I296265 * % 九、發明說明： 發明所屬之技術領域 本發明係關於一種氫氧化鋁晶粒的製備方法。 先前技術 隨著歐盟對電子電器耗材用品之無4化進行立法，相 關法規在2004年開始生效。世界各國，尤其8〇1^¥與 • 公司亦相繼頒布高難燃、低煙霧與無害化的新難燃標準， 因此含函難燃劑已漸漸被禁用，而無機無由難燃劑則趨重 要。無機無齒難燃劑中以氫氧化鋁為最大宗。 2000年北京化工大學陳建峰等人發表以超重力法製備 氫氧化紹微粉（CN1258639A)，製程包括碳分分解與水熱處 理二部分。經過水熱處理後，粒徑可以控制在丨〜5打瓜，長 仏比為5〜1 0 〇的針狀結晶。 卜北京化工大學陳建峰等人於2002年發表超細改性氫 • 氧化銘及其製備方法（彻02094715)，是以飽和銘酸納水溶 液為原料，在超重力反應器中通人c〇2進行批式化學反應 先製備奈米氫氧化鋁粉體，再以草酸或草酸鹽進行改性反 應，所獲得的改性氫氧化紹超細粉體，其熱分解溫度由原 來未改性氫氧化鋁的熱分解溫度在23〇〜235<t範圍上升至 3 00 C附近，於是大大改善了氫氧化鋁作為無機無鹵 難燃劑的應用潛力。 前述北京化工大學陳建峰等人所使用的超重力反應器 (旋轉填充床）於操作時會出現：⑴質傳效率不均勻，愈靠 1296265 旋轉床外部效率愈差；（2)由於持續進行旋轉的離心力作 用，容易產生填充料外圍密度高於内層的情況；（3)旋轉填 充床構造複雜，容易失去動態平衡，造成常須停車維修。 本案申請人於台灣新型專利205722 (中國大陸新型專利 598954)揭示一種新型超重力反應器，其可改善前述超重力 反應器（旋轉填充床）的缺點，其中的實施例三中並測試評 估此新型超重力反應器用於製備氫氧化鋁晶粒的可行性， φ 但仍未能掌握製備不同晶型的奈米氫氧化鋁晶粒的技術。 發明内容 本發明的一主要目的在提出一種連續製備不同晶型的 氮氧化銘晶粒的方法。 本發明的另一目的在提出一種可使用同一生產線連續 製備不同晶型的氫氧化銘晶粒的方法。’ 本發明揭示一種可控制氫氧化鋁晶粒的晶型的製備方 Φ 法，包括將鋁酸鈉（NaA1〇2)和硫酸鋁（Ai2(s〇4)3)水溶液同時 注入一超重力場反應器進行液相化學反應，收集所獲得的 反應產物漿體，調整該漿體的pH值及溫度，使得該漿體中 的氫氧化鋁晶粒具有一想要的晶型，例如三水鋁石 (bayerite)、boemite 或 pseudoboemite 晶型。 本發明也包括使用本發明的具有一想要的晶型的氫氧 化鋁晶粒來製備改性氫氧化鋁晶粒的方法。 實施方式 6 1296265 於本發明的一較佳具體實施例中本案申請人揭示於台 灣新型專利205722 (中國大陸新型專利598954)的新型超口 力反應盗被使用，該專利的内容以參考方式被併入本 案該新型冑重力反應器的一較佳具體實施例被示於圖1 及2 ’其中圖2為僅顯示圖！中的反應器的部份元件的上 視圖。該新型超重力反應器包含：—密閉的反應艙ι〇、兩 液體進料管卜-位於該反應搶1"卜周壁上氣體入口 3、 • 八個多孔性旋轉葉片20、轉盤30、旋轉軸6、一位於該反 應艙10外周壁且近其底部的反應產物出口 7、及一氣體 出管8。 1 ^該多孔性旋轉葉片20包含一長方形外框4及一支撐於 该外框的60-80網目的不鏽鋼網5所組成，其中該外框4 係垂直的固定於該轉Μ 3〇的上表面上。冑八個旋轉葉片 2〇相對於該旋轉軸6的軸心係徑向、呈等角度間隔開的被 固定於該轉盤30的上表面上。於本發明的另—較佳具體實 ,&例中It夕孔性旋轉葉片包含固定於該轉盤的上表面的 兩垂直柱及套於該兩垂直柱的一不鏽鋼網的環帶。 忒轉盤30通過固定於其下表面的旋轉軸6而為一外界 馬達（未示於圖中）所驅動旋轉，於是該八個多孔性旋轉葉 片20跟著繞該旋轉軸6的軸心高速旋轉。 該兩液體進料管！的每一根包含一伸出於該反應驗ι〇 的一進料端部份la及為該八個旋轉葉片2〇所包圍的穿孔 部ib。该穿孔部lb沿該軸心方向被設有面向該旋轉葉片 2〇的複數個穿孔2;且該穿孔部lb的底端係被封閉。 1296265 該氣體排出管8係連接於該反應艙10並與該軸心呈一 直線。該氣體排出管8包圍該兩進料管〗的進料端部份“， 於是形成一用於排出該反應艙3〇内的氣體的環形通道。 進行氣液接觸時，液體由該液體進料管1的進料端部 伤la的上方入口進入該反應臉10,經過該等穿孔2喷入包 括該夕孔性旋轉葉片2〇的反應區域，於此處液體為該多孔 性疑轉葉片20所拍擊、分割為微液滴並與由該氣體入口 3 φ /主入的反應氣體接觸、反應。反應完畢後的產物由該反應 產物出口 7流出，氣體則由該氣體排出管8排出。 進行液液接觸時，該氣體入口 3被封住，兩不同液體 分別由該兩液體進料管丨被導入該反應艙丨〇，分別通過該 等穿孔2喷入包括該多孔性旋轉葉片2〇的反應區域，於此 處液體為該多孔性旋轉葉片20所拍擊、分割為微液滴，並 互相接觸、反應。反應完畢後的產物由該反應產物出口 7 流出。若同時有氣體產生，則由該氣體排出管8排出，若 • 無，則封住該氣體排出管8。 一依本發明内容來製備改性氫氧化鋁晶粒的方法將配 合圖3所示的流程方塊圖說明如下。 將銘酸鈉（NaA102)水溶液由儲槽41和硫酸銘 (Ah(S〇4)3)水溶液由儲槽42同時注入前述超重力場反應器 100進行液相化學反應。由該超重力場反應器丨00流出的 反應產物漿體被收集於一接收槽5 0，藉由設置於該接收槽 50的pH值控制單元5 1及溫度控制單元52調整該漿體的 pH值及溫度，使得該漿體中的氫氧化鋁晶粒具有一想要的 1296265 晶型。該pH值控制栗； 1及溫度控制單元5 2可使用化工 業界所習用者。一播挺突一 見评裔（未示於圖中）亦被設置於該接收 槽内以均勻此合該接收槽5〇内的聚體。該接收槽Μ 内的漿體接著被送至-過壚清洗單元61進行漿體的過濾、 及/月 '先戶斤獲知的氫氧化在呂晶粒被送至一改性反應器Ν 内於其中與來自一儲槽43的二元酸進行反應。所獲得反 應產物裝體接著被送至一過據清洗單元62進行漿體的過I296265 * % Nine, the invention belongs to the technical field of the invention. The present invention relates to a method for preparing aluminum hydroxide crystal grains. Prior Art With the EU's legislation on the lack of electronic and electrical consumable supplies, the relevant regulations came into effect in 2004. Countries around the world, especially the company, have also issued new flame retardant standards for high flame retardance, low smoke and harmlessness. Therefore, the letter-containing flame retardant has been gradually banned, while the inorganic flame retardant has become more and more important. Among the inorganic toothless flame retardants, aluminum hydroxide is the largest. In 2000, Chen Jianfeng and others from Beijing University of Chemical Technology published a super-gravity method to prepare sodium hydroxide (CN1258639A). The process includes carbon decomposition and hydrothermal treatment. After hydrothermal treatment, the particle size can be controlled in 丨~5 dozen melons, and the long 仏 ratio is 5~10 〇 acicular crystals. In 2002, Chen Jianfeng and others from Beijing University of Chemical Technology published the ultra-fine modified hydrogen • oxidation and its preparation method (Chen 02097715), which was made from saturated aqueous solution of sodium sulphate and passed through a c-reactor in a supergravity reactor. The batch chemical reaction first prepares the nanometer aluminum hydroxide powder, and then the modification reaction is carried out with oxalic acid or oxalate, and the obtained superfine powder of the modified hydrogen peroxide has a thermal decomposition temperature of the original unmodified hydrogen peroxide. The thermal decomposition temperature of aluminum rises from 23 〇 to 235 lt to the vicinity of 300 ° C, thus greatly improving the application potential of aluminum hydroxide as an inorganic halogen-free flame retardant. The above-mentioned supergravity reactor (rotary packed bed) used by Chen Jianfeng et al. of Beijing University of Chemical Technology and others will appear during operation: (1) the mass transfer efficiency is not uniform, and the efficiency is worse under the rotating bed of 1296265; (2) due to continuous rotation The centrifugal force is easy to produce the case where the peripheral density of the filler is higher than that of the inner layer; (3) The structure of the rotating packed bed is complicated, and it is easy to lose the dynamic balance, resulting in frequent parking maintenance. The applicant of the present invention discloses a new type of supergravity reactor which can improve the shortcomings of the aforementioned supergravity reactor (rotary packed bed), and the new type of patent 205, 722 (Chinese mainland patent 598954), which is tested and evaluated in the third embodiment. The feasibility of a supergravity reactor for the preparation of aluminum hydroxide grains, φ but still fails to master the technique of preparing nanocrystalline aluminum hydroxide grains of different crystal forms. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a method for continuously preparing nitrogen oxide crystal grains of different crystal forms. Another object of the present invention is to provide a method for continuously preparing hydroxide crystal grains of different crystal forms using the same production line. The invention discloses a preparation method for controlling the crystal form of aluminum hydroxide crystal grains, which comprises simultaneously injecting an aqueous solution of sodium aluminate (NaA1〇2) and aluminum sulfate (Ai2(s〇4)3) into a supergravity field. The reactor performs a liquid phase chemical reaction, collects the obtained reaction product slurry, adjusts the pH and temperature of the slurry, so that the aluminum hydroxide crystal grains in the slurry have a desired crystal form, such as aluminum trihydrate. Bayerite, boemite or pseudoboemite crystal form. The invention also includes a method of preparing modified aluminum hydroxide grains using the aluminum hydroxide grains of the present invention having a desired crystalline form. Embodiment 6 1296265 In a preferred embodiment of the present invention, the applicant of the present invention discloses a novel super-power reaction pirate used in Taiwan's new patent 205722 (Chinese mainland new patent 598954), the content of which is referred to by reference. A preferred embodiment of the novel helium gravity reactor of the present invention is shown in Figures 1 and 2' wherein Figure 2 is a view only! A top view of some of the components of the reactor. The novel supergravity reactor comprises: a closed reaction chamber ι, two liquid feed tubes - a gas inlet 3 on the wall of the reaction, and eight porous rotating blades 20, a turntable 30, a rotating shaft 6. A reaction product outlet 7 located at the outer peripheral wall of the reaction chamber 10 near the bottom thereof and a gas outlet pipe 8. 1 ^ The porous rotating blade 20 comprises a rectangular outer frame 4 and a stainless steel mesh 5 of 60-80 mesh supported by the outer frame, wherein the outer frame 4 is vertically fixed to the switch 3〇 On the surface. The eight rotary blades 2 are fixed to the upper surface of the turntable 30 in a radial direction at equal angular intervals with respect to the axis of the rotary shaft 6. In another embodiment of the present invention, the Italic Rotary Blade includes two vertical columns fixed to the upper surface of the turntable and an annular band of a stainless steel mesh sleeved over the two vertical columns. The turntable 30 is driven to rotate by an external motor (not shown) by a rotary shaft 6 fixed to its lower surface, so that the eight porous rotary vanes 20 are rotated at a high speed around the axis of the rotary shaft 6. The two liquid feed tubes! Each of the roots includes a feed end portion 1a extending from the reaction chamber and a perforated portion ib surrounded by the eight rotary vanes 2''. The perforated portion lb is provided with a plurality of perforations 2 facing the rotating blade 2 in the axial direction; and the bottom end of the perforated portion 1b is closed. 1296265 The gas discharge pipe 8 is connected to the reaction chamber 10 and is in line with the axis. The gas discharge pipe 8 surrounds the feed end portion of the two feed pipes, thereby forming an annular passage for discharging the gas in the reaction chamber 3. When the gas-liquid contact is made, the liquid is fed from the liquid. The upper inlet of the feed end of the tube 1 enters the reaction face 10, through which the reaction zone including the illuminating rotor blade 2〇 is sprayed, where the liquid is the porous suspect blade 20 The slap is divided into micro droplets and brought into contact with the reaction gas which is introduced by the gas inlet 3 φ / main. The product after completion of the reaction flows out from the outlet 7 of the reaction product, and the gas is discharged from the gas discharge pipe 8. When the liquid-liquid contact is made, the gas inlet 3 is sealed, and two different liquids are respectively introduced into the reaction chamber by the two liquid feed tubes, and the porous rotating blades are sprayed through the perforations 2, respectively. a reaction zone where the liquid is slapped by the porous rotating blade 20, divided into micro-droplets, and brought into contact with each other and reacted. The product after completion of the reaction flows out from the outlet of the reaction product 7. If gas is generated at the same time, The gas The outlet pipe 8 is discharged, and if not, the gas discharge pipe 8 is sealed. A method for preparing modified aluminum hydroxide crystal grains according to the present invention will be described below in conjunction with the flow block diagram shown in Fig. 3. The sodium (NaA102) aqueous solution is simultaneously injected into the above-mentioned supergravity field reactor 100 from the storage tank 42 by a storage tank 41 and an aqueous solution of sulphuric acid (Ah(S〇4)3) for liquid phase chemical reaction. From the supergravity field reactor 丨00 The effluent reaction product slurry is collected in a receiving tank 50, and the pH value and temperature of the slurry are adjusted by the pH control unit 51 and the temperature control unit 52 disposed in the receiving tank 50, so that the slurry is in the slurry. The aluminum hydroxide crystallites have a desired crystal form of 1296265. The pH controls the pump; 1 and the temperature control unit 52 can be used by the chemical industry. A broadcast is very popular (not shown) It is also disposed in the receiving groove to evenly integrate the polymer in the receiving groove 5. The slurry in the receiving groove is then sent to the over-cleaning unit 61 for slurry filtration, and / month The oxidized water obtained by the first household is sent to a modified reactor in the granules. From two yuan an acid storage tank 43 is reacted. The reaction product is then sent to a packaging body according to the cleaning unit 62 through the slurry obtained through
濾、及清洗，於是獲得改性氫氧化紹晶粒。 於本發明的較佳具體實施例中，該銘酸鈉和硫酸銘水 溶液濃度約在0.1〜1Ν之間，在該超重力場反應器1〇〇内 的反應溫度約在30〜80。(：之間，及超重力場之G值約在9〇 〜200之間。當該接收槽5〇内的反應產物漿體的值被 控制在9〜11之間及溫度被控制在3〇〜8〇它之間會得到三 水鋁石（bayerite)晶型，當pH值被控制在6〜9之間溫度被 控制在30〜80°C之間會得到pseudo-boehmite晶型。如果 當pH值被控制在7〜9之間且溫度被控制在8〇〜i5(rc之 間則會得到boehmite晶型。該反應產物漿體内的粉體的粒 徑大小（particle size)在0.2〜1 μπι之間，及氫氧化鋁晶粒 大小（grain size)在40〜80 nm之間。其化學反應為： 6NaAl〇2+Al2(S〇4)3 + 12H20 8Al(〇H)3 + 3Na2S〇4 獲得之反應產物漿體經過滤清洗去除雜質後在反應器 70内在水中以有機二元酸或其二元酸酐或這兩者之衍生物 9 ⑧ 1296265 對氫氧化鋁晶粒進行官能化改性反應。有機二元酸或其二 凡酸軒或這兩者之衍生物的羧酸官能基對氫氧化鋁晶粒之 莫耳比為0·1〜2，兩者在水中之總濃度為2〜40重量％， 吕能化改性反應溫度為100〜300°c之間，反應時間約0.5〜 5小時之間。 適用於本發明之有機二元酸可為脂肪族或芳香族的飽 和鍵碳鏈或不飽和鍵碳鏈。飽和鍵碳鏈有機二元酸，例如 以HO〇C(CH2)nCO〇H表示者其碳鏈碳數n值為〇〜4。不飽 和鍵碳鏈有機二元酸，例如以（h〇〇c(ch=ch)(ch^c〇〇h) 表不者其碳鏈碳數η值為0〜2。以上碳鏈上可進一步含_〇H 吕月b基。該有機二元酸的酸酐，或這兩者之衍生物亦可用 於本發明，它們的典型例子如草酸、丙二酸、順丁烯二酸、 順丁烯二酐、反丁烯二酸、蘋果酸、琥珀酸、酒石酸、戊 一酸、己二酸、檸檬酸、間苯二甲酸、鄰苯二甲酸、鄰苯 二甲酸酐、對苯二甲酸。 經羧酸官能化改性後之氫氧化鋁晶粒，其熱分解起始 失重溫度與激烈失重溫度都有明顯的上升。若是三水鋁石 (bayerite)晶型會由原來未官能化氫氧化鋁的熱分解起始失 重溫度120〜235°C上升至270〜300°C。 本明可藉由下列實施例被進一步瞭解，其等僅作為 說明之用，而非用於限制本發明範圍。 以下實施例所使用的本發明的超重力場反應器，具有 6〇〜80網目的金屬網葉6片，葉片徑向的長度為，軸 向高度為2 cm;而反應器的内、外徑分別為2cm與4cm， 1296265 軸向高度為2 cm。 實施例一、數種不同晶型的氫氧化鋁晶粒的製備 0.25N鋁酸鈉水溶液，其pH值>n，溫度70°C，流量 約0 · 8升/分叙’與〇 ·25N硫酸铭水溶液，其pH值呈酸性， 溫度5 0 C ’被導入超重力場反應器之進料喷口，反應器轉 速為 1 800 rpm。 i)製備 pseudo_boehmite 氫氧化鋁·· 調整硫酸銘水溶液流量（流量約〇 · 6升分鐘），使接收槽 50内的漿體的pH維持在6.5及溫度維持在7(TC。過濾由 接收槽5 0流出的漿體及水洗所得到氫氧化銘粉體瀘餅。以 X射線繞線（XRD)分析粉末，由圖4的XRD光譜看出其信 號波峰成錯齒狀I波’因此是不定形的pSeud〇_]3〇ehmite晶 型，其晶粒大小經推算約3 5〜45 nm。由電子顯微鏡觀測 該氫氧化鋁粉體，如圖5所示其出為30〜60 nm球型顆粒。 此pseudo-boehmite晶型氫氧化鋁粉體進一步以熱重分析 儀（TGA)進行分析，其結果被示於圖6。從圖6可看出，此 pseudo_boehmite氫氧化鋁粉體5在30〜90°C其熱失重為 1 〇重里A ’隨者溫度升南失重漸漸增加，約在6 0 0 °C附近， 其熱失重達32重量❶/〇。 H)製備boehmite晶型氫氧化銘：Filtration, and cleaning, thus obtaining modified hydrogenated grains. In a preferred embodiment of the invention, the concentration of the sodium sulphate and the aqueous solution of sulphuric acid is between about 0.1 and about 1 Torr, and the reaction temperature in the enthalpy of the supergravity field reactor is about 30 to 80. (Between, and the G value of the supergravity field is between about 9 〇 and 200. When the value of the reaction product slurry in the receiving tank 5 被 is controlled between 9 and 11, and the temperature is controlled at 3 〇 ~8〇 It will get the bayerite crystal form. When the pH is controlled between 6~9 and the temperature is controlled between 30~80°C, the pseudo-boehmite crystal form will be obtained. The pH value is controlled between 7 and 9 and the temperature is controlled between 8 〇 and i5 (the rib between the rc yields the boehmite crystal form. The particle size of the powder in the reaction product slurry is 0.2~ Between 1 μm, and the grain size of aluminum hydroxide is between 40 and 80 nm. The chemical reaction is: 6NaAl〇2+Al2(S〇4)3 + 12H20 8Al(〇H)3 + 3Na2S The reaction product slurry obtained in 〇4 is subjected to filtration cleaning to remove impurities, and then functionalized in the reactor 70 by using an organic dibasic acid or a dibasic anhydride thereof or a derivative of the two 9 8 1296265 in water. Sexual reaction. The molar ratio of the carboxylic acid functional group to the aluminum hydroxide crystal grain of the organic dibasic acid or its dibasic acid or a derivative thereof is from 0.1 to 2, both of which are The total concentration in the range is 2 to 40% by weight, the modification reaction temperature is between 100 and 300 ° C, and the reaction time is between about 0.5 and 5 hours. The organic dibasic acid suitable for use in the present invention may be aliphatic. Or an aromatic saturated bond carbon chain or an unsaturated bond carbon chain. A saturated bond carbon chain organic dibasic acid, for example, represented by HO〇C(CH2)nCO〇H, has a carbon chain carbon number n value of 〇~4. A saturated bond carbon chain organic dibasic acid, for example, wherein (h〇〇c(ch=ch)(ch^c〇〇h) has a carbon chain carbon number η of 0 to 2. The above carbon chain can be further An acid anhydride of the organic dibasic acid, or a derivative of the two, may also be used in the present invention, and typical examples thereof are oxalic acid, malonic acid, maleic acid, and maleic acid. Di-anhydride, fumaric acid, malic acid, succinic acid, tartaric acid, valeric acid, adipic acid, citric acid, isophthalic acid, phthalic acid, phthalic anhydride, terephthalic acid. The carboxylic acid functionalized modified aluminum hydroxide crystallites have a significant increase in the thermal decomposition initial weight loss temperature and the intense weight loss temperature. If it is a bayerite crystal form The thermal decomposition initial weight loss temperature of the unfunctionalized aluminum hydroxide is raised from 120 to 235 ° C to 270 to 300 ° C. The present invention can be further understood by the following examples, which are for illustrative purposes only, rather than To limit the scope of the invention. The supergravity field reactor of the present invention used in the following examples has 6 metal mesh leaves of 6 〇 80 mesh, the radial length of the blade is 2 cm in axial direction; The inner and outer diameters of the device are 2cm and 4cm respectively, and the 1296265 axial height is 2 cm. Example 1. Preparation of aluminum hydroxide crystal grains of different crystal forms 0.25N sodium aluminate aqueous solution, pH value > n, temperature 70 ° C, flow rate of about 0 · 8 liters / quotient ' and 〇 · 25N The aqueous solution of sulphuric acid was acidic, and the temperature of 50 C was introduced into the feed nozzle of the supergravity field reactor at a reactor speed of 1 800 rpm. i) Preparation of pseudo_boehmite Aluminium hydroxide · Adjusting the flow rate of the aqueous solution of sulfuric acid (flow rate about 6 liters per minute), maintaining the pH of the slurry in the receiving tank 50 at 6.5 and maintaining the temperature at 7 (TC. Filtering by the receiving tank 5 The slurry which was discharged from 0 and the water was washed to obtain a powder of oxyhydroxide powder. The powder was analyzed by X-ray diffraction (XRD), and the X-ray spectrum of Fig. 4 showed that the signal peak became an erroneous I-wave 'is therefore amorphous. The crystal form of pSeud〇_]3〇ehmite, whose grain size is estimated to be about 3 5 to 45 nm. The aluminum hydroxide powder is observed by an electron microscope, and as shown in Fig. 5, it is a spherical particle of 30 to 60 nm. The pseudo-boehmite crystalline aluminum hydroxide powder was further analyzed by a thermogravimetric analyzer (TGA), and the results are shown in Fig. 6. As can be seen from Fig. 6, the pseudo_boehmite aluminum hydroxide powder 5 was at 30~ At 90 °C, its thermal weight loss is 1 〇 里 里 A ' 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,
製備程序同上述i)，只是接收槽5〇内的漿體的溫度被 維持在1 60°C，pH為9。產物以水洗與過濾得到氫氧化鋁 粉體濾餅。以X射線繞線（XRD)分析粉末，由圖7的XRD 11 1296265 光禮看出其為boehmite晶型，其晶粒大小經推算約35〜45 nm 〇 u0製備三水鋁石（bayerite)晶型氫氧化鋁： 製備程序同上述i)，只是調整硫酸鋁水溶液流量（流量 約〇·4升/分鐘），及使接收槽5〇内的漿體的pH維持在9。 以動態雷射光散射法（DLS)測粒徑儀測量所獲得的氫氧化 紹粉體的粒徑（particle size)，得到D50約209 nm。再由其 φ XRD圖譜（圖8)得知其為三水鋁石晶型，此三水鋁石晶型氫 氧化銘晶粒大小（grain size)經推算約35〜45 nm。此三水銘 石晶型氫氧化鋁粉體進一步以熱重分析儀（TGA)進行分 析，其結果被示於圖9。從圖9可看出在a段$ 〇〜2 5 0 °C其 熱失重為ίο重量％，其激烈失重溫度約在25〇r附近開始 至300°C附近（B段>，其熱失重達30重量0/〇。 實施例二：對實施例一（iii)的三水鋁石晶型氫氧化鋁以草酸 • 進行官能基改性 在反應器70，100 g之實施例一（Hi)的三水鋁石晶型氫 氧化鋁粉體濾餅加入90 g草酸與600 g水、充分混合，於 150〜160°C進行羧酸官能基改性反應，反應時間i小時。將 所獲得的產物過滤水洗後’以TGA進行分析，結果如圖1〇 所示，在80〜240°C(A段）其熱失重為！重量％，激烈失重 溫度約在370°C附近開始，至430°C附近（B段）其熱失重達 45重篁％，咼於500 C以後其熱失重趨緩。改性後粉體樣 品以XRD儀器分析，如圖丨丨的XRI)光譜所示在〇值為 12 1296265 4·727、6·512和3.733A有繞射峰，其2Θ角分別為18·758、 13·588與23·817 ’而在2Θ角分別為13.588與23.817的繞 射峰強度分別為2Θ角1 8.758的32.98%和29.96% 。 只^例三··對實施例一（Ui)的三水鋁石晶型氫氧化鋁以草酸 進行官能基改性 除了二水鋁石晶型氳氧化鋁粉體被減量為5 0 g外，其 • 餘實驗條件同實施例二。所獲得的粉體樣品的TGA分析結 。果被示於圖12,其中在8〇〜27(rc(A段）其熱失重為i重量 %，激烈失重溫度約在385t：附近開始，至45(rc附近其熱 失重達50重量％(B段），高於50〇°c以後其熱失重達趨緩。 改丨生後粉體樣品以XRD儀器分析，如圖13的XRD光譜所 不’在D值為6.526、4.739和4.3 04A有繞射峰，其2Θ角 分別為13.558、18.709與20.619,而在2Θ角分別為13·558 與20·619的繞射峰強度分別為20角7〇9的3〇·94%和 ® 6’6〇% 。以紅外線（IR)儀器分別測量三水銘石晶型氫氧化 紹粉體與羧酸官能基改性後產物樣品，結果如圖14。從 1 4 i ° 甲可知在1300 cm·1附近有C-0化學鍵，在17〇〇 cnT1 附近有C = 0化學鍵，在2800〜3600 cm·1附近有〇_h化學 鍵’故草酸的羧酸官能基與三水鋁石晶型氫氧化鋁之間有 化學鍵結。 實施例四：對實施例一（iii)的三水鋁石晶型氫氧化鋁以己二 酸進行官能基改性The preparation procedure was the same as i) above, except that the temperature of the slurry in the receiving tank 5 was maintained at 1 60 ° C and the pH was 9. The product was washed with water and filtered to give an aluminum hydroxide powder cake. The powder was analyzed by X-ray winding (XRD). It was found to be boehmite crystal form by XRD 11 1296265 of Fig. 7, and its grain size was estimated to be about 35~45 nm 〇u0 to prepare bayerite crystal. Aluminium hydroxide: The preparation procedure is the same as i) above except that the flow rate of the aqueous solution of aluminum sulfate is adjusted (flow rate is about 4 liters/min), and the pH of the slurry in the receiving tank 5 is maintained at 9. The particle size of the obtained oxidized powder was measured by a dynamic laser light scattering (DLS) particle size measuring instrument to obtain a D50 of about 209 nm. It is also known by its φ XRD pattern (Fig. 8) as a gibbsite crystal form. The crystal size of the gibbsite crystal form is estimated to be about 35 to 45 nm. This Sanshui stone-type aluminum hydroxide powder was further analyzed by a thermogravimetric analyzer (TGA), and the results are shown in Fig. 9. It can be seen from Fig. 9 that the thermal weight loss is ίο wt% in the a segment $ 〇~2 5 0 °C, and the intense weight loss temperature starts around 25 〇r to around 300 ° C (B segment >, its thermal weight loss) Up to 30 wt%/〇. Example 2: Example 1 (Hi) of the gibbsite crystal form aluminum hydroxide of Example 1 (iii) modified with oxalic acid in a reactor 70, 100 g The gibbsite crystal form aluminum hydroxide powder filter cake is added with 90 g of oxalic acid and 600 g of water, and thoroughly mixed, and the carboxylic acid functional group modification reaction is carried out at 150 to 160 ° C for a reaction time of 1 hour. The product was filtered and washed with water. The results were analyzed by TGA. The results are shown in Fig. 1A. At 80~240 °C (stage A), the thermal weight loss is !% by weight, and the intense weight loss temperature starts around 370 °C to 430 °. Near C (B), its thermal weight loss reached 45% 咼%, and its thermal weight loss slowed down after 500 C. The modified powder sample was analyzed by XRD instrument, as shown by the XRI spectrum of Figure 〇. There are diffraction peaks for 12 1296265 4·727, 6·512 and 3.733A, and their 2 Θ angles are 18·758, 13·588 and 23·817 ', respectively, and around the 2 corners are 13.588 and 23.817. The peak intensity is 32.98% and 29.96% of 2 Θ1 8.758, respectively. Only Example 3··The functional modification of gibbsite crystal form aluminum hydroxide of Example 1 (Ui) with oxalic acid except that the gibbsite crystal form 氲 alumina powder was reduced to 50 g, The remaining experimental conditions are the same as in the second embodiment. TGA analysis of the obtained powder samples. The results are shown in Fig. 12, where 8〇~27 (rc (paragraph A) its thermal weight loss is i% by weight, the intense weight loss temperature starts around 385t: to 45 (the thermal loss weight near rc is 50% by weight ( Section B), after 50〇°c, its thermal weight loss is slowed down. After the change, the powder sample is analyzed by XRD instrument, and the XRD spectrum of Fig. 13 does not have a D value of 6.526, 4.739 and 4.3 04A. The peaks of the peaks are 13.558, 18.709 and 20.619, respectively, and the diffraction peak intensities of 13·558 and 20·619 at the 2 corners are respectively 3角·94% and® 6′6 of 20 degrees 7〇9. 〇%. The infrared hydrate (IR) instrument was used to measure the sample of the modified product of Sanshui Mingshijing type sulphate powder and carboxylic acid functional group. The result is shown in Fig. 14. From 1 4 i ° A can be seen at 1300 cm·1 There is a C-0 chemical bond nearby, a C=0 chemical bond near 17〇〇cnT1, and a 〇h chemical bond near 2800~3600 cm·1. The carboxylic acid functional group of oxalic acid and gibbsite crystal form aluminum hydroxide. There is a chemical bond between them. Example 4: Functional modification of the gibbsite crystalline aluminum hydroxide of Example 1 (iii) with adipic acid
13 1296265 在反應器70，100 g之實施例一（iii)的三水鋁石晶型氫 氧化铭粉體濾餅加入73 g己二酸與1000 g水、充分混合， 於1 60。(：進行羧酸官能基改性反應，反應時間2小時。將 所獲得的產物過濾水洗後，以TGA進行分析，結果如圖15 所示，在80〜26〇°C(A段）其熱失重為2重量％(未改性前熱 失重為10重量％)，激烈失重溫度約在38〇它附近開始，至 530 C附近（B段）其熱失重達60重量％。改性後粉體樣品以 鲁 XRD儀器分析，結果如圖1 6。 實施例五：對實施例一（iii)的三水鋁石晶型氫氧化鋁以反丁 烯二酸進行官能基改性 在反應器70 ’ 1 6 g之實施例一（iii)的三水銘石晶型氫 氧化銘粉體濾餅加入24 g反丁浠二酸與300 g水、充分混 合，於150〜160°C進行羧酸官能基改性反應，反應時間2 小時。將所獲得的產物過濾水洗後，以TGA進行分析，結 • 果如圖17所示，從80〜247°C(A段）其熱失重為i重量0/〇， 激烈失重溫度約在460°C附近開始，至600°C附近其熱失重 達53重量。/◦ (b段），高於6〇〇。〇以後其熱失重達趨緩。改 性後粉體樣品以XRD儀器分析，如圖18的XRD光譜所示， 在D值為8.42035、4.22882和2.82229A有繞射峰，其2Θ 角分別為10·498、20·991與31.678,而在2Θ角分別為2〇 991 與3 1.678的繞射峰強度分別為2Θ角10.498的16.37%和 13.07% 。以ir儀器測量三水鋁石晶型氫氧化鋁粉體與反 丁烯二酸進行官能基改性反應後的產物樣品，結果被示於 14 1296265 ' 圖19與圖20。從圖20可知在1400 cnT1附近有C-0化學 鍵，在1600 cnT1附近有C = 0化學鍵，在1700 cm·1附近有 C = C化學鍵，在28Q0〜3600 cnT1附近有0-H化學鍵，故 反丁烯二酸官能基與三水鋁石晶型氫氧化鋁之間有化學鍵 結。 實施例六：對實施例一⑴的pseudo-boehmite晶型氫氧化|呂 • 以草酸進行官能基改性 在反應器70 ’ 580 g的實施例一⑴的pSeud〇_b〇ehmite 晶型氫氧化銘漿液（固含量為7.72%)，與32 g草酸及1 500 g 水充分混合，於150°C進行官能基改性應，反應時間1小 日守。所獲得的粉體樣品以TGA儀器分析，結果被示於圖 21 ’其中在80〜360 C其熱失重為5重量％，激烈失重溫度 約在39(TC附近開始，至60(rc附近其熱失重達48重量％， n於600 C以後其熱失重達趨緩。改性後粉體樣品以xrd • 儀器分析，如圖22的XRD光譜所示，在D值為6·7433、 4.8427和3.8099A有繞射峰，其2Θ角分別為13 1186、 18.3 052 與 23.3 292，而在 2Θ角分別為 13·1186 與 23 3292 的繞射峰強度分別為20角18·3〇52的2〇·915%和ΐ8·3〇ι%。 圖式簡單說明 、圖1為顯示適用於本發明的-超重力場反應器的示意 剖視圖。 圖2為僅顯示圖1中的反應器的部份元件的示意上視 15 1296265 圖 圖3為依本發明内容來製備改性氫氧化鋁晶粒的流程 方塊圖。 圖4為本發明實施例一⑴所製備的pSeUd〇_b〇ehmite 晶型氫氧化銘粉末的χ射線繞線（XRD)光譜。 圖5為本發明實施例一⑴所製備的pseud〇_b〇ehmite 晶型氫氧化鋁粉末的電子顯微鏡觀照片。 圖6為本發明實施例一⑴所製備的pseudo-boehmite 晶型氫氧化鋁粉末的熱重分析儀（TGA)結果。 圖7為本發明實施例一（H)所製備的boehmite晶型氫氧 化銘粉末的X射線繞線（XRD)光譜。 圖8為本發明實施例一（^丨）所製備的三水鋁石晶型氫 氧化銘粉末的X射線繞線（XRD)光譜。 圖9為本發明實施例一（出）所製備的三水鋁石晶型氫 氧化鋁粉末的熱重分析儀（TGA)結果。 圖10為本發明實施例二所製備的改性氫氧化鋁粉末 的熱重分析儀（TGA)結果。 圖11為本發明實施例二所製備的改性氫氧化鋁粉末的 X射線繞線（XRD)光譜。 圖12為本發明實施例三所製備的改性氳氧化紹粉末 的熱重分析儀（TGA)結果。 圖1 3為本發明實施例三所製備的改性氫氧化銘粉末 的X射線繞線（XRD)光譜。 圖14為本發明實施例二所製備的改性氫氧化銘粉末13 1296265 In a reactor 70, 100 g of the gibbsite crystal form hydrogen oxyhydrin powder cake of Example 1 (iii) was added with 73 g of adipic acid and 1000 g of water, and mixed well at 1600. (: The carboxylic acid functional group modification reaction was carried out for 2 hours. The obtained product was filtered and washed with water, and analyzed by TGA, and the result is shown in Fig. 15 at 80 to 26 ° C (stage A). The weight loss is 2% by weight (the weight loss before unmodification is 10% by weight), the intense weight loss temperature starts around 38 〇, and the heat loss is 60% by weight near 530 C (B). The sample was analyzed by Lu XRD instrument and the results are shown in Fig. 16. Example 5: The gibbsite crystalline aluminum hydroxide of Example 1 (iii) was functionally modified with fumaric acid in reactor 70' 1 6 g of the Sanshui Mingshijing type hydroxide powder filter cake of the first example (iii), adding 24 g of the anti-butyric acid and 300 g of water, thoroughly mixing, and carrying out the carboxylic acid function at 150-160 ° C The reaction was modified for 2 hours. The obtained product was filtered and washed with water, and analyzed by TGA. The results are shown in Fig. 17. From 80 to 247 ° C (stage A), the thermal weight loss is i weight 0. /〇, the intense weight loss temperature starts around 460 °C, and its thermal weight loss reaches 53 weights near 600 °C. /◦ (paragraph b), higher than 6〇〇.〇 After that, the thermal weight loss is slowed down. The modified powder sample is analyzed by XRD instrument, as shown by the XRD spectrum in Fig. 18, and there are diffraction peaks at D values of 8.42035, 4.22882 and 2.82229A, respectively, and the 2Θ angle is 10· 498, 20·991 and 31.678, and the diffraction peak intensities of 2〇991 and 3 1.678 at 2Θ angles are 16.37% and 13.07% of 2Θ angle 10.498 respectively. The gibbsite crystal type aluminum hydroxide is measured by ir instrument. A sample of the product after the functional modification reaction of the powder with fumaric acid is shown in Fig. 19 and Fig. 20. It can be seen from Fig. 20 that there is a C-0 chemical bond near 1400 cnT1, near 1600 cnT1. There is a C=0 chemical bond with a C=C chemical bond around 1700 cm·1 and a 0-H chemical bond near 28Q0~3600 cnT1, so there is a relationship between the fumarate functional group and the gibbsite crystal form aluminum hydroxide. There is a chemical bond. Example 6: Pseudo-boehmite crystal form hydrogen hydroxide of Example 1 (1) | Lu • Functional modification of oxalic acid in reactor 70' 580 g of Example 1 (1) pSeud〇_b〇ehmite Crystalline oxyhydrin slurry (solids content 7.72%), thoroughly mixed with 32 g of oxalic acid and 1,500 g of water, at 150 ° C The functional group modification should be carried out, and the reaction time was 1 day. The obtained powder sample was analyzed by TGA instrument, and the result is shown in Fig. 21 'where the thermal weight loss was 5% by weight at 80 to 360 C, and the temperature loss temperature was about Starting at 39 (near TC, to 60 (the thermal weight loss near rc reached 48% by weight, n after 600 C, its thermal weight loss slowed down. The modified powder sample was analyzed by xrd • instrument, as shown by the XRD spectrum in Fig. 22, and had diffraction peaks at D values of 6.7433, 4.8427, and 3.8099A, and the two corners were 13 1186, 18.3 052, and 23.3, respectively. 292, and the diffraction peak intensities of 13·1186 and 23 3292 at 2 corners are respectively 2〇·915% and ΐ8·3〇ι% of 20 angles 18·3〇52. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a -supergravity field reactor suitable for use in the present invention. Figure 2 is a schematic top view showing only a portion of the elements of the reactor of Figure 1. Figure 1 is a block diagram of a process for preparing modified aluminum hydroxide grains in accordance with the present invention. 4 is a ray-ray winding (XRD) spectrum of a pSeUd〇_b〇ehmite crystalline hydroxide powder prepared in Example 1 (1) of the present invention. Fig. 5 is an electron microscopic view of a pseudopyrene-b〇ehmite crystalline aluminum hydroxide powder prepared in Example 1 (1) of the present invention. Fig. 6 is a thermogravimetric analyzer (TGA) result of the pseudo-boehmite crystalline aluminum hydroxide powder prepared in Example 1 (1) of the present invention. Fig. 7 is an X-ray winding (XRD) spectrum of a boehmite crystal form oxyhydroxide powder prepared in Example (H) of the present invention. Fig. 8 is an X-ray diffraction (XRD) spectrum of a gibbsite crystal form hydrogen oxyhydroxide powder prepared according to Example 1 of the present invention. Fig. 9 is a thermogravimetric analyzer (TGA) result of the gibbsite crystal form aluminum hydroxide powder prepared in the first embodiment of the present invention. Figure 10 is a graph showing the results of a thermogravimetric analyzer (TGA) of the modified aluminum hydroxide powder prepared in Example 2 of the present invention. Figure 11 is an X-ray diffraction (XRD) spectrum of a modified aluminum hydroxide powder prepared in Example 2 of the present invention. Figure 12 is a graph showing the results of a thermogravimetric analyzer (TGA) of a modified cerium oxide powder prepared in Example 3 of the present invention. Fig. 13 is an X-ray winding (XRD) spectrum of the modified hydroxide powder prepared in Example 3 of the present invention. Figure 14 is a modified hydroxide powder prepared according to the second embodiment of the present invention
16 1296265 的紅外線（IR)光譜。 圖1 5為本發明實施例四所製備的改性氫氧化銘粉末 的熱重分析儀（TGA)結果。 圖1 6為本發明實施例四所製備的改性氯氧化銘粉末 的X射線繞線（XRD)光譜。 圖1 7為本發明實施例五所製備的改性氫氧化銘粉末 的熱重分析儀（TGA)結果。 φ 圖1 8為本發明實施例五所製備的改性氫氧化紹粉末 的X射線繞線（XRD)光譜。 圖1 9為本發明實施例五所製備的改性氫氧化鋁粉末 的紅外線（IR)光譜。 圖20為本發明實施例五所製備的改性氫氧化鋁粉末 的紅外線（IR)光譜。 圖21為本發明實施例六所製備的改性氫氧化鋁粉末 的熱重分析儀（TGA)結果。 _ 圖22為本發明實施例六所製備的改性氫氧化鋁粉末 的X射線繞線（XRD)光譜。 主要元件之圖號說明 1〇··反應艙 1··液體進料管 2.·穿孔 3··氣體入口 4··外框 5··不鏽鋼網 6··旋轉軸 7··反應產物出口 8··氣體排出管 20·••多孔性旋轉葉片 30··轉盤 41，42,43.·儲槽 5 0··接收槽 51.·ρΗ值控制單元 5 2 ··溫度控制單元 6 1，6 2 .·過濾、清洗單元 17 1296265 70..改性反應器 100..超重力場反應器16 Infrared (IR) spectrum of 1296265. Fig. 15 is a thermogravimetric analyzer (TGA) result of the modified hydroxide powder prepared in Example 4 of the present invention. Fig. 16 is an X-ray winding (XRD) spectrum of the modified chlorine-oxidized powder prepared in Example 4 of the present invention. Fig. 17 is a thermogravimetric analyzer (TGA) result of the modified hydroxide powder prepared in Example 5 of the present invention. φ Figure 18 is an X-ray diffraction (XRD) spectrum of the modified oxidized Shaoxing powder prepared in Example 5 of the present invention. Fig. 19 is an infrared (IR) spectrum of the modified aluminum hydroxide powder prepared in Example 5 of the present invention. Figure 20 is an infrared (IR) spectrum of a modified aluminum hydroxide powder prepared in Example 5 of the present invention. Figure 21 is a graph showing the results of a thermogravimetric analyzer (TGA) of the modified aluminum hydroxide powder prepared in Example 6 of the present invention. Fig. 22 is an X-ray winding (XRD) spectrum of the modified aluminum hydroxide powder prepared in Example 6 of the present invention. Description of the main components: 1〇··Reaction chamber 1··Liquid feed tube 2.·Perforation 3··Gas inlet 4··Outer frame 5··Stainless steel mesh 6··Rotary shaft 7··Reaction product outlet 8 · Gas discharge pipe 20·•• Porous rotating blade 30·· Turntable 41, 42, 43.·Storage tank 5 0··Receiving tank 51.·ρΗ value control unit 5 2 ·· Temperature control unit 6 1,6 2 .·Filtering and cleaning unit 17 1296265 70..Modification reactor 100..Supergravity field reactor