201226451 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有中空粗糙表面結構的有機矽烷 微球及其製備方法。 【先前技術】 有機矽烷是一類具有分子水準的有機-無機雜化結 構，其中矽原子構成無機矽氧“骨架”，矽原子可以通過 側基引入多種有機官能團構成有機結構部分。這種結構使 其兼具無機材料與有機材料的優異性能，其無機内核能抑 制聚合物分子的鏈運動而賦予雜化材料良好的财熱性能， 有機取代基和高分子鏈賦予雜化材料良好的韌性和可加工 性。有機矽烷還具有很好的光學性質、耐熱性、耐候性、 增濕性以及電絕緣性和介電性質，近年來廣泛應用於電子 封裝，光學傳導等領域。有機矽烷材料在受熱分解後的殘 餘物主要為不燃性Si02，且Si02的重量百分比可高達 87%。因此，與通常的阻燃高分子材料相比，含有有機矽 烷的聚合物能延長點火時間並大大降低燃燒放熱程度，阻 燃性能非常好。所以，有機矽烷不但可作為複合材料直接 使用，也可加入傳統的填料如玻璃纖維後使用。 中空有機矽烷顆粒由於其低密度、穩定的熱、光、電、 磁性能，故可以廣泛應用於微反應器、藥物載體，亦可作 為染料分散劑、吸波材料、有機樹脂的改性劑之用。模板 輔助法是合成中空有機矽烷微囊的一種典型方法，以模板 作為支架材料，最終所得中空微球的形狀和空腔尺寸可以 201226451 通過模板控制。通常用作模板的材料主要有聚合物乳膠 粒、無機金屬奈米粒子、嵌段共聚物膠束、表面活性劑有 序聚集體等等。先製備得到這些模板材料之後，矽烷前體 在模板表面水解聚合得到有機矽烷的包覆層，這種核殼結 構複合物再經過鍛燒或有機溶劑蝕刻掉模板，得到中空微 球。模板法不但煩瑣，而且製備的中空微球外觀不規整， 不止會出現大量破損，模板本身的團聚行為也使得中空微 球在尺寸大小均勻性的控制上變得極為困難。 【發明内容】 有鑒於此，經本案申請發明人廣泛研究和反覆實驗後 發現，一種表面具有皺褶、内部具有中空的有機矽烷微球， 粒徑均勻度高，且合成方法簡單，解決了採用傳統中空微 球製備方法所造成的粒徑不均及大量球體破損的問題。 本發明的主要目的在於提供一種具有粗糙表面結構中 空有機矽烷微球，其特徵在於提供pH值為10〜B的鹼性 溶液，混合至少兩種有機矽烷而得到有機矽烷混合物，將 該有機梦烧混合物加入到該鹼性溶液中，進行水解縮聚反 應後’靜置陳化而得。 本發明的又一目的為提供一種製備具有粗糙表面結構 之中空有機矽烷微球之方法，該方法包含： 提供PH值為10〜13的鹼性溶液； 混合至少兩種有機矽烷而得到有機矽烷混合物； 將所述有機矽烷混合物加入到所述鹼性溶液中’在0 〇l22645i 以及。下攪拌Η)分鐘〜10小時，進行水解縮聚反應； 所^置陳化1小時〜2〇小時’離心，洗條，冷束乾燥。 中進/兩種有機雜包含至少一種有機魏在驗性溶液 鹼性=水解縮聚反應後具有親水性和至少一種有機石夕炫在 溶液巾騎水解㈣職後具有疏水性，且水解縮聚 應後具有親水性的㈣钱與水解縮聚反錢具有疏水 性的有機矽烷的重量比為1 : 1〜1 : 1〇。 本^月揭露之-種具有粗缝表面結構之中空有機石夕炫 微球的製備方法所製得的有機石夕燒微球，藉由簡單的方法 及溫和的反應條件得到粒徑均勻度高的有機石夕燒微球，解 決先前技術-模板法中煩瑣的製程步驟。另外，也解決了先 前技術中因模板本身的團聚行為而造成中空微球在尺寸大 小均勻性不易控制的問題。 【實施方式】 本發明之具有粗縫表面結構之中空有機石夕燒微球，上 述中空有機矽烷微球係藉由包括下列步驟之方法所形成： 提供pH值為10〜13的驗性溶液，混合至少兩種有機石夕炫 而得到有機石夕燒混合物，將該有機石夕燒混合物加入到該驗 性溶液中，進行水解縮聚反應後，靜置陳化而得，該微球 具有高均勻性的粒徑，粒徑分佈範圍窄，根據體均粒徑與 201226451 * 數均粒徑之比（Dv/Dn)計算的多分散系數值小於1.05， 式中Dv為體積平均粒徑，Dn為數目平均粒徑，較佳的， 體積平均粒徑與數目平均粒徑的比值為1〇〜1〇5。在使用 不同的有機矽烷搭配之下，本發明所提供的有機矽烷微球 的平均粒徑可以為50奈米〜5微米。 使用於本發明中之鹼性溶液包含鹼性物質和溶劑，上 述的鹼性物質，可以為無機鹼或有機鹼，較佳是使用無機 鹼。上述的溶劑可以選擇水或是醇。 本發明中所使用的有機矽烷，可以是單體或是寡聚 物，本發明將至少兩種的有機矽烷置於鹼性溶液體系中， 以鹼性/谷液為1〇重量份計，所述的有機石夕燒的含量為〇 6 〜5重量份。上述至少兩種有機矽烷包含至少一種有機矽 燒在驗性溶液t進行水解縮聚反應後具有親水性和至少一 種有機矽烷在鹼性溶液中進行水解縮聚反應後具有疏水 性’且所有水解縮聚反應後具有親水性的有機矽烷與所有 水解縮聚反應後具有疏水性的有機矽烷的重量比為丨：j〜 後具有親水性的有機矽烷的反應速度較快， 後具有疏水性的有機石夕燒的反應速度較慢201226451 VI. Description of the Invention: [Technical Field] The present invention relates to an organic decane microsphere having a hollow rough surface structure and a preparation method thereof. [Prior Art] Organic decane is a kind of organic-inorganic hybrid structure with molecular level, in which ruthenium atoms constitute an inorganic ruthenium "skeleton", and ruthenium atoms can introduce various organic functional groups through side groups to form organic structural parts. This structure combines the excellent properties of inorganic materials and organic materials, and its inorganic core inhibits the chain motion of polymer molecules and imparts good thermal performance to hybrid materials. Organic substituents and polymer chains impart good hybrid materials. Toughness and workability. Organic germanes also have excellent optical properties, heat resistance, weather resistance, moisture absorption, electrical insulation and dielectric properties, and have been widely used in electronic packaging, optical conduction and the like in recent years. The residue of the organic decane material after thermal decomposition is mainly non-combustible SiO 2 , and the weight percentage of SiO 2 can be as high as 87%. Therefore, compared with the conventional flame-retardant polymer material, the organic decane-containing polymer can prolong the ignition time and greatly reduce the degree of combustion heat release, and the flame retardancy is very good. Therefore, organic decane can be used not only as a composite material but also as a conventional filler such as glass fiber. Hollow organic decane particles can be widely used in micro-reactors, drug carriers, and as dye dispersants, absorbing materials, and modifiers for organic resins due to their low density, stable thermal, optical, electrical, and magnetic properties. use. The template assisted method is a typical method for synthesizing hollow organic decane microcapsules. The template is used as a scaffold material, and the shape and cavity size of the resulting hollow microspheres can be controlled by the template in 201226451. The materials commonly used as templates are mainly polymer latex particles, inorganic metal nanoparticles, block copolymer micelles, surfactant aggregates, and the like. After preparing the template materials, the decane precursor is hydrolyzed and polymerized on the surface of the template to obtain a coating layer of an organic decane. The core-shell composite is then etched or etched away with an organic solvent to obtain hollow microspheres. The template method is not only cumbersome, but also the appearance of the prepared hollow microspheres is irregular, and not only a large amount of damage occurs, but also the agglomeration behavior of the template itself makes the hollow microspheres extremely difficult to control the size uniformity. SUMMARY OF THE INVENTION In view of this, after extensive research and repeated experiments by the inventors of the present application, it was found that a kind of organic decane microspheres having wrinkles on the surface and hollow inside have high uniformity of particle size, and the synthesis method is simple, and the adoption is solved. The problem of uneven particle size and a large number of spherical damage caused by the conventional hollow microsphere preparation method. The main object of the present invention is to provide a hollow organic decane microsphere having a rough surface structure, which is characterized in that an alkaline solution having a pH of 10 to B is provided, and at least two organic decanes are mixed to obtain an organic decane mixture, and the organic dolphine mixture is burned. The mixture is added to the alkaline solution, and after undergoing hydrolysis and polycondensation reaction, it is obtained by standing and aging. It is still another object of the present invention to provide a method for preparing hollow organodecane microspheres having a rough surface structure, the method comprising: providing an alkaline solution having a pH of 10 to 13; mixing at least two organic decanes to obtain an organic decane mixture Adding the organodecane mixture to the alkaline solution 'at 0 〇l22645i and . The mixture was stirred for Η) for 10 minutes to carry out a hydrolysis polycondensation reaction; the aging was carried out for 1 hour to 2 hours, and the mixture was centrifuged, washed, and dried by cold drying. The intermediate/two organic impurities comprise at least one organic Wei in the test solution alkaline = hydrolyzed polycondensation reaction has hydrophilicity and at least one organic stone Xi Xuan has hydrophobicity after the solution towel rides hydrolysis (four), and after hydrolysis and polycondensation The weight ratio of the hydrophilic (4) money to the hydrolyzed polycondensation anti-money organic decane is 1: 1~1 : 1〇. The organic stone-fired microspheres prepared by the preparation method of the hollow organic stone Xixuan microspheres having the rough surface structure disclosed in the present invention have high uniformity of particle size by a simple method and mild reaction conditions. The organic stone sizzling microspheres solve the cumbersome process steps of the prior art-template method. In addition, the problem that the hollow microspheres are difficult to control in size uniformity due to the agglomeration behavior of the template itself in the prior art is also solved. [Embodiment] The hollow organoceramic microspheres having a rough surface structure of the present invention, the hollow organodecane microspheres are formed by a method comprising the following steps: providing an experimental solution having a pH of 10 to 13, Mixing at least two organic stones to obtain an organic stone mixture, adding the organic stone mixture to the test solution, performing a hydrolysis polycondensation reaction, and then standing and aging, the microspheres have high uniformity The particle size distribution and the particle size distribution range are narrow. The polydispersity coefficient value calculated according to the ratio of the volume average particle diameter to the 201226451 * number average particle diameter (Dv/Dn) is less than 1.05, where Dv is the volume average particle diameter, and Dn is The number average particle diameter, preferably, the ratio of the volume average particle diameter to the number average particle diameter is 1 〇 1 to 1 〇 5. The organic decane microspheres provided by the present invention may have an average particle diameter of from 50 nm to 5 μm, using a combination of different organic decanes. The alkaline solution used in the present invention contains a basic substance and a solvent, and the above-mentioned basic substance may be an inorganic base or an organic base, and an inorganic base is preferably used. The above solvent may be selected from water or an alcohol. The organodecane used in the present invention may be a monomer or an oligomer. In the present invention, at least two kinds of organodecane are placed in an alkaline solution system, and the amount of the alkaline/cold solution is 1 part by weight. The content of the organic stone simmer is 〇6 to 5 parts by weight. The at least two organodecanes comprise at least one organic oxime which has hydrophilicity after the hydrolysis solution polycondensation reaction of the test solution t and at least one organic decane has hydrophobicity after hydrolysis and polycondensation reaction in an alkaline solution and after all the hydrolysis polycondensation reaction The weight ratio of the organic decane having hydrophilicity to the organic decane having hydrophobicity after all the hydrolysis polycondensation reaction is 丨:j~, and the reaction rate of the organic decane having hydrophilicity is faster, and then the reaction of the hydrophobic organic smelting Slower
1 : 1〇。一般而言，在鹼性極性質子溶劑中，水解縮聚反應 ’水解縮聚反應 差異’位於内部的親呔性聚合物 201226451 從内往外擴張’而疏水性聚合物從外往内遷移，進而使聚 合物矽烷微球内外翻轉，因此製得的有機矽烷微球具有粗 縫表面且中空的特殊結構，且形成的微球的粒徑非常均勺 上述的水解縮聚反應後具有親水性的有機發境可以θ 四乙氧基石夕烧(tetraethoxysilane，TEOS)、帶氫原子的石夕氧产戈者 帶氣原子的矽氧烷，較佳是四乙氧基矽烷。 上述的水解縮聚反應後具有疏水性的有機矽規可以是 乙稀基三曱氧基石夕烧(vinyltrimethoxysilane)、苯基三曱氧基石夕院 (phenyltrimethoxysilane)、二甲基二甲氧基石夕烧 (dimethyldimethoxysilane)、甲基三曱氧基矽烷(methyltrimeth〇Xysiiane)、 3 -氣基丙基二乙氧基石夕炫>(3-Aminopropyltriethoxysilane)或其混合 物。 由於有機矽烷微球的外表面帶有皺褶結構，具有吸油 的特性，可以用作紙張、塗料表面的處理劑；加入有機樹 内可以增加產品消光、耐磨、保溫、隔音等效果；同時， 有機矽烷微球具有中空結構，所以也可以作為充填催化劑 的載體、微型反應器’亦可作為藥物微膠囊、染料分散劑、 微波吸收材料等。 本發明另提供一種製備具有粗糙表面結構之中空有機 矽烷微球的方法’其包括下述步驟： (1) 提供PH值為丨〇〜13的鹼性溶液； (2) 混合至少兩種有機矽貌而得到有機矽炫混合物； 2012264511 : 1〇. In general, in the basic polar protic solvent, the hydrolysis polycondensation reaction 'hydrolysis polycondensation reaction difference' is located inside the affinity polymer 201226451 to expand from the inside out while the hydrophobic polymer migrates from the outside to the inside, thereby enabling polymerization The decane microspheres are inverted inside and outside, so the obtained organic decane microspheres have a special structure with a rough surface and a hollow shape, and the particle diameter of the formed microspheres is very uniform. The above organic hydrolytic polycondensation reaction has a hydrophilic organic environment. θ Tetraethoxysilane (TEOS), a gas atom-containing helioxane having a hydrogen atom, preferably tetraethoxy decane. The organic hydrazine having hydrophobicity after the above hydrolysis and polycondensation reaction may be vinyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane ( Dimethyldimethoxysilane), methyltrimeth〇Xysiiane, 3-Aminopropyltriethoxysilane or a mixture thereof. Since the outer surface of the organic decane microsphere has a wrinkle structure, it has the characteristics of oil absorption, and can be used as a treatment agent for paper and paint surface; adding organic tree can increase the effects of matting, abrasion resistance, heat preservation and sound insulation; Since the organic decane microspheres have a hollow structure, they can also serve as a carrier for charging a catalyst, and a microreactor can also be used as a drug microcapsule, a dye dispersant, a microwave absorbing material, or the like. The present invention further provides a method for preparing hollow organodecane microspheres having a rough surface structure, which comprises the steps of: (1) providing an alkaline solution having a pH of 丨〇~13; and (2) mixing at least two organic hydrazines. Appearance to obtain an organic bright mixture; 201226451
. (3)將該有機矽烷混合物加入到該鹼性溶液中，在〇°C . 〜70°C下攪拌10分鐘〜10小時，進行水解縮聚 反應，以及 (4)靜置陳化1小時〜20小時，離心，洗滌，冷凍乾 燥，即可得到中空有機矽烷微球。 本發明製程中步驟（1)之鹼性溶液包含鹼性物質，所使 用的鹼性物質，可以為無機鹼或有機鹼，較佳是使用無機 驗。 所述的無機驗可以為氨水、氫氧化納或氫氧化卸。 所述的有機鹼可以為乙二胺或三乙胺。 所述的鹼性溶液包含溶劑，所述的溶劑可以選擇水或 是醇，例如為乙醇。 本發明製程中步驟(2)之有機矽烷，可以是有機矽烷單 體或有機矽烷寡聚物。 本發明製程中步驟（2)之至少兩種有機矽烷包含至少 一種有機矽烷在鹼性溶液中進行水解縮聚反應後具有親水 性和至少一種有機矽烷在鹼性溶液中進行水解縮聚反應後 具有疏水性。 本發明使用至少兩種有機矽烷，並將之均勻混合，形 成有機矽烷混合物，當水解縮聚後所形成的聚合物間存在 • 著親疏水性差異，位於内部的親水性聚合物從内往外擴 - 張，而疏水性聚合物從外往内遷移，進而使聚合物矽烷微 9 201226451 球内外翻轉’因此製得的有機矽烷微球具有粗糙表面且中 空的特殊結構，且形成的微球粒徑非常均勻。 為在水解縮聚反應後，讓所述的有機矽烷存在著親疏水 性的差異，根據本發明的一實施態樣，所述的有機矽烷會 有不同的有機取代基，所述的有機取代基可以是簡單的烴 基，也可以是極性結構或官能基團，較佳的有機取代基包 括直鏈烷基'烯基、芳香烴基、烷氧基、胺基。 本發明製程中步驟(3)之水解縮聚反應後具有親水性的 有機矽烷可以是四乙氧基矽烷(tetraeth〇xysikne，TE〇s)、帶氫原 子的矽氧烷或者帶氣原子的矽氧烷，較佳是四乙氧基矽烷。 本發明製程中步驟(3)之水解縮聚反應後具有疏水性的 有機矽烷可以是乙烯基三曱氧基矽烷 (vinyltrimethoxysilane)、苯基三曱氧基矽烷 (phenyltrimethoxysilane)、二曱基二甲氧基石夕烧 (dimethyldimethoxysilane)、甲基三曱氧基矽烧 (methyltrimethoxysilane)、3 -氨基丙基三乙氧基矽烷 (3-Aminopropyltriethoxysilane)或其混合物。 上述的所有水解縮聚反應後具有親水性的有機石夕院與 所有水解縮聚反應後具有疏水性的有機矽烧的皇量比為 1 : 1〜1 : 10。 上述的有機矽烷，以鹼性溶液為10重量份計，其含量 為0.6〜5重量份。 201226451 根據本發明的一實施態樣，將有機矽烷混合物加入到 所述鹼性溶液中在〇〇C〜7(TC下，較佳的攪拌15小時〜9 小時後，進行水解縮聚反應；較佳的靜置陳化12小時〜18 小時，在反應完成後’以離心的方式分離有财烧微球及 驗性溶液’再w離子水反1洗條有機魏微球後，冷珠 乾燥，進行有機㈣微球的乾燥，並將驗性溶液中未反應 的有機矽烷’回收再利用。 根據本發明的-實施態樣，採用弱驗做為水解催化劑 所得到的中空有機矽烷顆粒粒徑較小，另外，採用較言的 溫度，也可以得到粒徑較小的中空有機魏微球，因此，、 可以運用反應條件的改變來控制所要得到的中空有機矽烷 微球的粒徑尺寸大小。 1"" 上述製程所製得的有機矽烷微球，藉由簡單的方法及 溫和的反應條件，得到粒徑均勻度高的中空有機矽烷微 球，解決先刖技術-模板法中煩瑣的製程步驟，而且，無需 鍛燒或有機溶劑蝕刻掉模板，製備的中空微球形貌規整， 不會出現破損。另外，也解決了先前技術中因模板本身的 團聚行為而造成中空微球的粒徑大小均勻性不易控制的門 題。 實施例 參考以下内容敍述與申請專利範圍，能對上述提及之 本發明特色與其他特性、觀點和益處有更明確的瞭解。 ^4 201226451 需明白’以上整體敍述及往下將提到之細節推述，僅為示 範例。為了讓本發明所提供之—種具有粗链表㈣構中* 有機雜微球及其製備方法更加清楚起見，在下述較^ 施例中對本發明所揭露之運Μ时機钱單體及驗性溶 液組成之應用做進-步介紹，並湘μ實施例中所得到 的有機石浅微球的粒徑分佈量測資料及掃描式電子顯微鏡 圖來驗證本發明所提供之有機魏微球的結構特徵及粒徑 的均-性。這裡所指的平均粒徑是根冑謝㈣⑽測試 所得的數目平均粒徑，—主要分佈是餘料95%以上 的顆粒的粒徑分佈範圍。 實施例1: 0.01克25%氨水分散到1G克去離子水中形成均句溶 液’乙稀基二曱氧基錢與四乙氧基石浅以41的重量比 混合’在200啊轉速下搜拌3〇分鐘，然後將15克上述 有機石夕燒的混合物緩慢滴加到預先混合的氨水溶液中，升 溫至7(TC ’ 200 rpm轉速下反應8小時之後在7代下陳 化15小時’最麟心，用去離子水反覆鎌，冷;東乾燥， 生成的顆粒平均粒徑為，粒徑分佈在0.7㈣u ，收率為37%。 實施例2 : 〇.5克25%氨水分散到1Q克去離子水中形成均句溶 12 201226451 液，苯基三曱氧基矽烷與四乙氧基矽烷以4:丨的重量比混 合’在200 rpm轉速下攪拌30分鐘，然後將16克上述有 機石夕烧的混合物緩慢滴加到預先混合的氨水溶液中，放置 故冰水混合液中，200 rpm轉速下反應8小時，之後在〇 C冰水混合液中陳化15小時，最後離心，用去離子水反 覆洗滌，冷凍乾燥，生成的顆粒平均粒徑為2.48“m，粒 徑主要分佈在2.2 μ m-2.6 // m，收率為41%。 實施例3 :(3) adding the organodecane mixture to the alkaline solution, stirring at ～°° C. to 70° C. for 10 minutes to 10 hours to carry out hydrolysis polycondensation reaction, and (4) standing for aging for 1 hour~ After 20 hours, centrifugation, washing, and lyophilization, hollow organic decane microspheres were obtained. The alkaline solution of the step (1) in the process of the present invention contains a basic substance, and the alkaline substance to be used may be an inorganic base or an organic base, and an inorganic test is preferably used. The inorganic test may be ammonia water, sodium hydroxide or hydrogen hydroxide. The organic base may be ethylenediamine or triethylamine. The alkaline solution contains a solvent, and the solvent may be selected from water or an alcohol such as ethanol. The organodecane of the step (2) in the process of the present invention may be an organic decane monomer or an organic decane oligomer. The at least two organodecanes of the step (2) in the process of the present invention comprise at least one organodecane having hydrophilicity after undergoing hydrolysis polycondensation reaction in an alkaline solution and at least one organodecane having hydrophobicity after undergoing hydrolysis polycondensation reaction in an alkaline solution . The present invention uses at least two kinds of organodecane and uniformly mixes them to form an organic decane mixture. When hydrolyzed and polycondensed, the formed polymer has a difference in hydrophilicity and hydrophobicity, and the hydrophilic polymer located inside expands from the inside to the outside. The hydrophobic polymer migrates from the outside to the inside, thereby inverting the polymer decane micro 9 201226451 inside and outside. The organic silane microspheres thus obtained have a rough surface and a hollow special structure, and the formed microspheres have a very uniform particle size. . In order to make the organic decane have a difference in hydrophilicity and hydrophobicity after the hydrolysis polycondensation reaction, according to an embodiment of the present invention, the organic decane may have different organic substituents, and the organic substituent may be The simple hydrocarbon group may also be a polar structure or a functional group. Preferred organic substituents include a linear alkyl 'alkenyl group, an aromatic hydrocarbon group, an alkoxy group, and an amine group. The organic decane having hydrophilicity after the hydrolysis polycondensation reaction of the step (3) in the process of the present invention may be tetraeth〇xysikne (TE〇s), a hydrogen atom-containing helium oxide or a gas atom-containing helium oxygen. The alkane is preferably tetraethoxydecane. The organodecane having hydrophobicity after the hydrolysis polycondensation reaction in the step (3) in the process of the present invention may be vinyltrimethoxysilane, phenyltrimethoxysilane or dimercaptodimethoxysilane. Dimethyldimethoxysilane, methyltrimethoxysilane, 3-Aminopropyltriethoxysilane or a mixture thereof. All of the above-mentioned hydrolyzed polycondensation reactions have a hydrophilic organic zexiyuan with a hydrophobic polycondensation reaction and a hydrophobic organic smoldering ratio of 1 : 1 to 1 : 10. The above organic decane is contained in an amount of from 0.6 to 5 parts by weight based on 10 parts by weight of the alkaline solution. 201226451 According to an embodiment of the present invention, the organodecane mixture is added to the alkaline solution at 〇〇C~7 (TC, preferably after stirring for 15 hours to 9 hours, followed by hydrolysis and polycondensation reaction; preferably After standing for 12 hours to 18 hours, after the reaction is completed, 'the centrifugal microspheres and the test solution are separated by centrifugation', then w ion water is used to wash the organic Wei microspheres, and the cold beads are dried and organic (4) The microspheres are dried, and the unreacted organic decane in the test solution is recovered and reused. According to the embodiment of the present invention, the hollow organic decane particles obtained by using the weak test as the hydrolysis catalyst have a small particle size, and The hollow organic Wei microspheres having a smaller particle size can also be obtained by using a relatively high temperature. Therefore, the change of the reaction conditions can be used to control the particle size of the hollow organic decane microspheres to be obtained. 1"" The prepared organic decane microspheres can obtain hollow organic decane microspheres with high uniformity of particle size by a simple method and mild reaction conditions, and solve the problem of the prior art-template method The process steps, and without the need for calcination or organic solvent etching away the template, the prepared hollow microspheres are regular and without damage. In addition, the hollow microspheres caused by the agglomeration behavior of the template itself in the prior art are also solved. The problem is that the particle size uniformity is not easy to control. The embodiments refer to the following description and the scope of the patent application, and can clearly understand the characteristics and other features, viewpoints and advantages of the invention mentioned above. ^4 201226451 Need to understand' The above general description and the detailed descriptions which will be mentioned below are merely exemplary examples. In order to make the present invention provide a thick-chained (four) structure, the organic microspheres and the preparation method thereof are more clearly described below. In the example, the application of the composition of the money and the composition of the test solution disclosed in the present invention is further introduced, and the particle size distribution measurement of the shallow microspheres of the organic stone obtained in the embodiment of the present invention is measured. The data and scanning electron micrographs were used to verify the structural characteristics and the uniformity of the particle size of the organic Wei microspheres provided by the present invention. The average particle diameter referred to herein is the root test (4) (10) test. The number average particle size obtained, the main distribution is the particle size distribution range of the particles of more than 95% of the residual material. Example 1: 0.01 g of 25% ammonia water is dispersed into 1 G of deionized water to form a homogenous solution of 'Ethyl diterpene Mix the oxy money with the tetraethoxy stone in a weight ratio of 41. Mix at a speed of 200 rpm for 3 minutes, then slowly add 15 grams of the above organic stone mixture to the premixed aqueous ammonia solution. Up to 7 (after 8 hours of reaction at TC '200 rpm, aged for 15 hours in 7th generation', the most entangled, repeated with deionized water, cold; east dry, the average particle size of the particles is, the particle size distribution is 0.7(tetra)u, yield 37%. Example 2: 55 g of 25% aqueous ammonia was dispersed in 1Q g of deionized water to form a homogenous solution 12 201226451 solution, phenyl trimethoxy decane and tetraethoxy decane to 4 : The weight of the crucible is mixed and stirred at 200 rpm for 30 minutes, then 16 g of the above organic stone mixture is slowly added dropwise to the premixed aqueous ammonia solution, and placed in an ice water mixture at 200 rpm. After 8 hours of reaction, it was aged in a mixture of 〇C ice water. , The last centrifugation, washed with deionized water and counter-cover, freeze-dried, the resulting particles of average particle diameter of 2.48 "m, particle size mainly distributed in the 2.2 μ m-2.6 // m, 41% yield. Example 3:
0.5克25%氣水分散到1 〇克去離子水中形成均句、、容 液’甲基三曱氧基矽烷與四乙氧基矽烷以4··1的重量比現 合，在200 rpm轉速下攪拌30分鐘，然後將1.2克上述有 機矽烷的混合物緩慢滴加到預先混合的氨水溶液中，放置 於20°C的室溫中’ 200 rpm轉迷下反應2小時，之後在室 溫下陳化15小時；最後離心，用去離子水反覆洗條，A 凍乾燥，生成的顆粒平均粒徑為1.5 // m，粒徑主要分佈在 1.3//m-1.7/zm，收率為 46%。 實施例4 : 0.5克25%氨水分散到10克去離子水中形成均勻溶 液，二甲基二甲氧基矽烷、苯基三甲氧基矽烷與四乙氧基 石夕烧以2:2:1的重量比混合’在200 rpm轉速下授摔3〇八 13 201226451 鐘，然後將0.78克上述有機石夕烷的混合物緩慢滴加到預先 混合的氨水溶液中，放置於20°C的室溫中，200 rpm轉速 下反應2小時，之後在2〇。(：的室溫下陳化15小時；最後 離心，用去離子水反覆洗滌，冷凍乾燥，生成的顆粒平均 粒徑為1.88μηι，粒徑主要分佈在l.6#m-2.2em，收率為 40%。 實施例5 : 0.1克40%氫氧化鈉水溶液分散到1〇克去離子水中形 成均勻溶液’ 一曱基一曱氧基石夕烧、乙稀基三曱氧基梦烧 與四乙氧基石夕烧以2:2:1的重量比混合，在2〇〇 rpm轉速下 攪拌30分鐘，然後將0.8克上述有機矽烷的混合物緩慢滴 加到預先混合的氫氧化鈉水溶液中，放置於20°C的室溫 中，200 rpm轉速下反應2小時，之後在20°C的室溫下陳 化15小時；最後離心，用去離子水反覆洗滌，冷凍乾燥， 生成的顆粒平均粒控為1.75 // m，粒徑主要分佈在1.4 /z m-2.3# m，收率為 51%。 實施例6 : 0.1克40%氫氧化鈉水溶液分散到1〇克去離子水中形 成均勻溶液，二甲基二甲氧㈣院與乙婦基三甲氧基石夕烧 與四乙氧基矽烷以2:2:1的重量比混合，在200 rpm轉速下 201226451 攪拌30分鐘，然後將0.8克上述有機矽烷的混合物緩慢滴 加到預先混合的氫氧化納水溶液中，放置於5〇°C下’ 200 rpm轉速下反應2小時，之後在50°C下陳化15小時；最 後離心，用去離子水反覆洗滌，冷凍乾燥，生成的顆粒平 均粒徑為1.22" m，粒徑主要分佈在，收 率為53%。 實施例7 : 0.1克40%氫氧化鉀水溶液分散到1〇克去離子水中形 成均勻溶液，曱基三曱氧基矽烷與四乙氧基矽烷以4:1的 重量比混合，在200 rpm轉速下攪拌3〇分鐘，然後將1.2 克上述有機矽烷的混合物緩慢滴加到預先混合的氫氧化鉀 水溶液中，放置於2〇t：的室溫中，超音波震盪反應器中反 應2小時，之後在室溫下陳化15小時；最後離心，用去 離子水反覆洗滌，冷凍乾燥，生成的顆粒平均粒徑為〇 87 ㈣，粒徑主要分佈在〇.5/zm_4.3/zm，收率為23%。 實施例8 : 0.1克40%氫氧化鉀水賴分散到1G克去離子水中形 液，苯基三甲氧基魏與四乙氧基料以4:1的 罝比成合’在200聊轉速下_ 3G分鐘，然後將】6 上逃有機魏的混合物錄滴加咖先混合的氫氧化奸 15 201226451 水溶液中，放置於冰水混合液中，200 rpm轉速下反應§小 時，之後在〇°C冰水混合液中陳化15小時；最後離心，用 去離子水反覆洗滌，冷凍乾燥，生成的顆粒平均粒徑為2 63 μιη，粒徑主要分佈在2.2em-3.1vm，收率為30%。 實施例9 : 0.01克25%氨水分散到1〇克去離子水中形成均勻溶 液，氨丙基二乙氧基矽烷與四乙氧基矽烷以3:1的重量比 混合，在200 rPm轉速下攪拌2〇分鐘，然後將12克上述 有機矽烷的混合物緩慢滴加到預先混合的氨水溶液中，放 置於20°C的室溫中，60〇rpm轉迷下反應2小時，之後在 室溫下陳化15小時；最後離心，用去離子水反覆洗滌， 冷凍乾燥，生成的顆粒平均粒徑為〇 52/zm，粒徑主要分 佈在 0.25#m-1.2//m ’ 收率為 23%。 實施例10 : 〇·〇1克25%luJc分散到1G克去離子水中形成均句溶 液，乙烯基三乙氧基矽烷與四乙氧基矽烷以4:1的重量比 混合，在200 rPm轉速下攪拌2〇分鐘，然後將15克$上述 有機石夕炫的混合物緩慢滴加到預先混合的氨水溶液中，放 置於2(TC的室溫中，200 rpm轉速下反應8小時，之後在 2(TC下陳化丨5小時；最後離心’用去離子水反覆洗條， 201226451 冷凍乾燥，生成的顆粒平均粒徑為1.57从讯，粒徑主要分 佈在 1.2"ιη-1.8μιη，收率為 21%。 實施例11 : 0.1克40%氫氧化鈉水溶液分散到10克去離子水中形 成均勻溶液，曱基三曱氧基矽烷與四乙氧基石夕燒以4:1的 重量比混合，在200 rpm轉速下攪拌30分鐘，然後將i 2 克上述有機矽烷的混合物緩慢滴加到預先混合的氮氧化納 水溶液中’放置於2(TC的室溫中，200 rPm轉速下反應8小 時，之後在2(TC下陳化15小時；最後離心，用去離子水 反覆洗滌，冷凍乾燥，生成的顆粒平均粒徑為l 67“m， 粒徑主要分佈在1.5ym-2.0"m，收率為30%。 請參見第1圖，第1圖是實施例3所得到的具有粗糙 表面結構中空有機矽烷微球的掃描式電子顯微鏡照片。由 第1圖可看出所形成的有機矽烷微球具有粗糙表面結構， 且粒經大小相當的均勻，約在1.5微米左右。帛2圖是實 施例3的中空有機雜微球切片掃插式電子顯微鏡照片， 由第2圖可以看出所形㈣具有—表面結構有機石夕燒微 球是中空的。 請參見第3圖，第3圖是實施例3的中空有機石夕烧微 球的极徑分佈量測圖。由第3圖可以看出，實施例3的中 17 201226451 粒徑主要 空有機矽烷微球的主要微球粒徑大約為15//m 分佈在 1.3//m-1.7/zm。 請參見第4圖，帛4圖是實施例7的中空有機砂燒微 球穿透式電子顯微鏡照片。由第4圖可以看七，ώ香 韦，田貫施例 7所得的有機矽烷微球確實是中空的。所以，由第丨_ 第2圖和第4圖的電子顯微鏡照片可知，藉由本發明所揭 露的方法確實可以得到粒徑大小㈤的具有減表面結構 中空有機矽烷微球。 由上述實施例所得到的結果可知，藉由本發明所揭露 的方法不止可以得到粒徑大小均勻的具有粗録面結構中 空有機傾微球’更崎*反應條件⑽變來㈣所欲形 成中空有機矽烷微球的尺寸大小。 由別述可知，本發明是將有機矽烷單體或寡聚物，在 驗性條件下進行水解縮聚形成的聚合物，實施例2和實施 例8的比較可以看出，兩者的差異在於實施例2所使用鹼 性溶液為氨水溶液，而實施例8所使用的鹼性溶液為氳氧 化鉀溶液，因此，由實施例2和實施例8的比較結果可知， 採用氨水溶液作催化劑製備的中空有機矽烷顆粒粒徑小於 採用氫氡化鉀溶液。 頁施例3和實施例u的比較也顯示出採用弱鹼做為水 解催化劑所得到的中空有機矽烷顆粒粒徑較小。實施例3 所使用蛉性溶液為氨水溶液，而實施例11所使用的鹼性溶 201226451 液為氫氧化鈉溶液，因此，由實施例3和實施例u的比較 結果可知，採用氨水溶液作催化劑製備的中空有機魏顆 粒粒徑小於採用氳氧化鈉溶液。 反應溫度是影響中空有機矽烷微球粒徑大小的另一因 素。由實施例1和實施例1〇相較，兩個實施例中的差異在 於實施例丨的反應溫度為7(rc，而實施例1〇的反應溫度 則為20°C。實_ 1巾所得到財线機料顆粒平均粒 徑只有0.87微米而實施例10中所得到的中空有機矽烷顆 粒平均粒徑則為1.57微米，且兩者的粒徑分佈也分別為 0.7-1.2微米及1.2·1.8微来。據此，在較高的溫度下進行有 機石夕烧單體或寡聚物的水解聚合可以得到粒徑較小的中空 有機魏微球，反之，採用較低的水解聚合溫度則能得到 粒徑較大的中空有機矽烷微球。 即使在使用強驗催化的水解聚合反應，反應溫度亦對 反應有著相同的影響。實施例5和實施例6是採用相同的 起始物、相同的催化劑’兩者的差異在於實施例5的反應 溫度為2〇°C ’而實施例6的反應溫度為贼。由實驗結果 可以看出’實&例5所彳㈣的中空有機石找顆粒平均粒徑 為1.75微米’粒徑分佈為H2.3微米；實施例6所得到的 中空有機轉顆粒平均粒徑為U2微米，粒徑分佈為 ⑽微米。由實施例5和實施例6的比較結果可知，不 論使用強鹼或弱驗來進行中空有财院顆粒的合成，溫度 201226451 對反應的影響都是一 得到粒徑較小的中1㈣=是，採讀高的溫度可以 得到粒徑較大的中*古 微球’採用較低的溫度則能 較大的中空有機矽烷微球。 粒的^^用不同的起始物對所生成的中空有機石夕燒顆 粒的大小亦有影響。眚 同，唯有在起⑼ 實施例1〇的反應條件相 m 分贼用了甲基三甲祕我、乙稀 土 *石燒與四乙氧基石夕燒以41的比例混合。由實 施，3所㈣的中空有機魏顆粒平均粒徑為1 $微米， 粒控分佈為1.3·1.7微米；實施例1()所得到的中空有機石夕 貌顆粒平均粒役為157微米，粒徑分佈為HU微米。將 甲基一曱氧基;5續上的甲基換成乙稀基後可以得到粒經更 大的中空有機矽烷微球。 然而，當矽烷上的烷基有雜原子取代時，對於中空有 機石夕烧微球粒徑大小的影響方向又起了變彳卜實施例9中 將實施例3中起始物之一的甲基三甲氧基石夕貌上的甲基換 成氨丙基，其他的條件完全相同。由實施例3所得到的中 空有機矽烷顆粒平均粒徑為1.5微米，粒徑分佈為1 ^ 7 微米；實施例9所得到的中空有機魏顆粒平均粒徑僅有 為0.52微米，而粒徑分佈為〇25_12微米。因此，由實施 例3和實施Μ 9的t匕較結果可知’採用帶丙氨基的有機石夕 烷可以得到比帶甲基的有機矽烷粒徑更小的有機矽烷微 球。 20 201226451 實施例1-6,8-11都是利用攪拌的方式，將有機矽烷單 體或寡聚物置於鹼性條件下進行水解縮聚形成的聚合物， 以σ成中空有機石夕燒微球。而超音波振盪是一種用來取代 授拌來進行混合的方式，下述則是探討超音波振盪對此一 水解縮聚反應的影響。現將由實施例3、實施例7和實施 例11來做比較，實施例7和實施例11都是採用強鹼催化， 實施例3則是採用弱鹼催化，實施例3和實施例丨丨採用緩 ‘陵授拌（200 rpm轉速）的方式將有機矽烷的混合物分散到 驗性溶液中的方式，而實施例7則是改為採用超音波振盪 的方式將有機矽烷的混合物分散到鹼性溶液中。結果，由 實施例7所得到的中空有機矽烷微球的平均粒徑（0.87微 米）遠小於實施例11所得到的中空有機矽烷微球的平均粒 ( 1.67微米）’甚至小於以弱鹼進行水解催化聚合反應的 實施例3所得到的中空有機矽烷微球的平均粒徑（1.5微 米）。但是’實施例7所得到的中空有機矽烷微球的粒徑分 佈（〇.5-4.3微米）則較其他實施例中所得到的粒徑分佈來 知寬。因此’由實施例3和實施例11與實施例7的比較結 果可知’將有機石夕烧在驗性溶液中的分散方式也會影響所 得到的中空有機矽烷微球的粒徑大小及其粒徑分佈。 由以上的實施例所展現的結果可知，可以運用反應條 件的改變來控制所要得到的中空有機矽烷微球的粒徑尺 寸。例如’採用氨水溶液作催化劑可製備粒徑較小的中空 201226451 有機矽烷顆粒，採用氫氧化鈉溶液或氫氧化鉀溶液可以製 備粒徑較大的顆粒；採用較高的溫度可以得到粒徑較小的 中空有機矽烷微球，反之採用較低的溫度則能得到粒徑較 大的中空有機矽烷微球；採用帶乙烯基的有機矽烷得到的 中空有機魏微絲錄大，制帶聽基的有機魏得 到的微球粒徑較小；制超音波震盪的方式將有機我的 混合物分制祕溶液巾可以製備粒錄!、的中空有機石夕 烧顆粒’但切音波震齡散製備的齡純分佈較寬。 =在本技術領域具有通常知識者當可藉由本發明的揭 露’改變反應條件和起始物來製得所要求平均粒徑大 小及=佈的具有粗糖表面結構中空有機彻粒。 定本^ 財施方式揭露如上，㈣並非用以限 疋本發月，任何熟習此技藝 範圍内，當可作各種之更動ί纟不脫離本發明之精神和 圍舍視㈣^ 續，因此本發明之保護範 圍田視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 施方式得到的具有粗糙 式電子顯微鏡照片； 施方式的中空有機矽烷 施方式的中空有機矽烷 第1圖綠讀照本發明第三實 表面結構中空有機繼球的㈣ 第2圖綠示依照本發明第 微球切片掃描式電子顯微鏡^; 第3圖綠示依照本發明第三實 201226451 . 微球的粒徑分佈量測圖； . 第4圖繪示依照本發明第七實施方式的中空有機矽烷 微球穿透式電子顯微鏡照片； 【主要元件符號說明】 無 230.5 g of 25% gas water is dispersed into 1 gram of deionized water to form a uniform sentence, and the liquid liquid 'methyl trimethoxy decane and tetraethoxy decane are combined in a weight ratio of 4··1 at 200 rpm. After stirring for 30 minutes, a mixture of 1.2 g of the above organic decane was slowly added dropwise to the pre-mixed aqueous ammonia solution, and placed at room temperature of 20 ° C for 2 hours under the reaction of 200 rpm, followed by room temperature at room temperature. After 15 hours; finally centrifuged, and washed with deionized water, A freeze-dried, the average particle size of the particles is 1.5 // m, the particle size is mainly distributed in 1.3//m-1.7/zm, and the yield is 46%. . Example 4: 0.5 g of 25% aqueous ammonia was dispersed in 10 g of deionized water to form a homogeneous solution, dimethyldimethoxydecane, phenyltrimethoxydecane and tetraethoxy sulphur at a weight of 2:2:1. Than mixing 'at a speed of 200 rpm, throwing 3〇8 13 201226451 clocks, then slowly adding 0.78 grams of the above organic oxalate mixture to the premixed aqueous ammonia solution, and placing it at room temperature of 20 ° C, 200 The reaction was carried out at rpm for 2 hours, followed by 2 Torr. (: aging at room temperature for 15 hours; finally centrifugation, washing with deionized water, freeze-drying, the average particle size of the particles is 1.88μηι, the particle size is mainly distributed in l.6#m-2.2em, yield 40%. Example 5: Disperse 0.1 g of 40% aqueous sodium hydroxide solution into 1 gram of deionized water to form a homogeneous solution. Oxygen was mixed at a weight ratio of 2:2:1, stirred at 2 rpm for 30 minutes, and then 0.8 g of the above organic decane mixture was slowly added dropwise to the premixed aqueous sodium hydroxide solution, and placed in The reaction was carried out at room temperature of 20 ° C for 2 hours at 200 rpm, followed by aging at room temperature of 20 ° C for 15 hours; finally, centrifugation, washing with deionized water, lyophilization, and the average particle size of the resulting granules was 1.75 // m, the particle size is mainly distributed in 1.4 /z m-2.3# m, the yield is 51%. Example 6: 0.1 g of 40% aqueous sodium hydroxide solution is dispersed into 1 gram of deionized water to form a homogeneous solution, Methyl dimethyloxy (iv) and Ethyronyl trimethoxy zebra and tetraethoxy decane are 2:2:1 More than mixing, stirring at 201226451 for 30 minutes at 200 rpm, then slowly adding 0.8 g of the above organic decane mixture to the pre-mixed aqueous sodium hydroxide solution, and allowing to react at 200 ° C for 2 hours at 5 ° C. Then, it was aged at 50 ° C for 15 hours; finally, it was centrifuged, washed repeatedly with deionized water, and freeze-dried to obtain an average particle diameter of 1.22 " m, and the particle diameter was mainly distributed in a yield of 53%. Example 7: 0.1 g of a 40% aqueous potassium hydroxide solution was dispersed in 1 g of deionized water to form a homogeneous solution. The mercaptotrimethoxydecane and tetraethoxynonane were mixed in a weight ratio of 4:1 at 200 rpm. After stirring for 3 minutes, a mixture of 1.2 g of the above organic decane was slowly added dropwise to a pre-mixed aqueous potassium hydroxide solution, placed at room temperature of 2 Torr, and reacted in an ultrasonic oscillating reactor for 2 hours, after which It was aged at room temperature for 15 hours; finally centrifuged, washed repeatedly with deionized water, and freeze-dried to obtain an average particle size of 〇87 (4). The particle size was mainly distributed at 〇.5/zm_4.3/zm, and the yield was 23%. Example 8: 0.1 40% potassium hydroxide water is dispersed into 1G gram of deionized water. The phenyl trimethoxy Wei and tetraethoxy materials are combined at a ratio of 4:1 ' at 3 rpm for 3 GHz, then will be 】 6 The mixture of the escaping organic Wei and the smear of the first mixing of the squid 15 201226451 in an aqueous solution, placed in an ice water mixture, reacted at 200 rpm for § hours, then aged in a 〇 ° C ice water mixture 15 hours; finally centrifuged, washed repeatedly with deionized water, freeze-dried, the average particle size of the particles was 2 63 μηη, the particle size was mainly distributed in 2.2em-3.1vm, and the yield was 30%. Example 9: 0.01 g of 25% aqueous ammonia was dispersed in 1 g of deionized water to form a homogeneous solution, and aminopropyldiethoxydecane and tetraethoxydecane were mixed in a weight ratio of 3:1, and stirred at 200 rPm. 2 〇 minutes, then 12 g of the above mixture of organic decane was slowly added dropwise to the pre-mixed aqueous ammonia solution, placed at room temperature of 20 ° C, and reacted at 60 rpm for 2 hours, then at room temperature After 15 hours; finally centrifuged, washed repeatedly with deionized water, freeze-dried, the average particle size of the particles was 〇52/zm, and the particle size was mainly distributed at 0.25#m-1.2//m'. The yield was 23%. Example 10: 〇·〇1 g of 25% luJc was dispersed into 1 g of deionized water to form a homogenous solution, and vinyl triethoxy decane and tetraethoxy decane were mixed at a weight ratio of 4:1 at 200 rPm. Stir for 2 minutes, then slowly add 15 g of the above-mentioned organic Shi Xi Xuan mixture to the pre-mixed aqueous ammonia solution, and place it at 2 (TC at room temperature, 200 rpm for 8 hours, then at 2 (TC under TC for 5 hours; finally centrifuged 'repeated strips with deionized water, 201226451 freeze-dried, the average particle size of the particles is 1.57, the particle size is mainly distributed in 1.2"ιη-1.8μιη, yield 21%. Example 11: 0.1 g of 40% aqueous sodium hydroxide solution was dispersed into 10 g of deionized water to form a homogeneous solution, and decyltrimethoxy decane was mixed with tetraethoxy zephyr in a weight ratio of 4:1. After stirring at 200 rpm for 30 minutes, a mixture of i 2 g of the above organic decane was slowly added dropwise to the pre-mixed aqueous sodium nitrite solution and placed at 2 (TC at room temperature, reacted at 200 rPm for 8 hours, Then aged at 2 (TC for 15 hours; finally centrifuged, used The sub-water is repeatedly washed and freeze-dried to form an average particle size of 67 "m", and the particle size is mainly distributed at 1.5 ym - 2.0 " m, and the yield is 30%. See Fig. 1, Fig. 1 is an implementation A scanning electron micrograph of hollow organic decane microspheres having a rough surface structure obtained in Example 3. It can be seen from Fig. 1 that the formed organic decane microspheres have a rough surface structure, and the size of the particles is relatively uniform, about 1.5. The micrograph of the hollow organic microspheres of Example 3 is a scanning electron micrograph of the hollow organic microspheres of Example 3. It can be seen from Fig. 2 that the shape (4) has a surface structure. The organic stone sinter microspheres are hollow. 3, FIG. 3 is a measurement diagram of the polar diameter distribution of the hollow organic stone-fired microspheres of Example 3. As can be seen from FIG. 3, the medium-sized 17 201226451 particle diameter of the main empty organic decane microspheres of Example 3 The main microspheres have a particle size of about 15/m and are distributed at 1.3//m-1.7/zm. Please refer to Fig. 4, which is a transmission electron micrograph of the hollow organic sand-fired microsphere of Example 7. Figure 4 can be seen in the seven, Muxiang Wei, Tian Guan Example 7 obtained organic bismuth The alkane microspheres are indeed hollow. Therefore, it can be seen from the electron micrographs of the second and fourth figures that the hollow organic decane microparticles having a reduced surface structure can be obtained by the method disclosed in the present invention. From the results obtained in the above examples, it can be seen that the method disclosed in the present invention can obtain not only a hollow organic microsphere having a coarse-grained structure with a uniform particle size, but also a more realistic reaction condition (10). The size of the hollow organodecane microspheres. As will be understood from the above, the present invention is a polymer obtained by hydrolyzing polycondensation of an organodecane monomer or oligomer under an experimental condition, and the comparison between Example 2 and Example 8 can be It can be seen that the difference between the two is that the alkaline solution used in Example 2 is an aqueous ammonia solution, and the alkaline solution used in Example 8 is a potassium cerium oxide solution. Therefore, it is known from the comparison results of Example 2 and Example 8. The hollow organic decane particles prepared by using the aqueous ammonia solution as a catalyst have a smaller particle diameter than the potassium hydrogen hydride solution. A comparison of page 3 and Example u also shows that the hollow organodecane particles obtained by using a weak base as a hydrolysis catalyst have a small particle size. Example 3 The alkaline solution used was an aqueous ammonia solution, and the alkaline solution 201226451 used in Example 11 was a sodium hydroxide solution. Therefore, from the comparison results of Example 3 and Example u, it was found that an aqueous ammonia solution was used as a catalyst. The prepared hollow organic Wei particles have a particle size smaller than that of the sodium niobate solution. The reaction temperature is another factor that affects the particle size of the hollow organodecane microspheres. Comparing Example 1 with Example 1 ,, the difference between the two examples is that the reaction temperature of the Example 为 is 7 (rc, and the reaction temperature of Example 1 则 is 20 ° C. The average particle size of the pellets obtained was only 0.87 μm, and the average particle diameter of the hollow organodecane particles obtained in Example 10 was 1.57 μm, and the particle size distributions of the two were also 0.7-1.2 μm and 1.2·1.8, respectively. According to this, the hydrolyzed polymerization of the organic stone or the oligomer at a higher temperature can obtain hollow organic Wei microspheres having a smaller particle size, and conversely, the particles can be obtained by using a lower hydrolysis polymerization temperature. Hollow organodecane microspheres with larger diameters. Even with the use of strongly catalyzed hydrolysis polymerization, the reaction temperature has the same effect on the reaction. Example 5 and Example 6 use the same starting materials, the same catalyst' The difference between the two is that the reaction temperature of Example 5 is 2 〇 ° C ' and the reaction temperature of Example 6 is a thief. From the experimental results, it can be seen that the hollow organic stone of the 实 (4) The diameter is 1.75 micron' particle size The cloth was H2.3 μm; the hollow organic rotating particles obtained in Example 6 had an average particle diameter of U2 μm and a particle size distribution of (10) μm. It can be seen from the comparison results of Example 5 and Example 6 that no matter whether a strong base or a weak base is used. The test was carried out to carry out the synthesis of hollow granules. The effect of temperature 201226451 on the reaction was to obtain a medium particle size 1 (four) = yes, and a high temperature can be obtained to obtain a medium-sized microsphere with a larger particle size. At lower temperatures, larger hollow organic decane microspheres can be used. The different starting materials of the granules also have an effect on the size of the hollow organic granules produced by the granules. The same, only at the beginning (9) The reaction conditions of Example 1 m m 用 用 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基The particle size distribution is 1.3 1.7 μm, and the hollow organic stone granule particles obtained in Example 1 () have an average granulation of 157 μm and a particle size distribution of HU μm. 5 After the continuous methyl group is changed to the ethylene group, the larger diameter of the granule can be obtained. Methane microspheres. However, when the alkyl group on the decane is substituted with a hetero atom, the direction of influence on the particle size of the hollow organic stone microspheres is changed. The starting point in Example 3 will be the same in Example 9. The methyl group on one of the methyltrimethoxylates was changed to the aminopropyl group, and the other conditions were completely the same. The hollow organic decane particles obtained in Example 3 had an average particle diameter of 1.5 μm and a particle size distribution of 1 ^ 7 micrometers; the hollow organic Wei particles obtained in Example 9 have an average particle diameter of only 0.52 μm and a particle size distribution of 〇25_12 μm. Therefore, the results of Example 3 and Example 匕 9 are better than the results. The organic fluorene having a propylamino group can give an organic decane microsphere having a smaller particle diameter than the organic decane having a methyl group. 20 201226451 Examples 1-6, 8-11 are all formed by a method in which an organodecane monomer or an oligomer is subjected to hydrolysis and polycondensation under alkaline conditions by means of stirring, and σ is formed into a hollow organic stone sinter microsphere. . Ultrasonic oscillation is a method used to replace mixing, and the following is to investigate the effect of ultrasonic oscillation on this hydrolysis polycondensation reaction. Comparison will now be made between Example 3, Example 7 and Example 11, both Example 7 and Example 11 are catalyzed by a strong base, and Example 3 is catalyzed by a weak base, and Example 3 and Example are employed. The mixture of organic decane was dispersed into the test solution by means of slow mixing (200 rpm), while in Example 7, the mixture of organic decane was dispersed into an alkaline solution by ultrasonic vibration. in. As a result, the average particle diameter (0.87 μm) of the hollow organodecane microspheres obtained in Example 7 was much smaller than the average particle size (1.67 μm) of the hollow organodecane microspheres obtained in Example 11 even smaller than that of the weak base. The average particle diameter (1.5 μm) of the hollow organodecane microspheres obtained in Example 3 of the catalytic polymerization reaction. However, the particle size distribution (〇. 5-4.3 μm) of the hollow organodecane microspheres obtained in Example 7 was wider than that obtained in the other examples. Therefore, 'the results of the comparison between Example 3 and Example 11 and Example 7 show that the dispersion of the organic stone in the test solution also affects the particle size of the obtained hollow organic decane microspheres and the particles thereof. Path distribution. From the results exhibited by the above examples, it is understood that the change in the reaction conditions can be used to control the particle size of the hollow organodecane microspheres to be obtained. For example, 'Ultraaqueous ammonia solution can be used as a catalyst to prepare hollow 201226451 organic decane particles with small particle size. Particles with larger particle size can be prepared by using sodium hydroxide solution or potassium hydroxide solution; smaller particle size can be obtained by using higher temperature. The hollow organic decane microspheres, on the contrary, the hollow organic decane microspheres with larger particle size can be obtained at a lower temperature; the hollow organic Wei microwires obtained by using the organic decane with vinyl are recorded, and the organic Wei with the listening group is obtained. The microspheres have a small particle size; the method of making ultrasonic waves oscillates the organic mixture of my mixture into a secret solution towel to prepare the granules of the hollow organic stone granules, but the pure distribution of the cut-off wave width. = Those skilled in the art will be able to obtain the desired average particle size and size of the hollow organic granules having a coarse sugar surface structure by varying the reaction conditions and starting materials by the disclosure of the present invention. The method of financial disclosure is as disclosed above. (4) It is not intended to limit the present month. Anyone who is familiar with the skill of the art can make various changes without departing from the spirit and scope of the present invention. The scope of protection is defined by the scope of the patent application attached to the field. [Simplified description of the drawing] A rough electron micrograph obtained by the method; a hollow organic decane of a hollow organic decane application method of the present invention. Fig. 1 Green reading of the third solid surface structure of the hollow organic organic ball of the present invention (4) Figure 4 shows a microsphere slice scanning electron microscope according to the present invention; Fig. 3 shows a particle size distribution measurement chart of the microsphere according to the third embodiment 201226451 of the present invention; Transmissive electron micrograph of hollow organic decane microspheres of the embodiment; [Explanation of main component symbols] No 23