TWI735919B - Method for producing a hydrophilic aerogel particle and related application of its product - Google Patents
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本發明關於一種氣凝膠顆粒的製備方法，且特別攸關一種親水性氣凝膠顆粒的製備方法及其產物的相關應用。 The present invention relates to a preparation method of aerogel particles, and particularly relates to a preparation method of hydrophilic aerogel particles and related applications of the products thereof.
氣凝膠為一種具立體網狀結構的多孔隙材料，其具有低密度(0.005至0.2g/cm3)、高比表面積(500至2,000m2/g)、與低熱導率(0.02至0.036w/mK)等特性的高科技產品。氣凝膠因含多孔隙無機材料，故具有高隔熱與防火等機能；惟，實際使用時要達到上述機能，氣凝膠添加量須顯著增加。此外，目前國際上大量商品主要為疏水性氣凝膠粉末，其訴求隔熱穩定性。然而，疏水性氣凝膠粉末於後續加工應用上難混摻且具有粉塵與塵爆等危險。具體而言，疏水性氣凝膠粉末與高疏水性基材(如：混凝土、水泥漆等)無法完全混合或強迫混合後所得產品的強度嚴重降低而無法展現高隔熱效果。另外，疏水性氣凝膠粉末因含有大量碳氫化合物，這些易燃的碳羥結構會導致疏水性氣凝膠微細粉塵產生明顯的閃暴危害。 Aerogel is a porous material with a three-dimensional network structure. It has low density (0.005 to 0.2g/cm 3 ), high specific surface area (500 to 2,000m 2 /g), and low thermal conductivity (0.02 to 0.036 w/mK) and other high-tech products. The aerogel contains porous inorganic materials, so it has the functions of high heat insulation and fire prevention; however, to achieve the above functions in actual use, the amount of aerogel added must be significantly increased. In addition, a large number of international commodities are mainly hydrophobic aerogel powders, which demand thermal insulation stability. However, the hydrophobic aerogel powder is difficult to mix in subsequent processing applications and has the risk of dust and dust explosion. Specifically, the hydrophobic aerogel powder and highly hydrophobic substrates (such as concrete, cement paint, etc.) cannot be completely mixed or the strength of the resulting product after forced mixing is severely reduced and cannot exhibit high thermal insulation effect. In addition, because the hydrophobic aerogel powder contains a large amount of hydrocarbons, these flammable hydrocarbon structures will cause the hydrophobic aerogel fine dust to produce obvious flash damage.
傳統的氣凝膠製備方法為溶膠凝膠合成法，主要先由矽烷氧化合物(alkoxysilane)、正矽酸甲酯、或水玻璃等前驅物與有機溶劑進行混合後，再加入酸觸媒進行水解反應(hydrolysis)。待水解一段時間後，添加鹼觸媒進行縮合反應(condensation)，於縮合過程中會逐漸形成溶膠。溶膠內的分子繼續進 行鍵結，逐漸形成半固態的高分子凝膠。之後經一段時間熟化(aging)後，使溶膠形成結構穩定的立體網狀結構。最後，先利用正丁醇、正己醇、正己烷、或環己烷等溶劑進行溶劑置換，再以超臨界乾燥技術將立體網狀結構內的溶劑萃取乾燥，而獲得多孔性乾燥氣凝膠粉末。 The traditional aerogel preparation method is the sol-gel synthesis method, which mainly mixes precursors such as alkoxysilane, methyl orthosilicate, or water glass with an organic solvent, and then adds an acid catalyst for hydrolysis. Reaction (hydrolysis). After being hydrolyzed for a period of time, an alkali catalyst is added for condensation reaction (condensation), and a sol will gradually form during the condensation process. The molecules in the sol continue to enter Line bonding, gradually forming a semi-solid polymer gel. After a period of aging, the sol forms a stable three-dimensional network structure. Finally, first use solvents such as n-butanol, n-hexanol, n-hexane, or cyclohexane for solvent replacement, and then use supercritical drying technology to extract and dry the solvent in the three-dimensional network structure to obtain porous dry aerogel powder .
由於上述製備方法採用的乾燥技術為超臨界乾燥技術或多次溶劑置換，因此可避免氣凝膠於常壓乾燥過程受水分表面張力影響而破裂。但由於超臨界乾燥技術須於高壓下進行，因此僅適合極微少量的氣凝膠乾燥；此外，利用多次溶劑置換須耗費二至三天相當曠日費時，且不利於量產與降低氣凝膠的生產成本。 Since the drying technology adopted in the above preparation method is a supercritical drying technology or multiple solvent replacements, it can prevent the aerogel from rupturing due to the surface tension of water during the atmospheric drying process. However, because the supercritical drying technology must be carried out under high pressure, it is only suitable for drying a very small amount of aerogel; in addition, it takes two to three days to use multiple solvent replacements, which is very time-consuming, and is not conducive to mass production and reduction of aerogels. The production cost of glue.
疏水性氣凝膠的製備方法亦為溶膠凝膠合成法，其主要先由矽烷氧化合物(如：甲基三甲氧基矽烷(methyltrimethoxysilane，MTMS)或甲基三乙氧基矽烷(methyltriethoxysilane，MTES))等前驅物與有機溶劑混合後，再加入鹼觸媒進行水解反應。待水解一段時間後，進行縮合反應，於縮合過程中會逐漸形成凝膠；隨後以常溫常壓或高溫常壓進行乾燥。或者，亦先由矽烷氧化合物(如：四乙氧基矽烷(tetraethoxysilane，TEOS)或四甲氧基矽烷(tetramethoxysilane，TMOS))等前驅物與有機溶劑進行混合後，再加入酸觸媒進行水解反應。待水解一段時間後，再添加鹼觸媒進行縮合反應，而縮合過程中會逐漸形成結構穩定的立體網狀結構。最後，先利用正丁醇、正己醇、正己烷、或環己烷等溶劑進行溶劑置換，再以疏水性矽烷化合物(如：三甲基氯矽烷)進行疏水改質，使疏水性官能基結構與立體網狀結構化學鍵結。最後，利用常壓乾燥技術將氣凝膠內的溶劑乾燥，而獲得多孔性乾燥氣凝膠塊材。 The preparation method of hydrophobic aerogel is also a sol-gel synthesis method, which mainly consists of siloxane compounds (such as methyltrimethoxysilane (MTMS) or methyltriethoxysilane (MTES)). ) After the precursor is mixed with the organic solvent, an alkali catalyst is added to carry out the hydrolysis reaction. After being hydrolyzed for a period of time, a condensation reaction is carried out, and a gel is gradually formed during the condensation process; then, drying is carried out at normal temperature and normal pressure or high temperature and normal pressure. Alternatively, a silane oxygen compound (such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS)) and other precursors are mixed with an organic solvent, and then an acid catalyst is added for hydrolysis reaction. After being hydrolyzed for a period of time, an alkali catalyst is added to carry out the condensation reaction, and a stable three-dimensional network structure is gradually formed during the condensation process. Finally, first use solvents such as n-butanol, n-hexanol, n-hexane, or cyclohexane for solvent replacement, and then use hydrophobic silane compounds (such as trimethylchlorosilane) for hydrophobic modification to make the hydrophobic functional group structure It is chemically bonded to the three-dimensional network structure. Finally, the solvent in the aerogel is dried using atmospheric drying technology to obtain a porous dry aerogel block.
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。 The above hydrophobic modification is the use of room temperature and pressure multi-step solvent replacement technology, but this modification The technology must be carried out for more than 24 hours, and the time required for the process is too long to be cost-effective.
美國專利公告號US10295108B2所述之「改質混合矽氣凝膠」，主要提供一種氣凝膠混合物，包含官能基化的非高分子有機材料，其一端或兩端以C-Si共價鍵與矽氣凝膠網狀結構結合，透過有機材料的碳原子與氣凝膠網狀結構之間鍵結進行疏水改質，並利用超臨界技術製備取得。 The "modified hybrid silica aerogel" described in US Patent Publication No. US10295108B2 mainly provides an aerogel mixture containing functionalized non-polymer organic materials, one or both ends of which are covalently bonded with C-Si The silica aerogel network structure is combined, and it is hydrophobically modified through the bonding between the carbon atoms of the organic material and the aerogel network structure, and is prepared by supercritical technology.
大陸專利公開號CN106794996A所述之「改良式疏水性氣凝膠材料」，主要提供一種氣凝膠組成物，其於水環境中具有良好性能，且亦具有良好的燃燒及自熱性。 The "Improved Hydrophobic Aerogel Material" described in the Mainland Patent Publication No. CN106794996A mainly provides an aerogel composition that has good performance in an aqueous environment, and also has good combustion and self-heating properties.
中華民國發明公開號200835648所述之「多孔材料及其製備方法」，主要將由矽烷氧化合物(如：TEOS)或矽酸鹽化合物(如：水玻璃)與有機溶劑以溶膠凝膠法合成，並經改質劑改質而製得多孔材料，藉此將多孔結構材料表面的親水性官能基置換成疏水性官能基，使氣凝膠可避免水分表面張力影響而破裂，因此可在室溫常壓下進行乾燥。 The "porous materials and their preparation methods" described in the Republic of China Invention Publication No. 200835648 are mainly synthesized from silanoxy compounds (such as TEOS) or silicate compounds (such as water glass) and organic solvents by the sol-gel method. The porous material is modified by the modifier, whereby the hydrophilic functional groups on the surface of the porous structure material are replaced with hydrophobic functional groups, so that the aerogel can be prevented from being broken due to the influence of the surface tension of water, so it can be kept at room temperature. Dry under pressure.
本發明之一目的在於改善傳統疏水性氣凝膠粉末於應用上的相關缺點，如：氣凝膠分散不均、氣凝膠高溫隔熱功能不明顯、氣凝膠粉體塵爆危害等問題。 One purpose of the present invention is to improve the related shortcomings of traditional hydrophobic aerogel powder in application, such as: uneven dispersion of aerogel, insignificant heat insulation function of aerogel at high temperature, dust explosion hazard of aerogel powder, etc. .
本發明之另一目的在於針對適用於結合混凝土(密度約1.3至2.0g/cm3)或親水性水泥漆(密度約1.15至1.55g/cm3)等應用所開發的親水性氣凝膠顆粒，並使親水性氣凝膠與混凝土或親水性水泥漆之間產生堅強作用力與優異混摻性，進而改善目前混摻不均與相分離問題。 Another purpose of the present invention is to develop hydrophilic aerogel particles suitable for applications such as binding concrete (density of about 1.3 to 2.0 g/cm 3 ) or hydrophilic cement paint (density of about 1.15 to 1.55 g/cm 3 ). , And make the hydrophilic aerogel and concrete or hydrophilic cement paint produce strong force and excellent mixing ability, thereby improving the current uneven mixing and phase separation problems.
本發明之再一目的在於開發改良式的溶膠凝膠合成技術來結合 不同親疏水性混合溶劑效應，以破壞混合溶劑中水分子的界面張力並降低親水性氣凝膠顆粒於製備過程中的收縮現象，藉此可連續式或批式大量生產極大顆粒的親水性氣凝膠顆粒。 Another purpose of the present invention is to develop an improved sol-gel synthesis technology to combine The effect of different hydrophilic and hydrophobic mixed solvents can destroy the interfacial tension of water molecules in the mixed solvent and reduce the shrinkage of hydrophilic aerogel particles during the preparation process, so that large-scale hydrophilic aerogels can be produced continuously or batchwise.胶粒。 Glue particles.
本發明之又一目的在於降低傳統疏水性氣凝膠製程中長時間的溶劑置換程序與不使用昂貴的超臨界乾燥技術即可生產高孔隙率與低密度的矽氣凝膠材料。 Another object of the present invention is to reduce the long-time solvent replacement procedure in the traditional hydrophobic aerogel manufacturing process and to produce high-porosity and low-density silicon aerogel materials without using expensive supercritical drying technology.
本發明之又一目的在於所生產的親水性氣凝膠顆粒粒徑介於數百微米至數十毫米，其可與一般水泥結合形成高隔熱與高防火的氣凝膠鋼筋(RC)混凝土、氣凝膠噴塗水泥混凝土、或氣凝膠粉光水泥，以應用於貨櫃屋隔熱、H型鋼骨結構防火、或可與親水性PU膠、親水性PMMA膠、或矽膠結合以應用於貨櫃屋隔熱或室內與室外隔熱等方面。 Another purpose of the present invention is to produce hydrophilic aerogel particles with a particle size ranging from hundreds of microns to tens of millimeters, which can be combined with general cement to form aerogel reinforced concrete (RC) with high heat insulation and high fire resistance. , Aerogel sprayed cement concrete, or aerogel powdered cement, used in container house heat insulation, H-shaped steel frame fire protection, or can be combined with hydrophilic PU glue, hydrophilic PMMA glue, or silicone glue to be used in containers House insulation or indoor and outdoor insulation.
準此，本發明提出一種結合混合溶劑效應與溶膠凝膠合成技術以製備粒徑介於數百微米到數十毫米大小之親水性氣凝膠顆粒的製程技術，此製備方法包含下列步驟：(1)混合步驟：將一矽氧烷類化合物添加至一混合溶劑，使矽氧烷類化合物分散在混合溶劑中而形成一均勻混合溶液；(2)水解步驟：將一酸觸媒加入混合溶液中進行水解反應；(3)縮合分散步驟：將一鹼觸媒加入水解後的混合溶液進行縮合反應，並於縮合反應過程中加入一疏水性分散溶媒，且經高速攪拌混合後靜置，使混合溶液中的矽氧分子縮合形成穩定的氣凝膠濕膠結構；(4)凝膠老化步驟：於一特定溫度範圍下進行氣凝膠濕膠老化，使氣凝膠濕膠形成穩定的濕膠結構；(5)破碎分散步驟：添加一大量疏水性溶媒，使濕膠破碎成數百微米到數十毫米之間，並使破碎濕膠分散於疏水性溶媒中；(6)高溫溶劑置換步驟：於一常壓高溫條件下進行疏水性溶媒與濕膠內的溶劑 萃取置換至濕膠呈現藍透狀或完全透明狀；以及(7)溶劑蒸發乾燥步驟：於常壓下對濕膠進行溶劑蒸發乾燥，而乾燥過程中利用親疏水混合溶劑效應使濕膠結構中的水分子快速脫離以抑制所得的氣凝膠結構收縮。 In view of this, the present invention proposes a process technology that combines the mixed solvent effect and sol-gel synthesis technology to prepare hydrophilic aerogel particles with a particle size ranging from hundreds of microns to tens of millimeters. The preparation method includes the following steps:( 1) Mixing step: adding a silicone compound to a mixed solvent to disperse the silicone compound in the mixed solvent to form a uniform mixed solution; (2) Hydrolysis step: adding an acid catalyst to the mixed solution (3) Condensation and dispersion step: add an alkali catalyst to the hydrolyzed mixed solution for condensation reaction, and add a hydrophobic dispersing solvent during the condensation reaction, and stir and mix at high speed before leaving it to stand still. The silica molecules in the mixed solution condense to form a stable aerogel wet gel structure; (4) Gel aging step: the aerogel wet gel is aged in a specific temperature range to make the aerogel wet gel form a stable wet gel. Glue structure; (5) Crushing and dispersing step: adding a large amount of hydrophobic solvent to break the wet glue into hundreds of microns to tens of millimeters, and disperse the broken wet glue in the hydrophobic solvent; (6) High temperature solvent replacement Step: Conduct the hydrophobic solvent and the solvent in the wet glue under a normal pressure and high temperature condition Extraction and replacement until the wet glue is blue or completely transparent; and (7) Solvent evaporation and drying step: the wet glue is evaporated and dried under normal pressure, and the hydrophilic and hydrophobic mixed solvent effect is used to make the wet glue structure in the drying process. The water molecules quickly detach to inhibit the shrinkage of the resulting aerogel structure.
進一步地，矽氧烷類化合物為一種或多種選自於由下列所組成之群組：矽氧烷化合物(alkoxysilane)，如：四甲氧基矽烷(tetramethoxysilane，TMOS)或四乙氧基矽烷(tetraethoxysilane，TEOS)、以及R-矽氧烷化合物(R-alkoxysilane)，R為親水性官能基，如：親水性官能基化矽酸甲酯(R-TMS)或親水性官能基化矽酸乙酯(R-TES)，且親水性官能基包含：酸基-COOH、胺基-NH2、亞胺基-NH-、多胺基-NH-NH2、羥基-OH、醯胺基-CONH-、環氧基-COH-COH、尿基-NHCONH-、異氰酸酯基-N=C=O、或異氰尿酸基-N-CO-N-，且親水性官能基的碳數由C1至C8。 Further, the silicone compound is one or more selected from the group consisting of: alkoxysilane, such as tetramethoxysilane (TMOS) or tetraethoxysilane ( tetraethoxysilane, TEOS), and R-alkoxysilane, R is a hydrophilic functional group, such as hydrophilic functional methyl silicate (R-TMS) or hydrophilic functional ethyl silicate Ester (R-TES), and hydrophilic functional groups include: acid group -COOH, amino group -NH 2 , imino group -NH-, polyamino group -NH-NH 2 , hydroxyl group -OH, amide group -CONH -, epoxy group -COH-COH, urea group -NHCONH-, isocyanate group -N=C=O, or isocyanurate group -N-CO-N-, and the carbon number of the hydrophilic functional group is from C1 to C8 .
進一步地，混合步驟中所用的混合溶劑為一種或多種選自於由下列所組成之群組：水、處理水、去離子水、二次水、C1至C10醇類、C2至C10醚類、以及C3至C10酮類。 Further, the mixed solvent used in the mixing step is one or more selected from the group consisting of water, treated water, deionized water, secondary water, C1 to C10 alcohols, C2 to C10 ethers, And C3 to C10 ketones.
進一步地，縮合分散步驟中所用的疏水性分散溶媒可依據製程需求包含親水性溶劑與疏水性溶劑調和而成的分散溶媒。於縮合反應過程中添加大量分散溶媒(如：醇類、芳香族類、烷類及有機鹵化物類之一種或多種)，可使氣凝膠濕膠在大量疏水性分散溶媒作用下擁有大量孔洞性質，並利用親水性溶劑與疏水性溶劑的調和比例控制分散溶媒與氣凝膠濕膠分子的相互作用，進而控制氣凝膠濕膠分子於聚集結合過程中的微相分離行為，從而控制所形成氣凝膠濕膠結構的分子顆粒大小與孔洞分布等特性。 Further, the hydrophobic dispersion solvent used in the condensation dispersion step may include a dispersion solvent prepared by a blend of a hydrophilic solvent and a hydrophobic solvent according to the requirements of the manufacturing process. Adding a large number of dispersing solvents (such as one or more of alcohols, aromatics, alkanes and organic halides) during the condensation reaction can make the aerogel wet glue have a large number of pores under the action of a large number of hydrophobic dispersing solvents Nature, and use the blending ratio of hydrophilic solvent and hydrophobic solvent to control the interaction between the dispersing solvent and the aerogel wet gel molecules, and then control the microphase separation behavior of the aerogel wet gel molecules in the aggregation and combination process, thereby controlling all The molecular particle size and pore distribution of the aerogel wet glue structure are formed.
進一步地，在本方法中利用一般常壓高溫疏水溶劑置換方式進行 溶劑置換。於濕膠分散在大量疏水性溶媒環境下，可利用常壓高溫下進行溶劑置換以加速溶劑置換效率，以降低氣凝膠製程時間。本方法利用不同親水性及疏水性溶劑之間混溶共沸效應下，在高溫溶劑置換過程中使濕膠內部的水分子或其他親水性分子與大量疏水性溶媒之間混溶共沸，進而快速置換濕膠中的溶劑直至呈現藍透狀或完全透明狀，因而製備出低密度且高孔隙率的親水性氣凝膠顆粒。 Further, in this method, the general atmospheric pressure and high temperature hydrophobic solvent replacement method is used to carry out Solvent replacement. When the wet glue is dispersed in a large amount of hydrophobic solvent environment, the solvent replacement under normal pressure and high temperature can be used to accelerate the solvent replacement efficiency and reduce the aerogel process time. This method utilizes the miscible azeotropic effect between different hydrophilic and hydrophobic solvents to make the water molecules or other hydrophilic molecules in the wet glue and a large number of hydrophobic solvents miscible azeotrope during the high-temperature solvent replacement process, and then Quickly replace the solvent in the wet glue until it appears blue and transparent or completely transparent, thereby preparing low-density and high-porosity hydrophilic aerogel particles.
進一步地，在本方法中利用一般常壓高溫方式進行溶劑蒸發及乾燥。乾燥後即可獲得粒徑介於數百微米到數十毫米的親水性氣凝膠顆粒。整體而言，製程簡易且可依基材性質進行不同親水性官能基表面改質的氣凝膠顆粒。製程速度可快速縮短於8至12小時內完成且可連續生產製備具有一般親水基或特殊親水基的氣凝膠顆粒，藉此提高生產效率。 Further, in this method, the solvent evaporation and drying are carried out by a general normal pressure and high temperature method. After drying, hydrophilic aerogel particles with a particle size ranging from hundreds of microns to tens of millimeters can be obtained. On the whole, the aerogel particles are easy to process and can be modified with different hydrophilic functional groups according to the nature of the substrate. The process speed can be quickly shortened to complete within 8 to 12 hours, and aerogel particles with general or special hydrophilic groups can be produced continuously, thereby improving production efficiency.
本發明具有下列功效： The present invention has the following effects:
1、本發明製備方法利用縮合步驟中親疏水混合溶劑效應，以不同比例的親水性溶劑與疏水性溶劑混合，使混合溶液於凝膠化過程降低水分子與矽氧分子的水合，因此可明顯避免濕膠結構於乾燥過程中收縮，以生產多孔隙率的親水性氣凝膠顆粒。藉此，可明顯提高親水性氣凝膠的隔熱與防火性能，且可明顯提高混摻材料中氣凝膠顆粒含量，提高氣凝膠的實用性質。 1. The preparation method of the present invention takes advantage of the hydrophilic and hydrophobic mixed solvent effect in the condensation step to mix hydrophilic solvents and hydrophobic solvents in different proportions to reduce the hydration of water molecules and silicon oxygen molecules during the gelation process of the mixed solution. Avoid the shrinkage of the wet gel structure during the drying process to produce hydrophilic aerogel particles with multiple porosity. Thereby, the heat insulation and fireproof performance of the hydrophilic aerogel can be obviously improved, and the content of aerogel particles in the mixed material can be obviously increased, and the practical properties of the aerogel can be improved.
2、本發明製備方法所得的親水性氣凝膠顆粒，其密度、粒徑、空孔率及孔洞大小可依製備條件(矽氧烷化合物含量、R-矽氧烷化合物含量、溶劑含量、溶劑黏度、酸觸媒或鹼觸媒含量、疏水性分散溶媒成分及其含量、疏水性溶媒成分及其含量、溶劑置換溫度、與攪拌速率等)進行調控。 2. The density, particle size, porosity and pore size of the hydrophilic aerogel particles obtained by the preparation method of the present invention can be determined according to the preparation conditions (silicone compound content, R-silicone compound content, solvent content, solvent Viscosity, acid catalyst or alkali catalyst content, hydrophobic dispersing solvent component and its content, hydrophobic solvent component and its content, solvent replacement temperature, and stirring rate, etc.) are regulated.
3、本發明製備方法於縮合分散步驟後藉由大量疏水性溶媒下進 行破碎與快速攪拌，隨後進行乾燥去除疏水性溶媒，即可生產粒徑大小介於數百微米到數十毫米的親水性氣凝膠顆粒。本方法所生產的親水性氣凝膠具有優異分散性且可高含量混摻於基材，並可於基材中保持氣凝膠內部的高空孔率，以提升親水性氣凝膠顆粒在各類基材中的隔熱及防火性質。 3. The preparation method of the present invention uses a large amount of hydrophobic solvent after the condensation and dispersion step. After crushing and rapid stirring, followed by drying to remove the hydrophobic solvent, hydrophilic aerogel particles with a particle size ranging from hundreds of microns to tens of millimeters can be produced. The hydrophilic aerogel produced by this method has excellent dispersibility and can be mixed into the substrate at a high content. Insulation and fireproof properties in similar substrates.
4、本發明製備方法所得的親水性氣凝膠顆粒外表可利用不同親水性官能基改質，因而使親水性氣凝膠輕易且均勻地分散於不同親水性溶劑中，如：水或其他親水性溶劑，或可添加至親水性膠類，如：水性PU膠、PMMA膠、或水泥漆，或可與親水性材料進行混合，如：水泥。所形成的複合材料具有結構安定、高強度、及耐候性質。 4. The appearance of the hydrophilic aerogel particles obtained by the preparation method of the present invention can be modified with different hydrophilic functional groups, so that the hydrophilic aerogel can be easily and uniformly dispersed in different hydrophilic solvents, such as water or other hydrophilic Solvents, or can be added to hydrophilic glues, such as: water-based PU glue, PMMA glue, or cement paint, or can be mixed with hydrophilic materials, such as cement. The formed composite material has a stable structure, high strength, and weather resistance.
5、本發明利用控制親疏水性質溶劑含量與溫度等條件，即可縮短整體氣凝膠的乾燥時間，最快可在8至12小時內即完成大量(體積約100至250m3)親水性氣凝膠顆粒的製備，藉此提高氣凝膠的生產效率。 5. The present invention can shorten the drying time of the whole aerogel by controlling the content and temperature of the hydrophilic and hydrophobic solvents, and can complete a large amount of hydrophilic gas (volume about 100 to 250 m 3) within 8 to 12 hours at the fastest. The preparation of gel particles can improve the production efficiency of aerogels.
(S1)‧‧‧混合步驟 (S1)‧‧‧Mixing Step
(S2)‧‧‧水解步驟 (S2)‧‧‧Hydrolysis step
(S3)‧‧‧縮合分散步驟 (S3)‧‧‧Condensation and dispersion step
(S4)‧‧‧凝膠老化步驟 (S4)‧‧‧Gel aging steps
(S5)‧‧‧破碎分散步驟 (S5)‧‧‧Crushing and dispersing step
(S6)‧‧‧高溫溶劑置換步驟 (S6)‧‧‧High temperature solvent replacement step
(S7)‧‧‧溶劑蒸發乾燥步驟 (S7)‧‧‧Solvent evaporation and drying step
圖1為本發明實施例之親水性氣凝膠顆粒製程的步驟流程示意圖。 FIG. 1 is a schematic diagram of the steps in the process of preparing hydrophilic aerogel particles according to an embodiment of the present invention.
圖2為本發明所製備之親水性氣凝膠顆粒的外觀照片圖。 Figure 2 is a photograph of the appearance of the hydrophilic aerogel particles prepared by the present invention.
圖3為本發明所製備之親水性氣凝膠顆粒的掃描式電子顯微鏡照片圖。 Figure 3 is a scanning electron micrograph of the hydrophilic aerogel particles prepared by the present invention.
圖4為水泥砂形成之混凝土與本發明以水泥與氣凝膠顆粒混合比例1：2所製備之混凝土的外觀照片圖。 Figure 4 is a photograph showing the appearance of concrete formed by cement sand and concrete prepared by the present invention at a mixing ratio of cement and aerogel particles of 1:2.
圖5為本發明以水泥與氣凝膠顆粒混合比例1：2所製備之混凝土的斷面照片圖。 Fig. 5 is a photograph of a cross-section of the concrete prepared with a mixture ratio of cement and aerogel particles of 1:2 according to the present invention.
本發明實施例之親水性氣凝膠顆粒及其製備方法可於下文清楚 呈現：請參閱圖1，揭示本發明實施例之親水性氣凝膠顆粒的製備方法，其包含下列步驟：混合步驟(S1)、水解步驟(S2)、縮合分散步驟(S3)、凝膠老化步驟(S4)、破碎分散步驟(S5)、高溫溶劑置換步驟(S6)、及溶劑蒸發乾燥步驟(S7)。 The hydrophilic aerogel particles of the embodiments of the present invention and the preparation method thereof can be clarified below Presentation: Please refer to Figure 1 to disclose the preparation method of hydrophilic aerogel particles according to the embodiment of the present invention, which includes the following steps: mixing step (S1), hydrolysis step (S2), condensation and dispersion step (S3), gel aging Step (S4), crushing and dispersing step (S5), high-temperature solvent replacement step (S6), and solvent evaporation and drying step (S7).
混合步驟(S1)：將矽氧烷化合物、R-矽氧烷化合物、或其混合物與一溶劑混合，以形成一混合溶液。矽氧烷化合物例如為四甲氧基矽烷、四乙氧基矽烷、或正矽酸甲酯；R-矽氧烷化合物例如為R-矽酸甲酯或R-矽酸乙酯，R為親水性官能基，其包含：酸基-COOH、胺基-NH2、亞胺基-NH-、多胺基-NH-NH2、羥基-OH、醯胺基-CONH-、環氧基-COH-COH、尿基-NHCONH-、異氰酸酯基-N=C=O、或異氰尿酸基-N-CO-N-，且親水性官能基的碳數由C1至C8。添加R-矽氧烷化合物主要為進行氣凝膠微細結構改質與控制官能基含量；以混合溶液的總含量計，矽氧烷化合物及R-矽氧烷化合物的總含量為3.0mol%至60.0mol%之間，溶劑的含量為97.0mol%至40.0mol%之間。 Mixing step (S1): mixing the silicone compound, R-silicone compound, or a mixture thereof with a solvent to form a mixed solution. The silicone compound is, for example, tetramethoxysilane, tetraethoxysilane, or methyl orthosilicate; the R-silicone compound is, for example, R-methyl silicate or R-ethyl silicate, and R is hydrophilic. A functional group, which includes: acid group -COOH, amino group -NH 2 , imino group -NH-, polyamino group -NH-NH 2 , hydroxyl group -OH, amide group -CONH-, epoxy group -COH -COH, urea group -NHCONH-, isocyanate group -N=C=O, or isocyanurate group -N-CO-N-, and the carbon number of the hydrophilic functional group is from C1 to C8. The addition of R-silicone compound is mainly for the modification of aerogel microstructure and the control of functional group content; based on the total content of the mixed solution, the total content of silicone compound and R-silicone compound is 3.0 mol% to Between 60.0 mol%, and the solvent content is between 97.0 mol% and 40.0 mol%.
混合步驟(S1)中所用的溶劑可為水、處理水、去離子水、二次水、C1至C10醇類、C2至C10醚類、或C3至C10酮類等。具體而言，醇類例如乙醇，酮類例如丙酮，醚類例如***或丁醚。 The solvent used in the mixing step (S1) can be water, treated water, deionized water, secondary water, C1 to C10 alcohols, C2 to C10 ethers, or C3 to C10 ketones, and the like. Specifically, alcohols such as ethanol, ketones such as acetone, and ethers such as diethyl ether or butyl ether.
水解步驟(S2)：將一酸觸媒加入混合溶液，以進行水解反應。其中，矽氧烷化合物與R-矽氧烷化合物之總含量與酸觸媒的含量比為1：0.5至1：0.0001；此外，某些特定的R-矽氧烷化合物可不須添加酸觸媒即可進行水解。 Hydrolysis step (S2): adding an acid catalyst to the mixed solution to carry out the hydrolysis reaction. Among them, the ratio of the total content of silicone compounds and R-silicone compounds to the content of acid catalyst is 1:0.5 to 1:0.0001; in addition, some specific R-silicone compounds do not need to add acid catalyst It can be hydrolyzed.
矽氧烷化合物與R-矽氧烷化合物之總含量與酸觸媒的含量比為1：0.0001時，水解反應的時間須達360分鐘；矽氧烷化合物與R-矽氧烷化合物之總 含量與酸觸媒的含量比為1：0.5時，水解時間須達5分鐘。由此可知，水解反應所須的時間可隨酸觸媒含量的增加而下降。 When the ratio of the total content of silicone compound and R-silicone compound to the content of acid catalyst is 1:0.0001, the hydrolysis reaction time must reach 360 minutes; the total of silicone compound and R-silicone compound When the ratio of content to acid catalyst content is 1:0.5, the hydrolysis time must reach 5 minutes. It can be seen that the time required for the hydrolysis reaction can decrease with the increase of the acid catalyst content.
縮合分散步驟(S3)：將一鹼觸媒加入混合溶液，以進行縮合反應。酸觸媒與鹼觸媒的莫耳比例如為1：1至1：4。 Condensation and dispersion step (S3): adding an alkali catalyst to the mixed solution to carry out a condensation reaction. The molar ratio of the acid catalyst to the alkali catalyst is, for example, 1:1 to 1:4.
於混合溶液中，鹼觸媒含量增加會明顯縮短縮合反應時間(即凝膠化時間)。鹼觸媒與酸觸媒的莫耳比為1：1時，凝膠化時間約1,600分鐘；鹼觸媒與酸觸媒的莫耳比值3：1時，凝膠化時間下降至約3分鐘。因此，可調配鹼觸媒含量以調整製程所需時間。 In the mixed solution, an increase in the alkali catalyst content will significantly shorten the condensation reaction time (ie, gelation time). When the molar ratio of alkali catalyst to acid catalyst is 1:1, the gelation time is about 1,600 minutes; when the molar ratio of alkali catalyst to acid catalyst is 3:1, the gelation time drops to about 3 minutes . Therefore, the content of alkali catalyst can be adjusted to adjust the time required for the process.
於縮合分散步驟(S3)中的縮合反應接近完成前，混合溶液會先形成溶膠溶液狀(solution-like sol)。於混合溶液控制於溶膠狀的條件下加入大量非相容體系的疏水性分散溶媒，並進行100rpm至500rpm轉速的快速攪拌，使混合溶液受分散溶媒的混合溶劑效應作用力影響，且使混合溶液中水分子的水合作用力受到抑制，隨後凝膠化形成親水性氣凝膠濕膠結構。混合溶劑與疏水性分散溶媒的體積比為1：0.05至1：0.5，而疏水性分散溶媒含量越高，後續所製備之氣凝膠結構收縮率越低，巨觀相分離行為越嚴重且呈現不透明外觀，但其結構孔隙度越高且密度越低。 Before the condensation reaction in the condensation dispersion step (S3) is nearly complete, the mixed solution will first form a solution-like sol. Under the condition that the mixed solution is controlled in a sol-like condition, a large amount of hydrophobic dispersing solvents of incompatible systems are added, and rapid stirring is performed at a speed of 100 to 500 rpm, so that the mixed solution is affected by the mixed solvent effect of the dispersing solvent, and the mixed solution The hydration force of the middle water molecules is inhibited, and then gelatinizes to form a hydrophilic aerogel wet gel structure. The volume ratio of mixed solvent and hydrophobic dispersing solvent is 1:0.05 to 1:0.5, and the higher the content of hydrophobic dispersing solvent, the lower the shrinkage rate of the aerogel structure prepared subsequently, the more severe the macroscopic phase separation behavior and the appearance Opaque appearance, but the higher the structural porosity and the lower the density.
縮合分散步驟(S3)中所用的疏水性分散溶媒可為C1至C10醇類、C6至C16芳香族類、C5至C10烷類、C7至C10芳香族醇類、C6至C16鹵化芳香族類、或C1至C6鹵化烷類等。具體而言，例如甲醇、乙醇、環己烷、正己烷、正戊烷、苯、甲苯、二甲苯、苯甲醇、苯乙醇、四氯化碳、或氯仿。 The hydrophobic dispersion solvent used in the condensation dispersion step (S3) can be C1 to C10 alcohols, C6 to C16 aromatics, C5 to C10 alkanes, C7 to C10 aromatic alcohols, C6 to C16 halogenated aromatics, Or C1 to C6 halogenated alkanes, etc. Specifically, for example, methanol, ethanol, cyclohexane, n-hexane, n-pentane, benzene, toluene, xylene, benzyl alcohol, phenethyl alcohol, carbon tetrachloride, or chloroform.
凝膠老化步驟(S4)：所形成之親水性氣凝膠濕膠結構於一特定溫度下進行老化，促使親水性氣凝膠濕膠結構穩定。舉例而言，老化溫度例如35 至80℃，再例如40至50℃。 Gel aging step (S4): The formed hydrophilic aerogel wet gel structure is aged at a specific temperature to promote the stability of the hydrophilic aerogel wet gel structure. For example, the aging temperature is 35 To 80°C, for example 40 to 50°C.
破碎分散步驟(S5)：於大量疏水性溶媒條件下進行破碎親水性濕膠，使親水性濕膠破碎成粒徑大小介於數百微米到數十毫米的顆粒並分散於疏水性溶媒中。 Crushing and dispersing step (S5): crushing the hydrophilic wet glue under the condition of a large amount of hydrophobic solvent, so that the hydrophilic wet glue is broken into particles with a particle size ranging from hundreds of microns to tens of millimeters and dispersed in the hydrophobic solvent.
破碎分散步驟(S5)所用的疏水性溶媒可為C6至C10芳香族類、C5至C10烷類、C7至C10芳香族醇類、C6至C16鹵化芳香族類、及C1至C6鹵化烷類之一或多種。具體而言例如環己烷、正己烷、正戊烷、苯、二甲苯甲苯、苯甲醇、苯乙醇、四氯化碳、或氯仿。 The hydrophobic solvent used in the crushing dispersion step (S5) can be C6 to C10 aromatics, C5 to C10 alkanes, C7 to C10 aromatic alcohols, C6 to C16 halogenated aromatics, and C1 to C6 halogenated alkanes. One or more. Specifically, for example, cyclohexane, n-hexane, n-pentane, benzene, xylene toluene, benzyl alcohol, phenethyl alcohol, carbon tetrachloride, or chloroform.
高溫溶劑置換步驟(S6)：利用常壓高溫對濕膠進行溶劑置換。高溫溶劑置換步驟(S6)利用親水性及疏水性溶劑之間的互溶性質，使得濕膠內部的水分子或其他親水性分子與大量疏水性溶媒之間混溶共沸，進而快速置換濕膠中的溶劑至呈現藍透狀或完全透明狀，因此於後續可製備出低密度且高孔隙率的親水性氣凝膠顆粒。舉例而言，溶劑置換溫度例如50至160℃。 High-temperature solvent replacement step (S6): the wet glue is solvent-replaced using normal pressure and high temperature. The high-temperature solvent replacement step (S6) utilizes the mutual solubility between hydrophilic and hydrophobic solvents, so that the water molecules or other hydrophilic molecules in the wet glue and a large number of hydrophobic solvents are miscible and azeotropic, thereby quickly replacing the wet glue. The solvent is blue and transparent or completely transparent. Therefore, low-density and high-porosity hydrophilic aerogel particles can be prepared later. For example, the solvent replacement temperature is 50 to 160°C.
溶劑蒸發乾燥步驟(S7)：高溫蒸餾排除前述剩餘的疏水性溶媒或用過濾器濾除前述剩餘的疏水性溶媒後，利用60至250℃且常壓條件下快速乾燥，即可獲得高密度的親水性氣凝膠顆粒。進一步地，以90至250℃流動床乾燥機、恆溫烘箱、滾筒式乾燥機、攪拌乾燥機、噴霧式乾燥機、或真空乾燥機進行氣凝膠顆粒乾燥，以獲得乾親水性氣凝膠顆粒。舉例而言，高溫蒸餾條件例如90至250℃且常壓。 Solvent evaporation and drying step (S7): After removing the aforementioned remaining hydrophobic solvent by high-temperature distillation or filtering out the aforementioned remaining hydrophobic solvent with a filter, it is quickly dried at 60 to 250°C and normal pressure to obtain a high-density Hydrophilic aerogel particles. Further, the aerogel particles are dried by a fluidized bed dryer, a constant temperature oven, a drum dryer, a stirring dryer, a spray dryer, or a vacuum dryer at 90 to 250°C to obtain dry hydrophilic aerogel particles . For example, the high-temperature distillation conditions are, for example, 90 to 250°C and normal pressure.
藉此，即可製備粒徑大小介於數百微米到數十毫米的多孔性親水性氣凝膠顆粒。另藉由本技術亦可製備出親水性官能基改質的氣凝膠顆粒以應用於各種親水性水泥、水泥漆、黏膠、漆類等有機材料混合，提高氣凝膠顆粒的 應用性質。特別是親水性氣凝膠顆粒可應用於高防火隔熱混凝土的製備，來明顯提升混凝土的隔熱及防火效果。 In this way, porous hydrophilic aerogel particles with a particle size ranging from hundreds of microns to tens of millimeters can be prepared. In addition, by using this technology, aerogel particles modified with hydrophilic functional groups can also be prepared to be used in the mixing of various hydrophilic cement, cement paint, viscose, paint and other organic materials to improve the performance of aerogel particles. Nature of application. In particular, the hydrophilic aerogel particles can be applied to the preparation of highly fireproof and heat-insulating concrete to significantly improve the heat-insulating and fire-proof effects of concrete.
請參閱圖2及圖3，利用一般相機或掃描式電子顯微鏡觀察親水性氣凝膠顆粒的外觀尺寸與微細結構，所拍攝的照片顯示所製備之親水性氣凝膠顆粒的尺寸在數毫米至數十毫米。 Please refer to Figure 2 and Figure 3, using a general camera or scanning electron microscope to observe the appearance size and fine structure of the hydrophilic aerogel particles. Tens of millimeters.
請續參閱圖4，觀察水泥及氣凝膠顆粒以混合體積比例1：2製備的混凝土外觀與重量。由照片顯示一般水泥砂混凝土重量為1420.5g，而本實施方式之混凝土的重量為788.2g。換言之，相同體積下本實施方式之混凝土的重量約為一般水泥砂混凝土的55%，具有優異輕量化效果。 Please continue to refer to Figure 4 to observe the appearance and weight of concrete prepared with cement and aerogel particles at a mixing volume ratio of 1:2. The photo shows that the weight of the general cement sand concrete is 1420.5g, while the weight of the concrete of this embodiment is 788.2g. In other words, the weight of the concrete of this embodiment under the same volume is about 55% of the general cement sand concrete, which has an excellent lightweight effect.
請續參閱圖5，呈現本實施方式上述之混凝土的斷面照片，由照片顯示氣凝膠顆粒於水泥中均勻分散。換言之，氣凝膠顆粒於水泥中不會呈現不均一分層。 Please continue to refer to FIG. 5, which presents a cross-sectional photograph of the above-mentioned concrete in this embodiment, which shows that the aerogel particles are uniformly dispersed in the cement. In other words, the aerogel particles will not exhibit uneven stratification in the cement.
本實施方式上述之混凝土與一般水泥砂混凝土各取厚度3cm後在70℃加熱板加熱初期與加熱6小時後的表面溫度進行比對。由比對結果顯示出室溫溫度為25℃，一般混凝土加熱6小時後的表面溫度約為47.4℃；相對地，本實施方式上述之混凝土加熱6小時後的表面溫度約為32℃，顯示本實施方式的產品具有極優異的隔熱性質。 The above-mentioned concrete and general cement sand concrete in this embodiment are each taken with a thickness of 3 cm and compared with the surface temperature of the heating plate at the initial stage of heating at 70°C and the surface temperature after heating for 6 hours. The comparison result shows that the room temperature is 25°C. Generally, the surface temperature of the concrete after heating for 6 hours is about 47.4°C; on the other hand, the surface temperature of the concrete heated for 6 hours in this embodiment is about 32°C, which shows that this embodiment The products of the method have extremely excellent thermal insulation properties.
另外，在1200℃高溫噴燈加熱1小時後的表面溫度進行比對。由比對結果顯示出本實施方式上述之混凝土加熱1小時後非加熱面的表面溫度約為74.7℃；相對地，一般水泥砂混凝土加熱1小時後非加熱面的的表面溫度約為321.1℃。由數據顯示本實施方式的產品具有相當優異的耐高溫隔熱性質。 In addition, the surface temperature after heating at a high temperature of 1200°C for 1 hour was compared. The comparison result shows that the surface temperature of the unheated surface of the concrete in this embodiment is about 74.7°C after heating for 1 hour; relatively, the surface temperature of the unheated surface of the general cement sand concrete is about 321.1°C after heating for 1 hour. The data shows that the product of this embodiment has quite excellent high temperature resistance and heat insulation properties.
綜合上述實施例之說明，當可充分瞭解本發明之製作、應用及本 發明產生之功效，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。 Based on the description of the above-mentioned embodiments, one can fully understand the production, application and nature of the present invention The effects of the invention, but the above-mentioned embodiments are only the preferred embodiments of the invention, and should not be used to limit the scope of implementation of the invention, that is, simple equivalent changes are made according to the scope of the patent application of the invention and the description of the invention. And modifications are all within the scope of the present invention.
(S1)‧‧‧混合步驟 (S1)‧‧‧Mixing Step
(S2)‧‧‧水解步驟 (S2)‧‧‧Hydrolysis step
(S3)‧‧‧縮合分散步驟 (S3)‧‧‧Condensation and dispersion step
(S4)‧‧‧凝膠老化步驟 (S4)‧‧‧Gel aging steps
(S5)‧‧‧破碎分散步驟 (S5)‧‧‧Crushing and dispersing step
(S6)‧‧‧高溫溶劑置換步驟 (S6)‧‧‧High temperature solvent replacement step
(S7)‧‧‧溶劑蒸發乾燥步驟 (S7)‧‧‧Solvent evaporation and drying step
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| CN102448883A (en) * | 2009-05-29 | 2012-05-09 | 赢创德固赛有限公司 | Process for the preparation of an aerogel in pellets |
| TW201536905A (en) * | 2014-02-26 | 2015-10-01 | Hitachi Chemical Co Ltd | Aerogel |
| TW201641544A (en) * | 2015-05-27 | 2016-12-01 | Univ Kun Shan | Aerogel granule and preparation method thereof |
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| CN102448883A (en) * | 2009-05-29 | 2012-05-09 | 赢创德固赛有限公司 | Process for the preparation of an aerogel in pellets |
| TW201536905A (en) * | 2014-02-26 | 2015-10-01 | Hitachi Chemical Co Ltd | Aerogel |
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