隔熱塗料之一或其組合清潔及表面保護等製程組合將兼具高強度、低熱傳、低介電、高防火的耐高溫薄膜包覆氣凝膠。Furthermore, in the surface treatment step (7), the high-strength, low-heat-transfer, low-dielectric, high-fire-resistant high-temperature-resistant film-coated aerogel and the material are treated by a combination of polishing, spraying, and surface spraying of aerogel fire-proof and heat-insulating coatings or a combination of cleaning and surface protection processes to obtain a high-strength, low-heat-transfer, low-dielectric, high-fire-resistant high-temperature-resistant film-coated aerogel.

進一步,上述製備方法中,兼具低熱傳與低介電多層包覆的氣凝膠成型複合材料內部氣凝膠材料係一多孔性結構,其孔隙率介於50.0~75.0%,其密度介於0.20~0.60g/cm3,其熱傳係數介於0.020~0.045W/mk,其介電常數介於1.30~1.85,耐燃性質在UL94-5VA等級以上,最高耐熱溫度可達1200度高溫等性質。當高溫熱點溫度約650度下,產品厚度在2mm~3mm條件下,隔熱溫度約下降至200度以下。Furthermore, in the above-mentioned preparation method, the internal aerogel material of the aerogel molding composite material with low heat transfer and low dielectric multi-layer coating is a porous structure, with a porosity between 50.0~75.0%, a density between 0.20~0.60g/cm3, a heat transfer coefficient between 0.020~0.045W/mk, a dielectric constant between 1.30~1.85, a flame retardancy above UL94-5VA level, and a maximum heat resistance temperature of 1200 degrees. When the high temperature hot spot temperature is about 650 degrees, the product thickness is 2mm~3mm, and the insulation temperature drops to about below 200 degrees.

本發明係提供一可快速生產高強度、耐高溫材料包覆氣凝膠複合材料,首先利用改良式凝膠-熔膠技術在低有機溶劑、低酸鹼離子濃度下以乳化機或均質機等設備進行快速縮合懸浮分散溶液技術,隨後將該縮合懸浮分散溶液含浸於預成型模具或一含纖維之預成型模具以製備出兼具高隔熱及低介電之特定成型結構的氣凝膠或氣凝膠/纖維複合結構材;更進一步,將該氣凝膠或氣凝膠/纖維複合結構材利用含浸或塗布膠材溶液在一纖維布或耐高溫薄膜/耐高溫薄板進行單層或多層包覆,隨後進行交聯固化及表面處理以製備出高防火、低熱傳且不掉粉塵之多層包覆氣凝膠複合結構材料,相關產品可提供於各類高科技產業無塵室應用以達到節能減碳功效,以及未來電動車或氫能源車安全防護等應用。The present invention provides a method for rapidly producing a high-strength, high-temperature-resistant material-coated aerogel composite materials. First, a modified gel-melt technology is used to rapidly condense a suspended dispersion solution using an emulsifier or a homogenizer under low organic solvent and low acid-base ion concentrations. The condensed suspended dispersion solution is then impregnated into a preform mold or a preform mold containing fibers to prepare an aerogel or aerogel/fiber composite structure having a specific molding structure with both high thermal insulation and low dielectric properties. Furthermore, the aerogel or aerogel/fiber composite structural material is coated with a fiber cloth or a high-temperature resistant film/high-temperature resistant sheet in a single layer or multiple layers by impregnating or coating the aerogel solution, and then cross-linked, cured and surface treated to prepare a multi-layer coated aerogel composite structural material with high fire resistance, low heat transfer and no dust. The related products can be provided for clean room applications in various high-tech industries to achieve energy saving and carbon reduction effects, as well as safety protection for future electric vehicles or hydrogen energy vehicles.

本發明所提供之製備方法具有以下功效:The preparation method provided by the present invention has the following effects:

1、本發明所提供的製備方法改善傳統氣凝膠隔熱材容易掉屑的缺點,以促進氣凝膠隔熱材料廣泛應用性質,本發明為製備一兼具高強度、高防火、不掉粉塵、高隔熱性質的氣凝膠複合材料。其中在氣凝膠複合材料為利用改良溶膠-凝膠技術,因此製程中不添加大量有機溶劑、界面活性劑及接著劑等物質,使其所製備氣凝膠複合材過程中無須長時間的溶劑置換及利用超臨界乾燥技術,僅利用含溶劑回收之常壓乾燥技術,整體製程簡易、安全性高且更具經濟優勢,批次製程速度可縮小至12至48小時內完成產品,或以連續生產方式製備氣凝膠或氣凝膠/纖維複合材料等,提高生產效率。1. The preparation method provided by the present invention improves the shortcoming of traditional aerogel insulation materials that they are easy to shed, so as to promote the wide application of aerogel insulation materials. The present invention is to prepare an aerogel composite material with high strength, high fire resistance, no dust and high thermal insulation properties. Aerogel composites use improved sol-gel technology, so a large amount of organic solvents, surfactants, adhesives and other substances are not added in the process. Therefore, the preparation of aerogel composites does not require long-term solvent replacement and supercritical drying technology. Only atmospheric pressure drying technology with solvent recovery is used. The overall process is simple, safe and economical. The batch process speed can be shortened to 12 to 48 hours to complete the product, or aerogels or aerogel/fiber composites can be prepared in a continuous production method to improve production efficiency.

2、本發明所提供的製備方法中,可利用矽氧烷化合物及疏水改質矽氧烷化合物的比例、水解溶劑含量、分散水溶液含量、乳化機或均質機等分散設備的攪拌速率、酸觸媒及鹼觸媒含量及比例等因素,進而可輕易調控多孔性氣凝膠顆粒內部的孔隙率、孔徑大小、氣凝膠顆粒之間的孔隙率與氣凝膠結構緻密性質。2. In the preparation method provided by the present invention, the porosity and pore size inside the porous aerogel particles, the porosity between the aerogel particles and the compactness of the aerogel structure can be easily adjusted by utilizing factors such as the ratio of the siloxane compound and the hydrophobically modified siloxane compound, the content of the hydrolysis solvent, the content of the dispersed aqueous solution, the stirring rate of the dispersing equipment such as an emulsifier or a homogenizer, and the content and ratio of the acid catalyst and the alkaline catalyst.

3、本發明所提供的製備方法中,利用親-疏水性質的排斥力以及快速攪拌使矽氧烷化合物及疏水改質矽氧烷化合物形成微細的濕凝膠顆粒,以提升其乾燥速率及降低收縮性質;因此,除醇類以外無添加其它疏水性有機溶劑,如環己烷、苯、異丙醇、氨水以及添加大量界面活性劑等,並將酸觸媒及鹼觸媒控制在極低濃度,可進一步調控氣凝膠材料的熱傳導、防火性質及其介電性質,以降低氣凝膠複合材料的製造成本。3. In the preparation method provided by the present invention, the repulsive force of the hydrophilic-hydrophobic property and rapid stirring are used to form fine wet gel particles of the silicone compound and the hydrophobically modified silicone compound to increase the drying rate and reduce the shrinkage property; therefore, no other hydrophobic organic solvents, such as cyclohexane, benzene, isopropyl alcohol, ammonia water, and a large amount of surfactants are added except for alcohols, and the acid catalyst and the alkaline catalyst are controlled at extremely low concentrations, which can further adjust the thermal conductivity, fire resistance and dielectric properties of the aerogel material to reduce the manufacturing cost of the aerogel composite material.

4、本發明所提供的製備方法中,提供一以乳化機或均質機進行快速縮合分散溶液技術,並在該縮合分散水溶液中也可添加微量水可分散之耐高溫膠材,並以此縮合分散溶液填充於一預成型模型中或一含纖維預成型模型中,進行凝膠化成型。進一步地,在後續凝膠化過程中使濕凝膠顆粒相互聚集在該預成型模型中或該含纖維預成型模型中,而形成一網狀氣凝膠結構。隨後進一步乾燥,即可製備成不同尺寸的管狀、板狀以及特定外觀型態的氣凝膠成型結構,利用此技術所製備之產品與其他技術相比較,不僅節省大量有機溶劑且製程快速。4. The preparation method provided by the present invention provides a technique for rapidly condensing a dispersed solution using an emulsifier or a homogenizer, and a high-temperature resistant rubber material that can be dispersed by a small amount of water can also be added to the condensed dispersed water solution, and the condensed dispersed solution is filled in a preformed mold or a fiber-containing preformed mold to perform gelation molding. Furthermore, in the subsequent gelation process, the wet gel particles are aggregated in the preformed mold or the fiber-containing preformed mold to form a mesh aerogel structure. After further drying, aerogel molding structures of different sizes, such as tubular, plate-shaped, and specific appearances, can be prepared. Compared with other technologies, the products prepared using this technology not only save a large amount of organic solvents but also have a fast process.

5、針對氣凝膠粉塵散落解決問題,本發明一方面在懸浮分散在水溶液中添加微量水可分散之耐高溫膠材包覆在氣凝膠結構表面以形成有機-無機複合結構。另一方面,提供一類纖維強化樹脂(LFRP)包覆技術,其中利用一耐高溫有機或無機膠體含浸塗布在一耐高溫金屬、無機或有機-無機複合薄膜、薄板或耐高溫纖維布,隨後進行氣凝膠預成型複合材料單層至多層包覆,並在常壓高溫環境下交聯固化之後,形成類纖維強化樹脂 (LFRP)多層包覆氣凝膠複合材料。以此技術可製備成兼具高強度、高隔熱、高防火且不掉粉塵的氣凝膠複合材。5. To solve the problem of aerogel dust scattering, the present invention, on the one hand, adds a small amount of water to the aqueous solution to dispersible high-temperature resistant adhesive material to coat the surface of the aerogel structure to form an organic-inorganic composite structure. On the other hand, a type of fiber-reinforced resin (LFRP) coating technology is provided, in which a high-temperature resistant organic or inorganic colloid is impregnated and coated on a high-temperature resistant metal, inorganic or organic-inorganic composite film, sheet or high-temperature resistant fiber cloth, and then a single layer or multiple layers of aerogel preformed composite material are coated, and after cross-linking and curing under normal pressure and high temperature environment, a fiber-reinforced resin (LFRP) multi-layer coated aerogel composite material is formed. This technology can be used to produce aerogel composites that have high strength, high thermal insulation, high fire resistance and are dust-free.

6、本發明所提供的製備方法中,此類纖維強化樹脂 (LFRP)包覆氣凝膠複合材,其中可通過樹脂種類及包覆材料的材質調控包覆外層的強度、耐用溫度、剛性、緻密性、導電導熱性或介電性等各種性質;其中,透過本發明所提供的製備技術,纖維強化樹脂 (LFRP)多層包覆氣凝膠複合其孔隙率介於50.0~75.0%,其密度介於0.20~0.60g/cm3,其熱傳係數介於0.020~0.045W/mk,其介電常數介於1.30~1.85,耐燃性質在UL94-5VA等級以上,最高耐熱溫度可達1200度高溫等性質。當高溫熱點溫度約850度下,產品厚度在2mm~3mm條件下,隔熱溫度約下降至200度以下。6. In the preparation method provided by the present invention, the fiber reinforced resin (LFRP) coated aerogel composite material can adjust the strength, durability temperature, rigidity, density, electrical and thermal conductivity or dielectric properties of the coated outer layer by the type of resin and the material of the coating material; wherein, through the preparation technology provided by the present invention, the fiber reinforced resin (LFRP) multi-layer coated aerogel composite has a porosity of 50.0~75.0%, a density of 0.20~0.60g/cm3, a heat transfer coefficient of 0.020~0.045W/mk, a dielectric constant of 1.30~1.85, a flame retardancy of UL94-5VA level or above, and a maximum heat resistance temperature of up to 1200 degrees. When the high temperature hot spot temperature is about 850 degrees, the insulation temperature drops to below 200 degrees when the product thickness is 2mm~3mm.

請參閱圖1,係本發明提供一種無塵室及電動車安全防護用無粉塵、高隔熱、高防火氣凝膠複合材料及其製備方法及其製備方法之實施態樣,其步驟包含:混合水解步驟(S1)、縮合分散步驟(S2)、結構成型步驟(S3)、常壓乾燥步驟(S4)、外層包覆步驟(S5)、固化成型步驟(S6) 、表面處理步驟(S7),其中:Please refer to FIG. 1, which is a dust-free, high heat insulation, high fireproof aerogel composite material for clean room and electric vehicle safety protection and its preparation method and its implementation mode of the preparation method, wherein the steps include: mixing and hydrolysis step (S1), condensation and separation step (S2), structure forming step (S3), atmospheric pressure drying step (S4), outer layer coating step (S5), curing and forming step (S6), surface treatment step (S7), wherein:

混合水解步驟(S1):於一乙醇水溶液中加入一矽氧烷前軀體以形成一混合溶液,其中,該矽氧烷前軀體包括一疏水改質矽氧烷化合物、一矽氧烷化合物或其組合,該疏水改質矽氧烷化合物包含不同鏈長疏水性改質矽氧烷化合物,隨後將一酸觸媒加入該混合溶液中以進行水解反應;在一些實施例中,該矽氧烷化合物包含四甲氧基矽烷(Tetramethoxysilane, TMOS)、四乙氧基矽烷(Tetraethoxysilane, TEOS)或其組合;該疏水性改質矽氧烷化合物包含甲基三甲氧基矽烷(Methyltrimethoxysilane,MTMS)、丙基三甲氧基矽烷(Propyltrimethoxysilane,PTMS)、己基三甲氧基矽烷(Hexyltrimethoxysilane,HTMS)、辛基三甲氧基矽烷(Octyltrimethoxysilane,OTMS)、六甲基二矽氮烷(Hexamethyldisilane,HMDS)等不同烷基鏈長取代的疏水性矽氧烷之一或其組合;添加該疏水改質矽氧烷的目的在於降低氣凝膠結構於乾燥過程的龜裂現象,而添加該矽氧烷的目的在於調控氣凝膠結構內部微細結構以增加結構中的孔洞含量;在一些實施例中,以整體混合溶液來說,該矽氧烷化合物及疏水改質矽氧烷的總含量莫耳百分比為0.5mol%至40mol%之間,而該乙醇水溶液的含量莫耳比為99.5mol%至60mol%之間。Mixing and hydrolysis step (S1): adding a siloxane precursor to an ethanol aqueous solution to form a mixed solution, wherein the siloxane precursor comprises a hydrophobic modified siloxane compound, a siloxane compound or a combination thereof, and the hydrophobic modified siloxane compound comprises hydrophobic modified siloxane compounds with different chain lengths, and then adding an acid catalyst to the mixed solution to perform a hydrolysis reaction; in some embodiments, the siloxane compound comprises tetramethoxysilane (Tetramethoxysilane, TMOS), tetraethoxysilane (Tetraethoxysilane, TEOS) or a combination thereof; the hydrophobic modified siloxane compound comprises methyltrimethoxysilane (MTMS), propyltrimethoxysilane (PTMS), hexyltrimethoxysilane (HTMS), octyltrimethoxysilane (OTMS), hexamethyldisilazane ( The invention relates to a hydrophobic siloxane or a combination thereof, wherein the hydrophobic siloxane is added to reduce the cracking of the aerogel structure during the drying process, and the hydrophobic siloxane is added to adjust the internal microstructure of the aerogel structure to increase the pore content in the structure. In some embodiments, the total molar percentage of the siloxane compound and the hydrophobic siloxane in the overall mixed solution is between 0.5 mol% and 40 mol%, and the molar ratio of the ethanol aqueous solution is between 99.5 mol% and 60 mol%.

在本實施例中,該矽氧烷化合物及該疏水改質矽氧烷化合物莫耳比由0:100至95:5;在一較佳實施例中,矽氧烷化合物及疏水改質矽氧烷化合物莫耳比為5:95;在另一較佳實施例中,矽氧烷化合物及疏水改質矽氧烷化合物莫耳比為介於0:100 mol%至40:60 mol%;該乙醇水溶液中,乙醇及水莫耳比由0:100至50:50;在一較佳實施例中,乙醇及水莫耳比為15:85。In this embodiment, the molar ratio of the siloxane compound to the hydrophobically modified siloxane compound is from 0:100 to 95:5; in a preferred embodiment, the molar ratio of the siloxane compound to the hydrophobically modified siloxane compound is 5:95; in another preferred embodiment, the molar ratio of the siloxane compound to the hydrophobically modified siloxane compound is between 0:100 mol% and 40:60 mol%; in the ethanol-water solution, the molar ratio of ethanol to water is from 0:100 to 50:50; in a preferred embodiment, the molar ratio of ethanol to water is 15:85.

在混合水解步驟(S1)中充分混合矽氧烷化合物或疏水改質矽氧烷化合物與大量之含微量酸觸媒乙醇水溶液的混合過程中,同時進行水解反應(hydrolysis),其中,該酸觸媒乙醇水溶液之溶劑包括乙醇、去離子水、處理水、二次處理水等之一種或不同組成的混合,該矽氧烷與疏水改質矽氧烷混合物之總含量與酸觸媒之含量的莫耳比為1:0.01至1:0.00005,當該矽氧烷與疏水改質矽氧烷混合溶液中該酸觸媒的含量比越高,水解速率越快;換句話說,酸觸媒的含量比越高,整體氣凝膠結構中離子含量越大,氣凝膠的介電損耗將會越大;於一較佳的實施例中,矽氧烷與疏水改質矽氧烷混合物之總含量與酸觸媒之含量的莫耳比為1:0.00014。In the mixing and hydrolysis step (S1), the siloxane compound or the hydrophobically modified siloxane compound is fully mixed with a large amount of an ethanol aqueous solution containing a trace amount of an acid catalyst, and a hydrolysis reaction is simultaneously carried out, wherein the solvent of the acid catalyst ethanol aqueous solution includes ethanol, deionized water, treated water, secondary treated water, etc. or a mixture of different compositions, and the total content of the siloxane and hydrophobically modified siloxane mixture and the content of the acid catalyst are 1:1. The molar ratio is 1:0.01 to 1:0.00005. The higher the content ratio of the acid catalyst in the mixed solution of the siloxane and the hydrophobically modified siloxane is, the faster the hydrolysis rate is. In other words, the higher the content ratio of the acid catalyst is, the greater the ion content in the overall aerogel structure is, and the greater the dielectric loss of the aerogel will be. In a preferred embodiment, the molar ratio of the total content of the mixture of siloxane and the hydrophobically modified siloxane to the content of the acid catalyst is 1:0.00014.

縮合分散步驟(S2):於該混合溶液中加入一分散水溶液,該分散水溶液包括一鹼觸媒,並利用乳化機或均質機等快速攪拌設備以高速攪拌進行縮合反應形成一分散溶膠溶液;需進一步說明的是,在縮合反應中,可通過控制該縮合反應溫度,所添加去離子水的含量以及攪拌速率以調節縮合反應的速率,來控制所獲得的該分散溶膠溶液內部氣凝膠微結構;該分散水溶液與該乙醇水溶液之體積比由75:25至30:70;在一較佳實施例中,該分散水溶液與該乙醇水溶液之體積比為50:50。Condensation and separation step (S2): a dispersed aqueous solution is added to the mixed solution, the dispersed aqueous solution includes an alkaline catalyst, and a rapid stirring device such as an emulsifier or a homogenizer is used to stir at a high speed to perform a condensation reaction to form a dispersed sol solution; it should be further explained that during the condensation reaction, the aerogel microstructure inside the dispersed sol solution can be controlled by controlling the condensation reaction temperature, the content of the added deionized water and the stirring rate to adjust the condensation reaction rate; the volume ratio of the dispersed aqueous solution to the ethanol aqueous solution is from 75:25 to 30:70; in a preferred embodiment, the volume ratio of the dispersed aqueous solution to the ethanol aqueous solution is 50:50.

在縮合分散步驟中,溫度的提升有助於明顯縮短縮合反應時間,即氣凝膠的凝膠化時間在該分散縮合步驟(S2)中有效地縮短;其中,於鹼觸媒與酸觸媒之含量當量數比為1.0:1.0時,該縮合反應溫度為20~55℃,縮合反應時間為20~250分鐘;在一些較佳實施例中,該縮合反應溫度為25℃,縮合反應時間約220分鐘,當該縮合反應溫度為50℃時,縮合反應時間約15分鐘。In the condensation dispersion step, the increase in temperature helps to significantly shorten the condensation reaction time, that is, the gelation time of the aerogel is effectively shortened in the dispersion condensation step (S2); wherein, when the content equivalent ratio of the alkaline catalyst to the acid catalyst is 1.0:1.0, the condensation reaction temperature is 20-55°C, and the condensation reaction time is 20-250 minutes; in some preferred embodiments, the condensation reaction temperature is 25°C, and the condensation reaction time is about 220 minutes; when the condensation reaction temperature is 50°C, the condensation reaction time is about 15 minutes.

在縮合分散步驟中,當該水解的矽氧烷分子及疏水性矽氧烷分子混合物在懸浮分散水溶液形成奈米級至次微米級的水解的濕凝膠顆粒下,可利用添加微量水可分散之耐高溫膠材在此懸浮分散水溶液中,使隨後凝膠化過程讓奈米級至次微米級的氣凝膠濕膠縮合聚集形成網狀結構後,使該微量水可分散之耐高溫膠材可包覆在氣凝膠三次元網狀結構的表面以形成有機-無機複合奈米結構材,其中,所添加微量水可分散之耐高溫膠材與分散水溶液的體積比介於0.01%至5%,且該耐高溫膠材能夠耐高溫300℃以上。In the condensation and decomposition step, when the hydrolyzed siloxane molecules and the hydrophobic siloxane molecule mixture form nano-scale to sub-micron-scale hydrolyzed wet gel particles in a suspended dispersed aqueous solution, a trace amount of water-dispersible high-temperature resistant adhesive material can be added to the suspended dispersed aqueous solution, so that the subsequent gelation process allows the nano-scale to sub-micron-scale aerogel wet gel to condense and aggregate to form a network structure, and then the trace amount of water-dispersible high-temperature resistant adhesive material can be coated on the surface of the aerogel three-dimensional network structure to form an organic-inorganic composite nanostructure material, wherein the volume ratio of the added trace amount of water-dispersible high-temperature resistant adhesive material to the dispersed aqueous solution is between 0.01% and 5%, and the high-temperature resistant adhesive material can withstand high temperatures above 300°C.

在另一些實施例中,鹼觸媒含量增加也會明顯縮短縮合反應時間,其中,1.0M鹼觸媒與1.0M酸觸媒的含量當量數比為0.8:1.0~2.0:1.0,縮合反應時間為360~約3分鐘;在一些實施例,該含量當量數比為0.8:1.0,縮合反應時間為360分鐘;在另一些較佳實施例中,該含量當量數比1.6:1.0,縮合反應時間約為10分鐘;需進一步說明的是,當該含量當量數比小於1.0:1.0時,縮合反應時間逐漸增加,而所製備的氣凝膠介電耗損會有明顯下降;當該含量當量數比大於1.0:1.0時,縮合反應時間逐漸減少,所製備之氣凝膠介電耗損卻會因離子含量提高而明顯上升;於本實施樣態之一較佳實施例中,該含量體積比為1.2:1.0。In other embodiments, the increase in the content of the alkali catalyst will also significantly shorten the condensation reaction time, wherein the content equivalent ratio of 1.0M alkali catalyst to 1.0M acid catalyst is 0.8:1.0~2.0:1.0, and the condensation reaction time is 360~about 3 minutes; in some embodiments, the content equivalent ratio is 0.8:1.0, and the condensation reaction time is 360 minutes; in other preferred embodiments, the content equivalent ratio is 1.6:1.0, and the condensation reaction time is 1.6:1.0. The time is about 10 minutes; it should be further explained that when the content equivalent ratio is less than 1.0:1.0, the condensation reaction time gradually increases, and the dielectric loss of the prepared aerogel will be significantly reduced; when the content equivalent ratio is greater than 1.0:1.0, the condensation reaction time gradually decreases, but the dielectric loss of the prepared aerogel will be significantly increased due to the increase in ion content; in a preferred embodiment of this implementation, the content volume ratio is 1.2:1.0.

結構成型步驟(S3):將該懸浮分散溶膠溶液注入一預成型模型中,促使該含微量耐高溫膠材之懸浮分散溶膠溶液在預成型模型中進一步縮合形成一類固態氣凝膠濕膠之預成型結構;在此成型步驟中,矽氧烷氣凝膠分子經過縮合反應而聚集形成矽氧烷氣凝膠分子聚集體,矽氧烷氣凝膠分子的初始結構尺寸可控制在5~10nm,初始結構再堆疊形成約50~100nm的氣凝膠濕膠分子,50~100nm氣凝膠濕膠分子更進一步堆疊而形成更大的聚集體,並相互連結成三次元網狀結構,形成穩定的含大量溶劑之耐高溫膠材包覆氣凝膠三次元網狀結構表面的有機-無機複合凝膠結構材料。Structural forming step (S3): injecting the suspended dispersed sol solution into a preformed mold, causing the suspended dispersed sol solution containing a trace amount of high temperature resistant adhesive material to further condense in the preformed mold to form a preformed structure of a solid aerogel wet glue; in this forming step, the silicone aerogel molecules aggregate to form silicone aerogel molecular aggregates through condensation reaction, and the initial size of the silicone aerogel molecules is reduced. The structure size can be controlled at 5~10nm. The initial structure is stacked to form aerogel wet gel molecules of about 50~100nm. The 50~100nm aerogel wet gel molecules are further stacked to form larger aggregates and interconnected into a three-dimensional network structure, forming a stable organic-inorganic composite gel structure material in which a large amount of solvent-containing high-temperature resistant glue material covers the surface of the aerogel three-dimensional network structure.

在另一些實施例中,將含微量耐高溫膠材之懸浮分散溶膠溶液注入含大量纖維預成型模型中;在此條件下,矽氧烷氣凝膠分子在纖維表面吸附,並在纖維表面縮合堆疊成50~100nm的氣凝膠濕膠分子,50~100nm氣凝膠濕膠分子更進一步在纖維與纖維結構之間堆疊以形成三次元氣凝膠網狀結構,進而形成穩定且含有大量纖維的耐高溫膠材包覆氣凝膠三次元網狀結構表面的有機-無機複合凝膠結構材料;在該成型步驟中,分子級氣凝膠溶液可利用含浸技術、壓吸、噴淋、灌注或真空吸附等技術於纖維材料上進行複合加工。因此,該預成型模型係可包括一成型模或一含纖維材料的成型模。In other embodiments, a suspended dispersed sol solution containing a trace amount of high temperature resistant rubber material is injected into a preformed model containing a large amount of fiber; under this condition, the silicone aerogel molecules are adsorbed on the fiber surface and condensed and stacked on the fiber surface to form 50-100nm aerogel wet gel molecules. The 50-100nm aerogel wet gel molecules further bind to the fiber and the fiber structure. The three-dimensional aerogel mesh structure is formed by stacking them together, and then forming an organic-inorganic composite gel structure material in which a stable and high-temperature-resistant gel material containing a large amount of fibers covers the surface of the aerogel three-dimensional mesh structure; in the molding step, the molecular-level aerogel solution can be composited on the fiber material using impregnation technology, pressure suction, spraying, infusion or vacuum adsorption technology. Therefore, the preformed model can include a molding mold or a molding mold containing fiber materials.

在一些實施例中,該纖維材料包括金屬纖維、無機纖維、液晶纖維、有機纖維,具體而言,例如微米至奈米尺度之各類金屬纖維或金屬棒、玻璃纖維、碳纖維、石英纖維、陶瓷纖維、岩棉纖維、Kevlar聚醯胺纖維、Nomex聚醯胺纖維、尼龍纖維、聚酯纖維、各類纖維素、生物可分解無機纖維或生物可分解有機纖維所製備之各類多孔隙散棉、蓆、紙、毯、繩、厚板等或其組合。In some embodiments, the fiber material includes metal fiber, inorganic fiber, liquid crystal fiber, organic fiber, specifically, various types of metal fibers or metal rods in the micron to nanometer scale, glass fiber, carbon fiber, quartz fiber, ceramic fiber, rock wool fiber, Kevlar polyamide fiber, Nomex polyamide fiber, nylon fiber, polyester fiber, various types of cellulose, various types of porous loose cotton, mats, paper, blankets, ropes, thick boards, etc. prepared from biodegradable inorganic fibers or biodegradable organic fibers, or a combination thereof.

常壓乾燥步驟(S4):於常壓下,在一成型乾燥溫度下使該類固體氣凝膠濕膠結構在一常壓條件下以高溫進行乾燥,以獲得結構均一之具低熱傳氣凝膠預成型複合材料,其包含氣凝膠板材或氣凝膠/纖維複合板;在一些實施例中,該乾燥溫度介於60~150℃。Normal pressure drying step (S4): drying the solid aerogel wet gel structure at a high temperature under normal pressure and at a forming drying temperature to obtain a uniform structure of a low heat transfer aerogel preformed composite material, which includes an aerogel sheet or an aerogel/fiber composite sheet; in some embodiments, the drying temperature is between 60 and 150°C.

進一步地,該乾燥步驟包括溶劑汽化步驟(S4-1)、溶劑回收步驟(S4-2)及溶劑突沸步驟(S4-3)。Furthermore, the drying step includes a solvent vaporization step (S4-1), a solvent recovery step (S4-2) and a solvent boiling step (S4-3).

汽化步驟(S4-1):將該類固態預成型氣凝膠濕膠體系放置於一常壓且混合溶劑共沸汽化溫度下,利用溫度讓大量含醇類水分子快速共沸汽化而將氣凝膠濕膠體系醇類水分子共沸蒸餾乾燥;在一些實施例中,該溶劑共沸溫度為60~90℃。Vaporization step (S4-1): placing the solid preformed aerogel wet gel system at a normal pressure and a mixed solvent azeotropic vaporization temperature, using the temperature to allow a large amount of alcohol-containing water molecules to quickly azeotropically vaporize and azeotropically distill and dry the alcohol water molecules in the aerogel wet gel system; in some embodiments, the solvent azeotropic temperature is 60-90°C.

溶劑回收步驟(S4-2):在該共沸汽化溫度環境下,令預成型結構中大量的含酒精水溶液快速共沸汽化下,並將汽化蒸氣引導至一熱交換回收設備;在該熱交換回收設備中促使含水酒精冷凝並回收;在本發明的一些實施例中,該冷凝之含水酒精為本製程的附加回收產品,該回收目的一方面回收有價值的酒精副產品以降低製造成本;另一方面,回收含酒精蒸氣以降低對環境及空氣的污染。Solvent recovery step (S4-2): In the azeotropic vaporization temperature environment, a large amount of alcohol-containing aqueous solution in the preformed structure is rapidly azeotropically vaporized, and the vaporized steam is guided to a heat exchange recovery device; in the heat exchange recovery device, the hydrous alcohol is condensed and recovered; in some embodiments of the present invention, the condensed hydrous alcohol is an additional recovered product of the process, and the purpose of the recovery is, on the one hand, to recover valuable alcohol by-products to reduce manufacturing costs; on the other hand, to recover alcohol-containing vapor to reduce pollution to the environment and air.

突沸步驟(S4-3):將該汽化完畢之含微量溶劑之預成型氣凝膠環境溫度調整至溶劑突沸溫度,使其內部所含有的微量溶劑產生快速汽化突沸現象;在一些實施例中,該突沸溫度為110~150℃;需進一步說明的是,在該突沸溫度所創造的高溫環境下,使該氣凝膠內部微量醇類水分子所產生的突沸現象,促使氣凝膠內部產生一正蒸氣壓力,該正蒸氣壓力可以抑制氣凝膠結構在乾燥過程中產生收縮或崩潰的現象;另一方面,該正壓力得令氣凝膠網狀結構膨脹而產生大量微細孔洞而呈多孔性,以獲得該氣凝膠預成型材料;是以,該製備方法可用以製備低密度且高孔隙率的氣凝膠或氣凝膠/纖維複合材料,其熱傳導性質k約為0.013~0.018W/mk;氣凝膠/纖維複合材料之熱傳導性質k約為0.022~0.032W/mk,耐燃性質在UL94-V0等級以上。Boiling step (S4-3): The ambient temperature of the preformed aerogel containing trace solvent after vaporization is adjusted to the solvent boiling temperature, so that the trace solvent contained therein undergoes rapid vaporization and boiling. In some embodiments, the boiling temperature is 110-150°C. It should be further explained that, under the high temperature environment created by the boiling temperature, the boiling phenomenon of trace alcohol water molecules inside the aerogel is generated, which promotes the generation of a positive vapor pressure inside the aerogel. The positive vapor pressure can inhibit the aerogel structure from drying. On the other hand, the positive pressure causes the aerogel network structure to expand and generate a large number of fine pores to become porous, so as to obtain the aerogel preform material. Therefore, the preparation method can be used to prepare low-density and high-porosity aerogel or aerogel/fiber composite materials, whose thermal conductivity k is about 0.013~0.018W/mk; the thermal conductivity k of the aerogel/fiber composite material is about 0.022~0.032W/mk, and the flame retardancy is above UL94-V0 level.

此外,由於無添加烷類、芳香苯類、胺類等大量有機溶劑以及界面活性劑,因此在乾燥過程較為安全,且可製備出更高純度的氣凝膠產品。因所製備的高孔隙率氣凝膠板材或氣凝膠/纖維複合板中不含各類雜質,所以產品的熱傳導性質、介電常數及介電損耗等性質均會更優異。In addition, since no large amount of organic solvents such as alkanes, aromatic benzenes, amines, and surfactants are added, the drying process is safer and aerogel products with higher purity can be produced. Since the high-porosity aerogel sheet or aerogel/fiber composite board produced does not contain various impurities, the thermal conductivity, dielectric constant, and dielectric loss of the product will be better.

外層包覆步驟(S5):準備一耐300℃以上高溫膠材溶液,將該耐高溫膠材溶液含浸塗布在一耐300℃以上高溫材料表面,使高溫膠材溶液均勻滲入該耐高溫材料內部,例如是耐高溫纖維布內部,隨後進一步利用含浸耐高溫膠材溶液之耐高溫材料進行氣凝膠預成型複合材料單層或多層包覆。其中,該耐高溫材料包含非有機薄膜、非有機薄板或耐高溫纖維之一或其組合,例如耐高溫薄膜,該耐高溫膠材溶液可為耐高溫無機膠材或熱固性樹脂溶液,其中該耐高溫膠材溶液中的耐高溫膠材能夠耐高溫300℃以上,而其他如耐高溫材料、耐高溫薄膜及耐高溫纖維所能夠達到耐高溫的溫度也是在300℃以上,具體而言,該耐高溫膠材溶液包含無機膠、熱塑性或熱固性樹脂之一或其組合,該無機膠材包含例如水玻璃膠、無機矽樹脂膠、氧化銅-磷酸膠、矽酸鹽膠、磷酸-矽酸鹽膠、硫酸鹽膠、氧化鎂-二氧化矽-硼砂無機膠,該熱固性樹脂包含環氧樹脂、聚醯亞胺樹脂、聚醚醯亞胺樹脂、聚苯醚樹脂、聚苯硫醚樹脂、聚醚酮液晶高分子樹脂、聚四氟乙烯樹脂、聚三聚氰胺樹脂、聚酚醛樹脂、聚三聚氰胺-甲醛樹脂、聚酯膠、聚醯胺膠、聚醯胺酯膠、矽膠等膠材之一或其組合。以該含浸膠材纖維布包覆步驟整體而言,該膠材溶液的濃度介於10 ~ 75.0wt%;其中,膠材溶液的濃度越低,膠材溶液滲入纖維布內部溶液效率越佳且加工較容易,但所製備的含浸膠材溶液之纖維布多層包覆的氣凝膠成型複合材料的緻密性越差,結構中孔洞含量越高,因此越容易產生氣凝膠粉塵洩漏;相對地,膠材溶液的濃度越高,膠材溶液披覆在纖維布表面含量越高,所製備的含浸膠材溶液之纖維布多層包覆的氣凝膠成型複合材料的強度越高、緻密性越佳,且越不易產生氣凝膠粉塵洩漏,但加工越困難,且膜厚較不易控制。是以,利用所含浸膠材溶液的濃度可以控制含浸膠材溶液之纖維布多層包覆的氣凝膠成型複合材料,其成型加工及不掉粉塵性質,最佳化的膠材溶液濃度介於30~50.0wt%。Outer layer coating step (S5): prepare a high temperature resistant rubber solution above 300°C, apply the high temperature resistant rubber solution to the surface of a high temperature resistant material above 300°C, and make the high temperature rubber solution evenly penetrate into the interior of the high temperature resistant material, such as the interior of the high temperature resistant fiber cloth, and then further use the high temperature resistant material impregnated with the high temperature resistant rubber solution to coat the aerogel preformed composite material in a single layer or multiple layers. The high temperature resistant material comprises one or a combination of non-organic film, non-organic sheet or high temperature resistant fiber, such as high temperature resistant film. The high temperature resistant adhesive solution can be a high temperature resistant inorganic adhesive or a thermosetting resin solution. The high temperature resistant adhesive in the high temperature resistant adhesive solution can withstand a high temperature of more than 300°C, and the temperature that other materials such as high temperature resistant materials, high temperature resistant films and high temperature resistant fibers can reach is also above 300°C. Specifically, the high temperature resistant adhesive solution comprises one or a combination of inorganic adhesive, thermoplastic or thermosetting resin. The inorganic adhesive material includes, for example, water glass adhesive, inorganic silicone adhesive, copper oxide-phosphate adhesive, silicate adhesive, phosphoric acid-silicate adhesive, sulfate adhesive, magnesium oxide-silicon dioxide-borax inorganic adhesive, and the thermosetting resin includes epoxy resin, polyimide resin, polyetherimide resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether ketone liquid crystal polymer resin, polytetrafluoroethylene resin, polymelamine resin, polyphenolic resin, polymelamine-formaldehyde resin, polyester adhesive, polyamide adhesive, polyamide adhesive, silicone adhesive, or a combination thereof. In the step of wrapping the impregnated rubber fiber cloth as a whole, the concentration of the rubber solution is between 10 and 75.0wt%; wherein, the lower the concentration of the rubber solution, the better the efficiency of the rubber solution penetrating into the internal solution of the fiber cloth and the easier it is to process, but the poorer the density of the prepared aerogel molding composite material of the fiber cloth impregnated with the rubber solution and coated with multiple layers, the higher the content of pores in the structure, and therefore the easier it is to produce aerogel dust leakage; relatively, the higher the concentration of the rubber solution, the higher the content of the rubber solution coated on the surface of the fiber cloth, the higher the strength of the prepared aerogel molding composite material of the fiber cloth impregnated with the rubber solution and coated with multiple layers, the better the density, and the less likely it is to produce aerogel dust leakage, but the more difficult it is to process, and the film thickness is more difficult to control. Therefore, the concentration of the impregnated rubber solution can be used to control the molding and dust-free properties of the aerogel molding composite material with multiple layers of fiber cloth impregnated with the rubber solution. The optimized concentration of the rubber solution is between 30 and 50.0 wt%.

於該外層包覆步驟(S5),該耐高溫非有機薄膜、耐高溫非有機薄板或耐高溫纖維之一或其組合,其中有關耐高溫非有機薄膜、耐高溫非有機薄板包含金屬、無機及有機-無機複合等耐高溫薄膜、薄板進行氣凝膠單層包覆、多層包覆或與氣凝膠進行多層積層堆疊包覆。值得一提的是,多層包覆指的是同一種耐高溫薄膜的多層堆疊包覆,而多層積層堆疊包覆則指的是多種耐高溫薄膜的多層堆疊包覆,換言之,本發明並不限定用來包覆氣凝膠預成型複合材料之耐高溫薄膜的種類是金屬膜板、無機膜板或有機-無機複合耐高溫薄膜板以及單層或多層,進一步,其中金屬膜板包含鋁、不鏽鋼、銅等金屬材料所製備的薄膜或其組合;無機膜板包含雲母薄片、石墨薄片、石墨烯薄片、玻璃薄片及各類陶瓷薄片、金屬氧化物、金屬氮矽化合物及金屬碳矽化合物所製備成薄片、薄板或其組合;有機-無機複合薄膜包含如鋁、不鏽鋼、銅、雲母片、石墨、石墨烯、玻璃及陶瓷等金屬、金屬氧化物、金屬氮矽化合物及金屬碳矽化合物微粒結合各類有機膠或各類無機膠所複合製造的耐高溫有機-無機複合薄膜、薄板或無機-無機複合薄膜、薄板等組合。更進一步,其中耐300度以上高溫纖維包含如石英纖維、玻璃纖維、陶瓷纖維、碳纖維、有機纖維如:尼龍纖維、聚酯纖維、聚氟纖維、液晶纖維如:Kevlar聚醯胺纖維、Nomex聚醯胺纖維及各類纖維素、生物可分解無機或有機纖維等複合所製備之各類多孔隙散棉、蓆、紙、毯、繩、厚板之一或其組合。In the outer layer coating step (S5), the high temperature resistant non-organic film, high temperature resistant non-organic sheet or high temperature resistant fiber or a combination thereof, wherein the high temperature resistant non-organic film, high temperature resistant non-organic sheet comprises metal, inorganic and organic-inorganic composite high temperature resistant film, sheet is coated with aerogel in a single layer, multiple layers or is stacked and coated with aerogel in multiple layers. It is worth mentioning that multi-layer coating refers to multi-layer stacking coating of the same high-temperature resistant film, while multi-layer stacking coating refers to multi-layer stacking coating of multiple high-temperature resistant films. In other words, the present invention does not limit the type of high-temperature resistant film used to coat the aerogel preformed composite material to metal film plates, inorganic film plates, or organic-inorganic composite high-temperature resistant film plates, as well as single layers or multiple layers. Furthermore, the metal film plates include films made of metal materials such as aluminum, stainless steel, copper, or a combination thereof; the inorganic film plates include mica flakes, stone flakes, or other materials. The invention relates to a thin sheet, a thin plate or a combination thereof prepared from graphite sheets, graphene sheets, glass sheets and various ceramic sheets, metal oxides, metal nitrogen silicon compounds and metal carbon silicon compounds; an organic-inorganic composite film comprises a high-temperature resistant organic-inorganic composite film, a thin plate or an inorganic-inorganic composite film, a thin plate and the like which are composited with metals such as aluminum, stainless steel, copper, mica sheets, graphite, graphene, glass and ceramics, metal oxides, metal nitrogen silicon compounds and metal carbon silicon compound particles in combination with various organic glues or various inorganic glues. Furthermore, the high temperature resistant fiber of 300 degrees or above includes one or a combination of quartz fiber, glass fiber, ceramic fiber, carbon fiber, organic fiber such as nylon fiber, polyester fiber, polyfluorinated fiber, liquid crystal fiber such as Kevlar polyamide fiber, Nomex polyamide fiber and various types of cellulose, biodegradable inorganic or organic fiber, etc., and various porous loose cotton, mats, paper, blankets, ropes, thick plates prepared by composites.

固化成型步驟(S6):將該含浸耐300度以上高溫膠材溶液之纖維布單層或多層的耐高溫薄膜等耐高溫材料包覆的氣凝膠預成型複合材料放置在含浸耐高溫膠材溶液的溶劑乾燥的沸點溫度下,促使該膠材溶液的溶劑汽化以降低成型缺陷或氣泡孔洞的形成,使該膠材溶液逐漸乾燥,此處溶劑乾燥溫度隨該膠材溶液的混合溶劑沸點而定;在一些實施例中,混合溶劑為乙醇,其溶劑乾燥溫度為60~75℃;在另一些實施例中,混合溶劑為丁酮,其溶劑乾燥溫度為80~90℃;在另一些實施例中,溶劑為水,其水溶劑乾燥溫度為80~102℃;是以,在實施例中的該溶劑乾燥溫度係可介於60~115℃,乾燥後所得之含浸膠材溶液之纖維布不會因乾燥溫度過高所產生的大量氣泡而產生孔洞,導致後續應用中氣凝膠粉塵的洩漏。隨後利用一更高的固化成型溫度進行含浸該耐高溫膠材溶液的固化成行型步驟,其中該固化成型溫度係高於該溶劑乾燥溫度,藉以獲得一具高強度、低熱傳、低介電、高防火的耐高溫薄膜包覆氣凝膠預成型複合材料。Curing and forming step (S6): placing the aerogel preformed composite material covered with a high temperature resistant material such as a single layer of fiber cloth or multiple layers of high temperature resistant film impregnated with a high temperature resistant rubber solution of more than 300 degrees at a boiling point temperature at which the solvent impregnated with the high temperature resistant rubber solution dries, promoting the solvent of the rubber solution to vaporize to reduce the formation of molding defects or bubbles and cavities, and gradually drying the rubber solution. The solvent drying temperature here depends on the boiling point of the mixed solvent of the rubber solution; in some embodiments, the mixed solvent is acetone. In some embodiments, the mixed solvent is butanone, and the solvent drying temperature is 60-75°C; in other embodiments, the mixed solvent is butanone, and the solvent drying temperature is 80-90°C; in other embodiments, the solvent is water, and the water solvent drying temperature is 80-102°C; therefore, the solvent drying temperature in the embodiments can be between 60-115°C, and the fiber cloth impregnated with the rubber solution obtained after drying will not generate holes due to a large number of bubbles generated by excessively high drying temperatures, resulting in leakage of aerogel dust in subsequent applications. Then, a higher curing molding temperature is used to perform a curing molding step of impregnating the high-temperature resistant adhesive solution, wherein the curing molding temperature is higher than the solvent drying temperature, so as to obtain a high-strength, low heat transfer, low dielectric, and high fire-resistant high-temperature film-coated aerogel preformed composite material.

在另一實施例,在 溶劑乾燥步驟中,含浸膠材溶液之纖維布內部的有機溶劑伴隨著汽化,例如是將含浸該耐高溫膠材溶液之該非有機薄膜、該非有機薄板或該耐300℃以上高溫纖維包覆該氣凝膠預成型材料所形成的該耐高溫薄膜包覆氣凝膠預成型材料的複合材料,在該耐高溫膠材之溶劑乾燥溫度下使該溶劑汽化。若為常溫固化型樹脂膠材,該含浸膠材溶液之纖維布在溶劑汽化過程中伴隨固化,即可獲得一具高強度無塵室及電動車安全防護用無粉塵、高隔熱氣凝膠複合材料。換言之,在此步驟中除了溶劑乾燥外還同時包含了膠材樹脂固化,故此步驟亦可稱為常溫乾燥固化步驟。In another embodiment, in the solvent drying step, the organic solvent inside the fiber cloth impregnated with the rubber solution is vaporized, for example, the non-organic film, the non-organic sheet or the high-temperature resistant fiber above 300°C impregnated with the high-temperature resistant rubber solution is coated with the aerogel preform material to form a composite material of the high-temperature resistant film-coated aerogel preform material, and the solvent is vaporized at the solvent drying temperature of the high-temperature resistant rubber material. If it is a room temperature curing resin rubber material, the fiber cloth impregnated with the rubber solution is cured during the solvent vaporization process, and a high-strength dust-free, high-insulation aerogel composite material for clean room and electric vehicle safety protection can be obtained. In other words, this step not only involves solvent drying but also the curing of the adhesive resin, so this step can also be called a room temperature drying and curing step.

於固化成型步驟(S6),將該含浸或塗布耐高溫膠材溶液在一耐高溫纖維布或耐高溫薄膜/耐高溫薄板多層包覆的氣凝膠預成型複合材料於一特定交聯固化溫度下,使無機膠或熱固性高分子鏈之間以及無機膠或熱固性分子與氣凝膠分子之間進行交聯反應並結合固化,如水玻璃膠、無機矽樹脂膠等無機膠以及熱固性高分子為環氧樹脂(epoxy),該交聯固化溫度約為120~200℃,在一些實施例中,最佳交聯固化溫度為150~180℃或185~190℃;另一方面,如氧化銅-磷酸膠、矽酸鹽膠、磷酸-矽酸鹽膠等無機膠以及熱固性高分子為聚醯亞胺(polyimide),該交聯固化溫度約為120~325℃一系列交聯固化溫度,在一些實施例中,最高交聯固化溫度為320~325℃。在該(S6)交聯固化步驟中,於特定的交聯溫度下,該含浸或塗布有機或無機膠材溶液在一耐高溫纖維布或耐高溫薄膜/耐高溫薄板分子間相互交聯反應,使形成一高隔熱性、高防火、高強度且不掉粉塵之含浸或塗布耐高溫膠材溶液在一耐高溫纖維布或耐高溫薄膜/耐高溫薄板多層包覆的氣凝膠成型複合材料。In the curing step (S6), the aerogel preformed composite material impregnated or coated with a high-temperature resistant adhesive solution and coated with a high-temperature resistant fiber cloth or a high-temperature resistant film/high-temperature resistant sheet is subjected to a specific crosslinking curing temperature to allow the inorganic adhesive or thermosetting polymer chains and the inorganic adhesive or thermosetting molecules and the aerogel molecules to undergo crosslinking reactions and bond curing. For example, when the inorganic adhesive such as water glass adhesive and inorganic silicone adhesive and the thermosetting polymer are epoxy resins, the crosslinking reaction is performed at a specific crosslinking curing temperature. The curing temperature is about 120-200°C. In some embodiments, the optimal crosslinking curing temperature is 150-180°C or 185-190°C. On the other hand, inorganic glues such as copper oxide-phosphate glue, silicate glue, phosphoric acid-silicate glue, and thermosetting polymers such as polyimide have a crosslinking curing temperature of about 120-325°C. In some embodiments, the highest crosslinking curing temperature is 320-325°C. In the (S6) crosslinking and curing step, at a specific crosslinking temperature, the impregnated or coated organic or inorganic adhesive solution crosslinks with each other between molecules on a high-temperature resistant fiber cloth or a high-temperature resistant film/high-temperature resistant sheet to form an aerogel molding composite material with high thermal insulation, high fire resistance, high strength and no dust, which is a high-temperature resistant adhesive solution impregnated or coated on a high-temperature resistant fiber cloth or a high-temperature resistant film/high-temperature resistant sheet with multiple layers.

請參閱圖2,係第一實施例前述製備方法所製備兼具高強度、高防火、高隔熱性質且不掉粉塵的管狀類纖維強化樹脂(LFRP)包覆氣凝膠複合材料外觀照片,圖2中由上至下分別是三種不同耐高溫膠材管狀多層包覆並交聯固化的具高強度、高防火、高隔熱性質且不掉粉塵之包覆氣凝膠複合材料。由圖中顯示最上面為白色矽膠系列玻璃纖維強化樹脂包覆的管狀氣凝膠複合材料;相對地,中間深顏色為聚醯亞胺系列玻璃纖維強化樹脂包覆的管狀氣凝膠複合材料;最下面淺黃顏色為環氧樹脂系列玻璃纖維強化樹脂包覆的管狀氣凝膠複合材料。Please refer to FIG. 2, which is an appearance photograph of a tubular fiber-reinforced resin (LFRP) coated aerogel composite material having high strength, high fire resistance, high thermal insulation and no dust prepared by the aforementioned preparation method of the first embodiment. From top to bottom in FIG. 2, there are three different high-temperature resistant plastic tubular multi-layer coated and cross-linked cured coated aerogel composite materials having high strength, high fire resistance, high thermal insulation and no dust. As shown in the figure, the top one is a white silicone series glass fiber reinforced resin coated tubular aerogel composite material; in contrast, the middle dark color is a polyimide series glass fiber reinforced resin coated tubular aerogel composite material; and the bottom light yellow color is an epoxy resin series glass fiber reinforced resin coated tubular aerogel composite material.

請參閱圖3,係第一實施例前述製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料內部低熱傳導純氣凝膠斷面的掃描式電子顯微鏡SEM觀測照片,放大倍率為300倍;在電子顯微鏡觀測下,其微觀結構呈現明顯的氣凝膠/纖維複合材料,在大量纖維之間以尺寸介於次微米至微米級圓球狀氣凝膠聚集的三次元網狀團聚體;此外,由圖3可看出,具低熱傳氣凝膠材料中除了氣凝膠團聚結構之外,還具備了微量的耐高溫膠材在數微米至次微米級氣凝膠顆粒之間披覆的串聯結構,以及在纖維及氣凝膠顆粒之間依然含有大量微米孔洞串聯而形成的孔洞結構賦予了其低熱傳導性質。Please refer to FIG. 3, which is a scanning electron microscope SEM observation photograph of a cross section of a low heat conduction pure aerogel inside a fiber-reinforced resin-coated aerogel composite material having high strength, high fire resistance, high heat insulation and dust-free properties prepared by the aforementioned preparation method of the first embodiment, with a magnification of 300 times; under electron microscope observation, its microstructure shows obvious aerogel/fiber composite material, with a large number of fibers separated by a large size. A three-dimensional network aggregate between sub-micron and micron-sized spherical aerogels. In addition, as shown in Figure 3, the low heat transfer aerogel material has not only the aerogel agglomeration structure, but also a series structure in which a small amount of high-temperature resistant rubber is coated between aerogel particles of several microns to sub-microns, and a pore structure formed by a large number of micron-sized holes in series between the fibers and aerogel particles, which gives it low heat transfer properties.

請參閱圖4,係第二實施例前述製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料的外觀照片,第二樣態實施例為上下二層為耐高溫無機膠塗布雲母片強化包覆氣凝膠複合材料,以提供一更耐高溫、高強度且高隔熱的雲母強化樹脂包覆層,在此外殼結構內部為低熱傳導係數氣凝膠/纖維複合材料。以上結構也可進行多層積層堆疊結構,以強化氣凝膠應用領域。Please refer to Figure 4, which is an appearance photo of a fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and dust-free prepared by the aforementioned preparation method of the second embodiment. The second embodiment is a high-temperature-resistant inorganic glue-coated mica sheet-reinforced coated aerogel composite material on the upper and lower layers to provide a mica-reinforced resin coating layer that is more resistant to high temperatures, high strength and high heat insulation, and the inside of the shell structure is a low thermal conductivity coefficient aerogel/fiber composite material. The above structure can also be stacked in multiple layers to enhance the application field of aerogel.

請參閱圖5,係第二實施態兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料內部斷面的SEM掃描式電子顯微鏡觀測照片,放大倍率為250倍;由圖5顯示本實施例中氣凝膠複合材料的內部為氣凝膠/纖維複合材料,該產品是由大量次微米級氣凝膠分子吸附在纖維表面並在纖維之間孔洞相互聚集成三次元的氣凝膠網狀結構,且在整體聚集結構中依然含有大量的孔洞,相關孔洞提供氣凝膠/纖維複合毯低熱傳之特性,且大量纖維提升了氣凝膠/纖維複合板適當強度等性質。Please refer to FIG5, which is a SEM scanning electron microscope observation photograph of the internal cross section of the fiber-reinforced resin-coated aerogel composite material of the second embodiment, which has high strength, high fire resistance, high heat insulation and does not drop dust, with a magnification of 250 times; FIG5 shows that the interior of the aerogel composite material in this embodiment is an aerogel/fiber composite material, and the product is a three-dimensional aerogel network structure composed of a large number of sub-micron-sized aerogel molecules adsorbed on the fiber surface and the holes between the fibers are aggregated to form a three-dimensional aerogel network structure, and the overall aggregated structure still contains a large number of holes. The relevant holes provide the aerogel/fiber composite blanket with low heat transfer characteristics, and the large number of fibers improve the appropriate strength and other properties of the aerogel/fiber composite board.

表面處理步驟:將該高強度、低熱傳、低介電、高防火的耐高溫薄膜包覆氣凝膠複合材料表面利用拋光、噴氣以及表面噴塗氣凝膠防火隔熱塗料之一或其組合,並進行清潔及表面保護等製程組合將以形成兼具高強度、低熱傳、低介電、高防火的耐高溫纖維布或耐高溫薄膜/耐高溫薄板多層包覆的氣凝膠成型複合材料。Surface treatment step: The surface of the high-strength, low-heat-transfer, low-dielectric, high-fire-resistant high-temperature-resistant film-coated aerogel composite material is polished, sprayed, and sprayed with aerogel fire-proof and heat-insulating coatings or a combination thereof, and then cleaned and surface protected to form a high-strength, low-heat-transfer, low-dielectric, high-fire-resistant high-temperature-resistant fiber cloth or high-temperature-resistant film/high-temperature-resistant sheet multi-layer coated aerogel molding composite material.

請參閱圖6,係第三實施例前述製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料的外觀照片,第三樣態實施例為上下二層為耐高溫無機膠塗布雲母片包覆層,隨後以石墨烯導熱片再貼合於耐高溫無機膠塗布雲母片外層以提供此材料一熱擴散機能。第三實施例之目的為一方面提供一更耐高溫、高強度且高隔熱的雲母強化樹脂包覆層;另一方面為提供一耐高溫、高強度且高導熱(高導電)的石墨烯片強化樹脂包覆層。以上包覆結構也可進行單面耐高溫雲母片、另一面為耐高溫石墨稀導熱片或多層積層堆疊結構,以強化氣凝膠應用領域。Please refer to Figure 6, which is an appearance photo of the fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and dust-free prepared by the aforementioned preparation method of the third embodiment. The third embodiment has two layers, the upper and lower layers, which are high-temperature-resistant inorganic glue-coated mica sheet coating layers, and then a graphene thermal conductive sheet is attached to the outer layer of the high-temperature-resistant inorganic glue-coated mica sheet to provide this material with a heat diffusion function. The purpose of the third embodiment is to provide a mica-reinforced resin coating layer that is more resistant to high temperatures, high strength and high heat insulation; on the other hand, to provide a graphene sheet-reinforced resin coating layer that is resistant to high temperatures, high strength and high thermal conductivity (high electrical conductivity). The above coating structure can also be a single-sided high-temperature resistant mica sheet and the other side a high-temperature resistant graphite thermal conductive sheet or a multi-layer stacking structure to enhance the application field of aerogel.

請參閱圖7,係第四實施例前述製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料的外觀照片,第四樣態實施例為上下二層為耐高溫無機膠塗布雲母片包覆層,隨後以金屬薄膜導熱片再貼合於耐高溫無機膠塗布雲母片外層以提供此材料一熱擴散及高導電機能。第四實施例之目的為一方面提供一耐高溫、高強度且高隔熱的雲母強化樹脂包覆層;另一方面為提供一耐高溫、高強度且高導熱(高導電)的金屬薄膜強化樹脂包覆層。以上結構也可進行單面耐高溫雲母片、另一面為耐高溫金屬導熱片或多層積層堆疊結構,以強化氣凝膠應用領域。Please refer to Figure 7, which is an appearance photo of a fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and dust-free prepared by the aforementioned preparation method of the fourth embodiment. The fourth embodiment has two layers, the upper and lower layers, which are high-temperature-resistant inorganic glue-coated mica sheet coating layers, and then a metal film thermal conductive sheet is attached to the outer layer of the high-temperature-resistant inorganic glue-coated mica sheet to provide this material with a heat diffusion and high electrical conductivity function. The purpose of the fourth embodiment is to provide a high-temperature-resistant, high-strength and high-heat-insulating mica-reinforced resin coating layer on the one hand; on the other hand, to provide a high-temperature-resistant, high-strength and high-thermal-conductivity (high-electrical-conductivity) metal film-reinforced resin coating layer. The above structure can also be made of a high-temperature resistant mica sheet on one side and a high-temperature resistant metal heat conductive sheet on the other side or a multi-layer stacking structure to enhance the application field of aerogel.

請參閱圖8,係第五實施例係前述第二至第四實施例所製備兼具高強度、高防火、高隔熱性質之類纖維強化樹脂包覆氣凝膠複合材料,隨後再進行表面噴塗氣凝膠防火隔熱塗料後的外觀照片,第五樣態實施例以氣凝膠防火隔熱塗料進行表面噴塗,以提供此材料更優異的防火隔熱機能。第五實施例之目的為一方面提供一可耐1200℃高溫的隔熱包覆層,經此製程的產品耐燃性質在UL94-V0等級以上,最高耐熱溫度可達1200℃高溫等性質。當高溫熱點溫度約650度下,產品厚度在2.78mm條件下,隔熱溫度約下降至200℃以下。Please refer to Figure 8, which is a fifth embodiment of the fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, and high heat insulation properties prepared in the second to fourth embodiments, and then sprayed with aerogel fireproof and heat insulation coating on the surface. The fifth embodiment is sprayed with aerogel fireproof and heat insulation coating to provide this material with better fireproof and heat insulation functions. The purpose of the fifth embodiment is to provide a heat insulation coating layer that can withstand high temperatures of 1200°C. The flame retardancy of the product produced by this process is above UL94-V0 level, and the maximum heat resistance temperature can reach 1200°C. When the hot spot temperature is about 650 degrees and the product thickness is 2.78mm, the insulation temperature drops to below 200 degrees Celsius.

請參閱圖9,係第五實施例產品在高溫火焰下進行防火隔熱測試,測試火焰熱點溫度約650℃下,第五實施例產品厚度在2.78mm條件下,在高溫火焰下進行測試3分鐘下,產品在燃燒過程中並無一般有機物在高溫下產生燃燒裂解以及產生碳化物濃煙等行為,經產品隔熱後,產品背面溫度下降至200℃以下,顯示所開發產品具有優異的防火隔熱效果可應用在電動車鋰電池模組的熱失控預防。Please refer to FIG. 9 , which is a fireproof and heat-insulating test of the product of the fifth embodiment under a high-temperature flame. The temperature of the flame hot spot is about 650°C. The thickness of the product of the fifth embodiment is 2.78 mm. When the product is tested under a high-temperature flame for 3 minutes, the product does not produce the behaviors of combustion and cracking of general organic matter at high temperatures and produces thick smoke of carbides. After the product is heat-insulated, the temperature of the back of the product drops to below 200°C, indicating that the developed product has excellent fireproof and heat-insulating effects and can be applied to the thermal runaway prevention of electric vehicle lithium battery modules.

綜上,本發明之製作、應用及產生之功效應已清楚揭露,惟以上所述實施例僅係為本發明之較佳實施例,當不能以此限定本發明實施之範圍,即依本發明申請專利範圍及發明說明內容所作簡單的等效變化與修飾,皆屬本發明涵蓋之範圍內。In summary, the manufacture, application and effects of the present invention should have been clearly disclosed. However, the above-mentioned embodiments are only preferred embodiments of the present invention and should not be used to limit the scope of implementation of the present invention. In other words, simple equivalent changes and modifications made according to the scope of the patent application and the content of the invention description are all within the scope of the present invention.

S1:混合水解步驟S1: Mixed hydrolysis step

S2:縮合分散步驟S2: Contraction and division

S3:結構成型步驟S3: Structural forming step

S4:常壓乾燥步驟S4: atmospheric pressure drying step

S5:外層包覆步驟S5: Outer layer coating step

S6:固化成型步驟S6: Curing step

S7:表面處理步驟S7: Surface treatment step

圖1係本發明第一實施態樣步驟流程圖,說明本發明為一高隔熱性、高防火、高強度且不掉粉塵之耐高溫膠材塗布纖維布或耐高溫薄膜/耐高溫薄板多層包覆的氣凝膠複合材料製備流程。 圖2係依本發明第一實施態樣製備方法所製備兼具高強度、高防火、高隔熱性質且不掉粉塵的管狀類纖維強化樹脂(LFRP)包覆氣凝膠複合材料外觀照片,第一樣態實施例為利用三種不同耐高溫膠材玻璃纖維包覆氣凝膠,以提供一具高強度、高硬度且耐高溫的類纖維強化樹脂(LFRP)的包覆外殼,在此包覆外殼內部為一具低熱傳導係數、低介電且較不掉粉屑的氣凝膠材料。 圖3係本發明第一實施態樣製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料內部低熱傳導純氣凝膠斷面的掃描式電子顯微鏡SEM觀測照片,放大倍率為300倍。 圖4係本發明第二實施態所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料的外觀照片,第二樣態實施例為上下二層皆為耐高溫無機膠塗布雲母片,強化包覆氣凝膠複合材料,以提供一更耐高溫、高強度且高隔熱的雲母強化樹脂包覆層,在此外殼結構內部為低熱傳導係數氣凝膠/纖維複合材料。 圖5係本發明第二實施態兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料內部斷面的SEM掃描式電子顯微鏡觀測照片,放大倍率為250倍。 圖6係本發明第三實施態製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料的外觀照片,第三樣態實施例為上下二層為耐高溫無機膠塗布雲母片包覆層,隨後以石墨烯導熱片再貼合於耐高溫無機膠塗布雲母片外層以提供此材料一熱擴散機能,以強化包覆氣凝膠複合材料的導熱性能。 圖7係本發明第四實施態製備方法所製備之兼具高強度、高防火、高隔熱性質且不掉粉塵之類纖維強化樹脂包覆氣凝膠複合材料的外觀照片,第四樣態實施例為上下二層為耐高溫無機膠塗布雲母片,在耐高溫雲母片強化包覆氣凝膠複合材料後,再進行導熱金屬箔膜貼覆以提供此材料一熱擴散機能,以強化包覆氣凝膠複合材料的導熱性能。 圖8係本發明第五實施例係前述第二至第四實施例所製備兼具高強度、高防火、高隔熱性質之類纖維強化樹脂包覆氣凝膠複合材料,隨後再進行表面噴塗氣凝膠防火隔熱塗料後的外觀照片,第五樣態實施例以氣凝膠防火隔熱塗料進行表面噴塗,以提供此材料更優異的防火隔熱機能。 圖9係本發明係第五實施例產品在高溫火焰下進行防火隔熱測試的示意圖。 Figure 1 is a flow chart of the steps of the first embodiment of the present invention, illustrating the preparation process of the present invention, which is a high-insulation, high-fireproof, high-strength and dust-free high-temperature resistant rubber coated fiber cloth or high-temperature resistant film/high-temperature resistant sheet multi-layer coated aerogel composite material. Figure 2 is a photograph of a tubular fiber-reinforced resin (LFRP)-coated aerogel composite material with high strength, high fire resistance, high heat insulation and no dust prepared according to the preparation method of the first embodiment of the present invention. The first embodiment uses three different high-temperature resistant plastic glass fibers to coat aerogel to provide a high-strength, high-hardness and high-temperature resistant fiber-reinforced resin (LFRP) coating shell. Inside the coating shell is an aerogel material with low thermal conductivity, low dielectric and less dust. Figure 3 is a scanning electron microscope SEM observation photograph of the cross section of the low thermal conductivity pure aerogel inside the fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and no dust prepared by the first embodiment of the present invention, with a magnification of 300 times. Figure 4 is an appearance photo of a fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and dust-free prepared by the second embodiment of the present invention. The second embodiment is that the upper and lower layers are both high-temperature resistant inorganic glue-coated mica sheets, which reinforce the coated aerogel composite material to provide a mica-reinforced resin coating layer that is more resistant to high temperatures, high strength and high heat insulation. The interior of the shell structure is a low thermal conductivity aerogel/fiber composite material. Figure 5 is a SEM scanning electron microscope observation photograph of the internal cross section of the fiber-reinforced resin-coated aerogel composite material of the second embodiment of the present invention, which has high strength, high fire resistance, high heat insulation properties and does not drop dust, with a magnification of 250 times. Figure 6 is an appearance photo of a fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and dust-free prepared by the third embodiment of the present invention. The third embodiment has two layers, the upper and lower layers, which are high-temperature-resistant inorganic glue-coated mica sheets. Then, a graphene thermal conductive sheet is attached to the outer layer of the high-temperature-resistant inorganic glue-coated mica sheets to provide the material with a heat diffusion function to enhance the thermal conductivity of the coated aerogel composite material. Figure 7 is an appearance photo of a fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance, high heat insulation and dust-free prepared by the fourth embodiment of the present invention. The fourth embodiment is a high-temperature-resistant inorganic adhesive coated mica sheet on the upper and lower layers. After the high-temperature-resistant mica sheet is used to strengthen the coated aerogel composite material, a heat-conductive metal foil film is applied to provide the material with a heat diffusion function to enhance the thermal conductivity of the coated aerogel composite material. FIG8 is a photograph of the fifth embodiment of the present invention, which is a fiber-reinforced resin-coated aerogel composite material with high strength, high fire resistance and high heat insulation properties prepared in the second to fourth embodiments, and then sprayed with aerogel fireproof and heat insulation coating on the surface. The fifth embodiment is sprayed with aerogel fireproof and heat insulation coating to provide this material with better fireproof and heat insulation functions. FIG9 is a schematic diagram of the fifth embodiment of the present invention undergoing a fireproof and heat insulation test under a high-temperature flame.

S1:混合水解步驟 S1: Mixed hydrolysis step

S2:縮合分散步驟 S2: Contraction and division walking

S3:結構成型步驟 S3: Structural forming step

S4:常壓乾燥步驟 S4: Normal pressure drying step

S5:外層包覆步驟 S5: Outer layer coating step

S6:固化成型步驟 S6: Curing and molding step

S7:表面處理步驟 S7: Surface treatment step

Claims (9)

一種耐高溫材料包覆氣凝膠隔熱複合材製備方法,包含下列步驟:混合水解步驟:於一乙醇水溶液中加入一矽氧烷前軀體以形成一混合溶液,其中,該矽氧烷前軀體包括一不同鏈長疏水性改質矽氧烷化合物、一矽氧烷化合物或其組合,隨後將一酸觸媒加入該混合溶液中以進行水解反應;縮合分散步驟:於該混合溶液中加入一分散水溶液,該分散水溶液包括一鹼觸媒,以進行縮合反應形成一分散溶膠溶液,隨後在該分散溶膠溶液中添加一微量水可分散之耐高溫膠材以獲得一含耐高溫膠材之分散溶膠溶液,其中該耐高溫膠材能夠耐高溫300℃以上,該耐高溫膠材包含無機膠、熱塑性樹脂或熱固性樹脂之一或其組合;結構成型步驟:將該含耐高溫膠材之分散溶膠溶液注入一預成型模型中,促使該含耐高溫膠材之分散溶膠溶液在該預成型模型中進一步縮合形成一類固態氣凝膠濕膠之預成型結構,該預成型模型包括一含纖維材料的成型模,該纖維材料包括微米至奈米尺度之金屬纖維、無機纖維、液晶纖維、有機纖維所製備之多孔隙散棉、蓆、紙、毯、繩、厚板之一或其組合;常壓乾燥步驟:於常壓及一乾燥溫度下,使該類固態氣凝膠濕膠之預成型結構乾燥,以獲得氣凝膠預成型材料,其包含氣凝膠/纖維複合板,其中,該乾燥溫度介於60~150℃,該常壓乾燥步驟包含:汽化步驟:將該類固態氣凝膠濕膠之預成型結構放置於一共沸汽化溫度的環境下,令該類固態氣凝膠濕膠之預成型結構中的溶劑共沸汽化而將溶劑蒸餾乾燥,該共沸汽化溫度為60~90℃;溶劑回收步驟:將該共沸的含水酒精溶液蒸汽,引導至一熱交換回收設備中 促使該含水酒精冷凝並回收;及突沸步驟:調整該乾燥氣凝膠之預成型結構之溫度至一突沸溫度,使該乾燥氣凝膠之預成型結構內部所含有微量溶劑與水分子快速突沸,並產生一正蒸氣壓力,促使氣凝膠結構抑制乾燥收縮以及產生大量微細孔洞,以獲得該氣凝膠預成型材料,其中,該突沸溫度為110~150℃;外層包覆步驟:準備一耐高溫膠材溶液,其中該耐高溫膠材溶液中的耐高溫膠材能夠耐高溫300℃以上,該耐高溫膠材溶液的濃度介於10~75.0wt%,將該耐高溫膠材溶液含浸塗布在一非有機薄膜、一非有機薄板或一耐300℃以上高溫纖維表面,以使該耐高溫膠材溶液均勻分布在該非有機薄膜、該非有機薄板或該耐300℃以上高溫纖維表面,隨後進一步利用含浸塗布該耐高溫膠材溶液之該非有機薄膜、該非有機薄板或該耐300℃以上高溫纖維進行該氣凝膠預成型材料包覆,其中,該非有機薄膜、該非有機薄板或該耐300℃以上高溫纖維係可對該氣凝膠預成型材料進行氣凝膠單層包覆、多層包覆或與氣凝膠進行多層積層堆疊包覆,以形成一耐高溫材料包覆氣凝膠預成型材料的複合材料;固化成型步驟:將該耐高溫材料包覆氣凝膠預成型材料的複合材料在該耐高溫膠材溶液之溶劑乾燥溫度下使該溶劑汽化,其中,該溶劑乾燥溫度介於60~115℃,隨後利用一固化成型溫度進行含浸該耐高溫膠材溶液的固化成型步驟,其中該固化成型溫度係高於該溶劑乾燥溫度,以獲得一耐高溫薄膜包覆氣凝膠預成型複合材料;及表面處理步驟:將該耐高溫薄膜包覆氣凝膠預成型複合材料表面利用拋光、噴氣以及表面噴塗氣凝膠防火隔熱塗料之一或其組合,進行清潔及表面保護製程組合以形成耐高溫材料包覆氣凝膠隔熱複合材。 A preparation method of a high temperature resistant material coated aerogel thermal insulation composite material comprises the following steps: a mixing and hydrolysis step: adding a siloxane precursor to an ethanol aqueous solution to form a mixed solution, wherein the siloxane precursor comprises a hydrophobic modified siloxane compound with different chain lengths, a siloxane compound or a combination thereof, and then adding an acid catalyst to the mixed solution to perform a hydrolysis reaction; a condensation and decomposition step: adding a dispersed aqueous solution to the mixed solution, wherein the dispersed aqueous solution comprises an alkaline catalyst to perform a condensation reaction; A dispersion sol solution is formed by a reaction, and then a trace amount of water-dispersible high-temperature resistant adhesive material is added to the dispersion sol solution to obtain a dispersion sol solution containing the high-temperature resistant adhesive material, wherein the high-temperature resistant adhesive material can withstand a high temperature of more than 300° C., and the high-temperature resistant adhesive material comprises one or a combination of inorganic adhesive, thermoplastic resin or thermosetting resin; a structural molding step: injecting the dispersion sol solution containing the high-temperature resistant adhesive material into a pre-molding mold, so that the dispersion sol solution containing the high-temperature resistant adhesive material is further formed in the pre-molding mold. A preformed structure of a solid aerogel wet gel is condensed and formed, the preformed model includes a molding die containing a fiber material, the fiber material includes porous loose cotton, mat, paper, blanket, rope, thick plate prepared from metal fiber, inorganic fiber, liquid crystal fiber, organic fiber of micrometer to nanometer scale, or a combination thereof; a normal pressure drying step: drying the preformed structure of the solid aerogel wet gel at normal pressure and a drying temperature to obtain an aerogel preformed material, which includes an aerogel/fiber composite board, wherein the The drying temperature is between 60 and 150°C. The atmospheric pressure drying step includes: a vaporization step: placing the preformed structure of the solid aerogel wet gel in an environment of azeotropic vaporization temperature, so that the solvent in the preformed structure of the solid aerogel wet gel is azeotropically vaporized and the solvent is distilled and dried. The azeotropic vaporization temperature is 60 to 90°C; a solvent recovery step: directing the azeotropic aqueous alcohol solution vapor to a heat exchange recovery device to condense and recover the aqueous alcohol; and a sudden boiling step: adjusting the drying gas The temperature of the preformed structure of the aerogel is raised to a sudden boiling temperature, so that the trace solvent and water molecules contained in the preformed structure of the dry aerogel are rapidly sudden boiling, and a positive vapor pressure is generated, which prompts the aerogel structure to inhibit drying shrinkage and generate a large number of fine pores to obtain the aerogel preformed material, wherein the sudden boiling temperature is 110-150°C; the outer layer coating step: preparing a high temperature resistant rubber material solution, wherein the high temperature resistant rubber material in the high temperature resistant rubber material solution can withstand a high temperature of more than 300°C, and the high temperature resistant rubber The concentration of the high-temperature resistant rubber material solution is between 10 and 75.0 wt %, and the high-temperature resistant rubber material solution is impregnated and coated on a non-organic film, a non-organic thin plate, or a high-temperature resistant fiber surface of 300° C. or higher, so that the high-temperature resistant rubber material solution is evenly distributed on the surface of the non-organic film, the non-organic thin plate, or the high-temperature resistant fiber surface of 300° C. or higher, and then the non-organic film, the non-organic thin plate, or the high-temperature resistant fiber surface of 300° C. or higher, which is impregnated and coated with the high-temperature resistant rubber material solution, is further coated with the aerogel preformed material. The non-organic film, the non-organic sheet or the high temperature resistant fiber above 300°C can coat the aerogel preform material with a single layer, multiple layers or stacked with aerogel to form a composite material of the high temperature resistant material coating the aerogel preform material; the curing step: the composite material of the high temperature resistant material coating the aerogel preform material is subjected to the solvent drying temperature of the high temperature resistant glue solution to vaporize the solvent, wherein the solvent drying temperature is between 60 and 11 5℃, and then use a curing molding temperature to perform a curing molding step of impregnating the high temperature resistant adhesive solution, wherein the curing molding temperature is higher than the solvent drying temperature, so as to obtain a high temperature resistant film-coated aerogel preformed composite material; and a surface treatment step: the surface of the high temperature resistant film-coated aerogel preformed composite material is polished, sprayed, and sprayed with aerogel fireproof and heat-insulating coatings or a combination thereof, and a cleaning and surface protection process combination is performed to form a high temperature resistant material-coated aerogel heat-insulating composite material. 如請求項1所述之製備方法,其中,若該耐高溫膠材溶液為常溫固化型,含浸該耐高溫膠材溶液之該非有機薄膜、該非有機薄板或該耐300℃以 上高溫纖維在該溶劑汽化過程中伴隨固化,即可獲得該耐高溫材料包覆氣凝膠隔熱複合材。 As described in claim 1, in the preparation method, if the high-temperature resistant adhesive solution is a room temperature curing type, the non-organic film, the non-organic sheet or the high-temperature fiber resistant to 300°C or above impregnated with the high-temperature resistant adhesive solution is cured during the evaporation process of the solvent, and the high-temperature resistant material-coated aerogel thermal insulation composite can be obtained. 如請求項1所述之製備方法,其中,該固化成型步驟包含:一溶劑乾燥步驟:將含浸該耐高溫膠材溶液之該非有機薄膜、該非有機薄板或該耐300℃以上高溫纖維包覆該氣凝膠預成型材料所形成的該耐高溫薄膜包覆氣凝膠預成型材料的複合材料,在該耐高溫膠材之溶劑乾燥溫度下使該溶劑汽化;及一交聯固化步驟:在一特定的交聯固化高溫環境下,使包覆於該氣凝膠預成型材料外層之含浸該耐高溫膠材溶液的該非有機薄膜、該非有機薄板或該耐300℃以上高溫纖維以及內部熱固化樹脂之間進行交聯反應固化而相互結合,而在該交聯固化溫度反應後,將獲得該耐高溫材料包覆氣凝膠隔熱複合材,其外部為類-纖維強化樹脂(LFRP)耐高溫包覆表層以及內部為氣凝膠/纖維複合板。 The preparation method as described in claim 1, wherein the curing step comprises: a solvent drying step: the non-organic film, the non-organic sheet or the high-temperature resistant fiber above 300°C impregnated with the high-temperature resistant adhesive solution is coated with the aerogel preform material to form a composite material of the high-temperature resistant film-coated aerogel preform material, and the solvent is vaporized at the solvent drying temperature of the high-temperature resistant adhesive material; and a cross-linking curing step: in a specific cross-linking curing high-temperature environment Under the condition of crosslinking reaction and curing, the non-organic film, the non-organic sheet or the high-temperature resistant fiber above 300°C impregnated with the high-temperature resistant rubber solution coated on the outer layer of the aerogel preformed material and the internal thermosetting resin are combined with each other. After the crosslinking and curing temperature reaction, the high-temperature resistant material coated aerogel thermal insulation composite material is obtained, the outer surface of which is a high-temperature resistant coating layer of LFRP and the inner part is an aerogel/fiber composite board. 如請求項1所述之製備方法,其中,當該耐高溫膠材溶液係包含無機膠樹脂或熱固性樹脂,該固化成型步驟進一步包括:常溫交聯固化步驟:在常溫環境下,使溶劑汽化並伴隨固化劑交聯固化,固化後即可獲得具該耐高溫材料包覆氣凝膠隔熱複合材;或高溫交聯固化步驟:在一交聯固化溫度下,使該熱固性樹脂與該非有機薄膜、該非有機薄板或該300℃以上耐高溫纖維內部纖維之間進行化學反應結合固化,當熱固性樹脂為環氧樹脂(epoxy),該交聯固化溫度為150~180℃一系列交聯固化溫度;當熱固性樹脂為聚醯亞胺(polyimide),該交聯固化溫度為120~325℃一系列交聯固化溫度;固化交聯後即可獲得該耐高溫材料包覆氣凝膠隔熱複合材。 The preparation method as described in claim 1, wherein when the high temperature resistant adhesive material solution comprises an inorganic adhesive resin or a thermosetting resin, the curing step further comprises: a room temperature crosslinking curing step: in a room temperature environment, the solvent is vaporized and the curing agent is crosslinked and cured, and after curing, the aerogel thermal insulation composite material coated with the high temperature resistant material can be obtained; or a high temperature crosslinking curing step: at a crosslinking curing temperature, the thermosetting resin is crosslinked with the non-organic film, the non-organic sheet Or the internal fibers of the high-temperature resistant fiber above 300°C undergo chemical reaction and curing. When the thermosetting resin is epoxy resin, the crosslinking curing temperature is a series of crosslinking curing temperatures of 150~180°C; when the thermosetting resin is polyimide, the crosslinking curing temperature is a series of crosslinking curing temperatures of 120~325°C; after curing and crosslinking, the high-temperature resistant material-coated aerogel thermal insulation composite can be obtained. 如請求項1至4中任一項所述之製備方法,其中,該矽氧烷化合物包含四甲氧基矽烷(Tetramethoxysilane,TMOS)、四乙氧基矽烷(Tetraethoxysilane,TEOS)或其組合;該疏水性改質矽氧烷化合物包含甲基三甲氧 基矽烷(Methyltrimethoxysilane,MTMS)、丙基三甲氧基矽烷(Propyltrimethoxysilane,PTMS)、己基三甲氧基矽烷(Hexyltrimethoxysilane,HTMS)、辛基三甲氧基矽烷(Octyltrimethoxysilane,OTMS)、六甲基二矽氮烷(Hexamethyldisilane,HMDS)之不同烷基鏈長取代的疏水性矽氧烷之一或其組合,其中,在矽氧烷前軀體中,該矽氧烷化合物與該疏水性改質矽氧烷化合物之含量莫耳比介於0:100mol%至40:60mol%。 The preparation method as described in any one of claims 1 to 4, wherein the siloxane compound comprises tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or a combination thereof; the hydrophobic modified siloxane compound comprises methyltrimethoxysilane (MTMS), propyltrimethoxysilane (PTMS), One or a combination of hydrophobic siloxanes substituted with different alkyl chain lengths such as hexyltrimethoxysilane (HTMS), octyltrimethoxysilane (OTMS), and hexamethyldisilane (HMDS), wherein in the siloxane precursor, the molar ratio of the siloxane compound to the hydrophobic modified siloxane compound is between 0:100 mol% and 40:60 mol%. 如請求項1至4中任一項所述之製備方法,其中,該無機膠包含水玻璃、無機矽樹脂、氧化銅-磷酸膠、矽酸鹽膠、磷酸-矽酸鹽膠、硫酸鹽膠或氧化鎂-二氧化矽-硼砂無機膠,該熱固性樹脂包含環氧樹脂、聚醯亞胺、聚醚醯亞胺、聚苯醚、聚苯硫醚、聚醚酮液晶高分子、聚四氟乙烯、聚三聚氰胺、聚酚醛、聚三聚氰胺-甲醛、聚醯胺、聚醯胺酯或矽膠。 The preparation method as described in any one of claims 1 to 4, wherein the inorganic glue comprises water glass, inorganic silicone resin, copper oxide-phosphate glue, silicate glue, phosphoric acid-silicate glue, sulfate glue or magnesium oxide-silicon dioxide-borax inorganic glue, and the thermosetting resin comprises epoxy resin, polyimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyetherketone liquid crystal polymer, polytetrafluoroethylene, polymelamine, polyphenolic formaldehyde, polyamide, polyamide or silicone. 如請求項1至4中任一項所述之製備方法,其中,該纖維材料包括微米至奈米尺度之金屬棒、玻璃纖維、碳纖維、石英纖維、陶瓷纖維、岩棉纖維、Kevlar聚醯胺纖維、Nomex聚醯胺纖維、尼龍纖維、聚酯纖維、生物可分解無機纖維或生物可分解有機纖維所製備之多孔隙散棉、蓆、紙、毯、繩、厚板或其組合。 A preparation method as described in any one of claims 1 to 4, wherein the fiber material includes porous loose wool, mat, paper, blanket, rope, thick plate or a combination thereof prepared from metal rods, glass fibers, carbon fibers, quartz fibers, ceramic fibers, rock wool fibers, Kevlar polyamide fibers, Nomex polyamide fibers, nylon fibers, polyester fibers, biodegradable inorganic fibers or biodegradable organic fibers of micrometer to nanometer scale. 如請求項1至4中任一項所述之製備方法,其中,該非有機薄膜及該非有機薄板包含金屬膜板、無機膜板及有機-無機複合耐高溫薄膜、薄板或其組合,該金屬膜板包含鋁、不鏽鋼、銅箔膜之一或其組合;該無機膜板包含雲母片、石墨、石墨烯、玻璃陶瓷、金屬氧化物、金屬氮矽化合物及金屬碳矽化合物所製備成薄膜或薄板之一或其組合;該有機-無機複合耐高溫薄膜包含鋁箔、不鏽鋼箔、銅箔、雲母薄板、石墨薄板、石墨烯薄板、玻璃薄板、陶瓷薄板、金屬以及金屬氧化物微粒與膠所複合製造的耐高溫薄膜及薄板之一或其組合,其中,該耐300℃以上高溫纖維包含石英纖維、玻璃纖維、陶瓷纖維、碳纖維、該 有機纖維包含尼龍纖維、聚酯纖維、聚氟纖維、Kevlar聚醯胺纖維、Nomex聚醯胺纖維或生物可分解無機、有機纖維複合所製備之各類多孔隙散棉、蓆、紙、毯、繩、厚板之一或其組合。 The preparation method as described in any one of claims 1 to 4, wherein the non-organic film and the non-organic thin plate include metal film plates, inorganic film plates and organic-inorganic composite high-temperature resistant films, thin plates or combinations thereof, the metal film plates include one or a combination of aluminum, stainless steel, and copper foil films; the inorganic film plates include one or a combination of films or thin plates prepared from mica sheets, graphite, graphene, glass ceramics, metal oxides, metal nitrogen silicon compounds and metal carbon silicon compounds; the organic-inorganic composite high-temperature resistant film includes aluminum foil, stainless steel foil, copper foil, mica thin plates, One or a combination of graphite sheets, graphene sheets, glass sheets, ceramic sheets, metals, and metal oxide particles and glue composites to produce high-temperature resistant films and sheets, wherein the high-temperature resistant fiber above 300°C includes quartz fiber, glass fiber, ceramic fiber, carbon fiber, the organic fiber includes nylon fiber, polyester fiber, polyfluorinated fiber, Kevlar polyamide fiber, Nomex polyamide fiber, or various porous loose cotton, mats, paper, blankets, ropes, thick plates prepared by biodegradable inorganic and organic fiber composites or one or a combination of these. 如請求項1至4中任一項所述之製備方法,其中,該耐高溫薄膜包覆氣凝膠預成型複合材料中,該耐高溫薄膜包覆包含單層包覆、多層包覆或多層多種耐高溫薄膜積層堆疊包覆,其中,該耐高溫薄膜包覆氣凝膠預成型複合材料為一類纖維強化塑膠(like-fiber reinforced plastic,LFRP)無機包覆矽基氣凝膠複合材料。 A preparation method as described in any one of claims 1 to 4, wherein in the high-temperature-resistant film-coated aerogel preform composite material, the high-temperature-resistant film coating includes a single-layer coating, a multi-layer coating, or a multi-layer stacking coating of multiple high-temperature-resistant films, wherein the high-temperature-resistant film-coated aerogel preform composite material is a type of fiber-reinforced plastic (like-fiber reinforced plastic, LFRP) inorganic coated silicon-based aerogel composite material.
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JP2014040750A (en) * 2012-08-23 2014-03-06 Panasonic Corp Heat insulating material using aerogel
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