¾齊部皆¾財lt^Rr.肖費釜乍;1‘印災 550246 五、發明説明（/ ) —___ 本發明是關於一種石夕氣層狀 &柏土 /聚峻 合物及其製造方法，特別是於 u U u $ 喊胺（pQiy alkyl amine)為插層劑改質矽氧層狀無機黏土 矽氧層狀無機黏土 /聚醚胺複合物、粘土之 ~ I造方法。 石夕氧層狀無機黏土以往常 饭應用於觸媒及高八」 材料之補強材，其可妹由右嫉 ° " 工由有機四級銨鹽之插層反万 (intercalating)鬆動黏土 夾層， . 吁之層間距離約） 1〇，A。此鬆動之夾層可允許單體進出，再經由… 應而得到脫層分散（exfoliate)之有機/無機奈米高^ 複合材料’ A種材料做為高分子材料之補強材可改 子材料之熱性能、機械特性、阻氣性及耐燃性等。有1 機7 無機奈米高分子複合材料被認為是新世紀之重要材料，士 種材料之開發及應用為學術界及工業界研發上極為重要白 課題，近年來，在此方面之文獻及專利的發表已有不少（ 曰本豐田公司開發出以[H3N+(CH2)uC〇〇-] —蒙脫土分散为 Nylon 6為首件商業成功之有機/無機奈米高分子複合诗 料。在日本公告特許8-22946號中有記載，以氨基羧g (aminocarboxylic acid)進行插層反應，將層狀石夕酸鹽」 層間距離擴大，再以己内醯胺單體（capi*olactam)於夾， 間進行縮合聚合反應，使層狀矽酸鹽薄片在聚醯胺（Ny 11 6 )樹脂中形成均一分散之構造。但是除了聚醯胺樹脂 本紙張尺度適用中國國家榡牟（Cns ) Μ規格（21〇’〆^97必釐）2 (請先閲讀背面之注意事項再填寫本頁)¾ 齐 部 部 ¾¾ 财 ^^ Rr. Xiao Feibucha; 1 'Yin disaster 550246 V. Description of the invention (/) —___ The present invention relates to a layer of Shixi gas & The manufacturing method, especially the method for modifying the silicic acid layered inorganic clay, the silicic acid layered inorganic clay / polyetheramine complex, and the clay by p ui u alkylamine. Shixi oxygen layered inorganic clay has been used as a reinforcing material for catalysts and high eighth materials in the past. It can be loosened by intercalating intercalating loose organic clay interlayers by the right-angled " workmanship and organic quaternary ammonium salt. ,. The distance between the layers is about 10), A. This loose interlayer allows monomers to come in and out, and then obtains an exfoliate of organic / inorganic nano-high ^ composite materials' A material as a reinforcing material for polymer materials can change the heat of the material Performance, mechanical characteristics, gas barrier properties and flame resistance. There are 1 machine 7 inorganic nano polymer composite materials are considered to be important materials in the new century. The development and application of scholarship materials are extremely important topics in research and development in academia and industry. In recent years, literature and patents in this regard There have been a lot of publications (say, this Toyota company developed [H3N + (CH2) uC〇-]-montmorillonite dispersed as Nylon 6) as the first commercially successful organic / inorganic nano polymer composite poetry. In Japan It is described in Announcement Patent No. 8-22946 that an intercalation reaction is performed with aminocarboxylic acid (glycolic acid) to expand the interlayer distance of the layered fossilate, and then capi * olactam is sandwiched between the layers. Condensation polymerization reaction is carried out to make the layered silicate flakes form a uniformly dispersed structure in polyamide (Ny 11 6) resin. However, in addition to polyamide resin, the paper size of this paper is applicable to China ’s national standard (Cns) M specifications. (21〇'〆 ^ 97 必 厘) 2 (Please read the notes on the back before filling this page)
550246 A7 B7 五、發明説明（Z ) ^ —-- (請先閲讀背面之注意事項再填寫本頁) 外，要使層狀矽酸鹽薄片在其他樹脂中分散均一是很困難 的。例如在非極性之聚乙烯或聚丙烯中使親水性高之層狀 矽酸鹽均一分散便是非常困灘。為解決此問題，日本公開 特許8-53572號中有記載，以有機鐺離子（〇nium丨⑽）進 線 订插層反應，將層狀矽酸鹽之層間距離擴大，再與溶融聚 烯烴樹脂混合，使層狀矽酸鹽薄片在樹脂中形成均一分散 之構造。雖然有機餚離子可將層狀矽酸鹽之層間距離擴 大’烯烴樹脂容易於夾層間連續插入，但因有機插層劑與 稀：^树月曰之親a力仍然不夠，而使層狀石夕酸鹽要無限膨潤 非常困難。又，曰本公開特許1〇_1 82892號中記載，有機 化層狀砍酸鹽與含氫鍵結合性官能基之烯烴寡聚物及聚埽 煙樹脂溶融混練，可使層狀矽酸鹽在樹脂中無限膨潤。此 因插層劑與含氫鍵官能基之烯烴聚合物（例如聚醯胺高分 子）之親和力較強之原因。但是為了使層狀矽酸鹽能夠均 一分散，必須有足量之寡聚物，然而樹脂中含多量的寡聚 物會使樹脂之機械特性特別是耐衝擊性下降。 【發明概要】 因此’本發明之目的即在提供以聚醚胺為插層劑 改質矽氧層狀無機黏土 ，使其帶親油性可與高分子 相容，並將層間距離擴大至50〜92A，有助於高分子 進入黏土夾層，使黏土達到奈米尺度分散於高分子 中’以獲得一種新型有機/無機高分子複合物。此 穩定之複合物由於同時具備極性親水結構與非極性 本紙張尺度適用中國國家標準（CNS ) A4規格（2^< 297么、廣）> ^' 550246 A7 經濟部智慧財產局員工消費合作社印製 五、發明説明GJ ) 親油結構，因此具有優異界面活性劑效能，可應用 於油性界面活性劑’如 pvc反應爐中之脫膜劑等。 同時還可做為高分子補強/劑，以提昇高分子之对熱 性、阻氣性、剛性、抗拉性及反撥回覆性等機械性 質。 習知之插層劑，包括12-氨基月桂酸（12-ami no 1 auric acid)、十六烧胺（hexadecylamine)、脂肪族胺（fatty amine)、雙（2-經基乙基）曱基牛脂烷基氣化銨（bis (2一 hydroxyethyl)methyl tallow alkyl ammonium chloride) 及十八烧胺（stearylamine)等胺類或銨鹽。此類低分子型 插層劑之極性基能與帶電荷之無機層狀分子形成極性價鍵 結合，並使黏土之親水性改變成為親有機溶劑之性質。換 言之，即提昇黏土對有機單體或高分子之親和性，以利下 一步之脫層反應。 然而，本發明人經銳意研究發現，插層劑之分子量 大小與插層效果有密切關係，插層劑之分子量越大，則黏 土夾層的高度也越大，而夾層高度盘杯 日门又，、插層劑之分子量大小 並成線性關係，即插層效果越佳。也就是當黏土灸層高度 越大，越有助於高分子進入黏土夾層中，以分散黏 土之石夕氧層狀結構’而達奈米尺度之分散。因此， 本發明乃使用分子量1 8 〇 〇以上之聚 灰喊胺（polyoxy- alkylene amine)為插層劑，其中以聚丙基鍵雙胺 (polyoxypr〇pylene diamine)為佳 業化產品Jeffamine D2000 [聚丙 i紙張尺度適用中國準（CNS )八4祕（21〇><297/膽） ’此種物質有商 二醇雙（2 -氨基丙 (請先閱讀背面之注意事項再填寫本頁) 線 UF. 550246 A7 經濟部智慧財產局員工消費合作社印災 ______B7 _五、發明説明（令） 基醚）(poly(propyleneglycol )bis(2-aminopropyl ether))，Mw 2000]、D4000[聚丙二醇雙（2-氨基丙 基 醚） （poly (propyleneglycol) bis (2-aminopropyl ether)) ， Mw 4000]等，其中又以 Jeffamine D2000為最佳（Jeffamine系列之結構式 如下所示）；其他還有如T3000 [三官能聚丙二醇2-氨基 丙基醚 （t r i - f u n c t i ο n a 1 poly(propyleneglycol)2-aminopropyl ether) ， Mw 3000]、T5000 [三官能聚丙二醇 2-氨基丙基醚 (tri-functional poly (propylene glycol) 2-aminopropyl ether)，Mw 5 0 0 0 ]等。h2nchch2(och2ch)nh2 ch3 ch3 X= 2-3 (Approx. Mw=230; Jeffamine® D-230) X= 5-6 (Approx. Mw=400; Jeffamine® D-400) X= 33 (Approx. Mw=2000； Jeffamine® D-2000) X= 68 (Approx. Mw-4000； Jeffamine® D-4000) 另外，T. J· Pinnavaia (Michigan State University) 發現雙S分A之二縮水甘油醚 （diglycidyl ether of BPA， 環氧樹脂Epon828)可以經插層劑CH3(CH2)n-NH3 +與蒙脫 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） !il? (請先閱讀背面之注意事¾再填寫本頁) 、\'*u 線 A7 550246 五、發明説明（夕） 土聚合成為奈米級聚醚—黏土複合材料。插層劑之結構式 不同’可達層間距離1 8 A，再經7 5 °C之環氧樹脂自行 聚合成為3 4 · 1 A之環氧樹脂/黏土材料，並證明其 熱變形溫度（heat distortion temperature)提昇， 在此插層劑之規則性，可由單層（m ο η ο 1 a y e r )至雙 b i layer (請先閱讀背面之注意事項再填寫本頁) 以至為三層結構 （p s e u d o tTimolecular)，層間距離為i3.8〜18〇A之間。在 此高度之插層，可讓環氧樹脂進入聚合，並更進一 步分散層狀無機物，以達到奈米材料之應用效果。 無機/有機奈米複合材料為兩相不同之材料，且至 ’ 相具有奈米規格（nanoscale regime)之分散。在均勻 之刀政下’即在高接觸面積（surface to volume ratio) 狀態下，增加機械性能。 因此，良好之複合結構，決定於有機與無機物兩相 之相谷（'生 般之蒙脫土結構以平均10層平行層狀 (lamel lae)，大約10 nm ( L e·， 1〇〇A )大小之層面直徑 存在，而層與層之間距只有12A左右，此為最小之第一 經濟部智慧財產局員工消费合作社印災 級結構（pr imary structure)。其親水性矽酸鹽（3丨1 ία。' 自行微細之凝集（aggregate)而成為二級結構，對有機 高分子之親和力很低。提高兩者之相容性需賴黏土本身層 距間存在離子與有機四級銨鹽之交換能力，而導入此有機 四級銨鹽，以插層提高層距，通常達2〇A力+ α石，而以離 子鏈生成非共軛價，此為插層改質黏 使兵成為具有有機 性質。插層狀態（i nterca i at i on)係層盘屏夕ρ日 -------'、曰 < 間以固定距 本紙張尺度適财關家鮮（CNS ) A4· ( 21GX297减）/ ^------ 550246 A7 B7 五、發明説明（G ) (請先閲讀背面之注意事項再填寫本頁) 離之結晶形分散存在。而分散脫層（e X f 〇丨i a t丨◦ n )狀熊 係每單一層以不規則之距離及方向存在，此為脫層過程， 通常需經插層狀您黏土與南分子再經由更進一步之；程而 得。 蒙脫土 （montmorillonite，MMT)為親水之矽叙酸 鹽黏土 （alumino-si 1 icate clay)，結構式具有二層四面 體二氧化矽 （tetrahedral silicate)及失層八面體氧化 鋁（octahedral alumina)。電子顯微鏡觀察為〇. 1〜1〇 μ大 小之凝集（aggregate)，而結構單位 （strutural units)為 16平面（planes)或8層狀（lamellae)，每一層狀厚度 為 9·6-10A。故一級結構（primaryparticle)有 80-1〇〇 A高度，及3 0 0 A半徑大小。 線 經濟部智慧財產局員工消費合作社印挺 本發明所使用之矽氧層狀無機黏土係選自蒙脫土 (montmorillonite)、高嶺土 （kaolin)、雲母（mica)及 滑石粉 （talc)，且其陽離子交換當量以 50〜200 meq/100g為佳。當陽離子交換當量低於50meci/100g 時，經由離子交換而達成的有機化便不充分，黏土 的膨潤不易；當陽離子交換當量高於200 meq/100g 時，夾層間結合力太高，也會使黏土的膨潤非常困難。 本發明之矽氧層狀無機黏土 /聚醚胺複合物之 製造方法，係將分子量 1 8 0 0以上之聚醚胺以無機 酸進行酸化處理，再混入經水膨潤之矽氧層狀無機 黏土 ，於 6 0〜8 0 °C下強力攪拌使其進行陽離子交換 反應以製得矽氧層狀無機黏土 /聚醚胺複合物。本發 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297分釐）7 A7 550246 B7 五、發明説明（7) 明中重要發現為分子量低於1 8 0 0 之聚醚胺並不能達到高 層距插層之效果，且聚醚胺必須為雙胺（d i a m i n e )，若 為單胺（m ο η o a m i n e )，亦不能達到滿意之效果。 (請先閏讀背面之注意事項再填寫本頁) 其中，若插層劑未經過酸化處理，則進行插層 反應時，大部分插層劑將無法進入黏土之夾層，而 使得插層效果不佳。可使用之無機酸如鹽酸、硫酸、 磷酸及硝酸。而且酸化處理之最適當條件為-N H 2 / Η + 在 2:1 莫耳比之下有最佳效果，即胺之酸化程度 在一半時，分子排列為b i 1 a y e r狀態時為最佳。 又，插層劑的量小於石夕氧層狀無機黏土之陽離 子交換當量 （CEC: cation exchange capacity of c 1 a y )時，黏土層由於層間之穩定正負電荷吸引， 使得插層劑已經進入黏土夾層中但仍無足夠能量將 層間距離撐得很大。因此，本發明中所使用之插層 劑聚醚胺之莫耳數至少為矽氧層狀無機黏土之陽離 子交換當量。如此所製得之矽氧層狀無機黏土 /聚 醚胺複合物其層間距離為5 0〜9 2 A。 經濟部智慧財產局員工消費合作社印!«- 天然黏土表面為親水性，因此能均勻分散於水 中。但與絕大部分之高分子不相容，因此在熔融混 練中將形成相分離而無法達到微觀之細微分散。改 質後之黏土由於有機分子之導入，而帶部分非極性 或有機性，可提高與高分子相容之程度。故，前述 反應後所得之複合物經由過濾可得白色蓬鬆固狀 物，其可與高分子摻混以‘改質高分子。乾燥後可得 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐）& 550246 at B7 五、發明説明（《） (請先閲讀背面之注意事項再填寫本頁) 土色黏性固狀物，可穩定分散於甲苯中。其乾燥與 否可隨應用之不同而作選擇。可與本發明複合物摻 混以改質之南分子如環氧樹脂（e ρ ο X y r e s i η )、聚 丙烯（PP)、聚對苯二甲酸乙二醇酯（PET)、聚苯乙 婦（PS)、間規聚苯乙烯（SPS)、聚氨基甲酸乙酯 (PU)、耐龍（Nylon)及苯乙稀一丙烯腈共聚物（san)等。 【較佳實施例之詳細說明】 為了更詳細說明本發明，以下特舉出較佳實施例， 當不能以此限定本發明實施之範圍，即大凡依本發明申請 專利範圍及發明說明書内容所作之簡單的等效變化與修 飾，皆應仍屬本發明專利涵蓋之範圍内。 【實施例卜6及比較例1〜5】 依下列步驟製造經由插層劑改質之矽氧層狀無機 黏土複合物。 1 ·矽氧層狀無機黏土之膨潤步驟： 經濟部智慧財產局員工消費合作社印¾. 將陽離子交換當量CEC = 115 meq/100 g之鈉陽離 子交換型蒙脫土 Kunipia F (Na + -MMT)分散於 1 0 0 0 m 1 8 0 °C之熱水中，強力攪拌4小時，使水 溶液形成土色之穩定均勻分散液。 2.插層劑之酸化處理步驟： 將插層劑溶於1 0 0 m 1己醇中，加入等莫耳數之鹽酸 (HC1 )，常溫下酸化3◦分鐘。 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐 ¾齊部.£曰鎏財l肖費圣泎ri印製 550246 A7 __ B7 五、發明説明（9 ) 3.插層反應步驟： 酸化完成之插層溶液倒入步驟1之分散液中，於 6 0〜7 0 °c下強力攪拌斤小時，進行陽離子交換反 應。反應液靜置，使其分層。過濾並以水及乙醇 清洗數次，以除去未反應之插層劑與蒙脫土。將 所得之產物置於真空烘箱中乾燥 2 4小時，以去 除水及乙醇得到經由插層劑改質之矽氧層狀無機 黏土複合物，且由SEM照像，金屬Na +均已不存 在於樣品中。 實施例1〜4及比較例卜3所用之插層劑，及插層劑 與蒙脫土之重量比載於表一。將所製得之複合物以X光繞 射（X-ray diffraction)分析，測得其層間距離，結果如 表一戶斤示。 由表一之數據顯示，分子量大小與插層效果有密切 的關係。插層劑之分子量越大，則黏土層間距離也越大。 實施例1、5、6及比較例4、5係以D20 00為插層劑， 其與蒙脫土之重量比載於表二。將所製得之複合物以乂光 繞射 （X-ray di f fraction)分析，測得其層間距離，結 果如表二所示。 由表一之數據顯示’在插層劑的量小於最大陽離子 交換當量（CEC)時，黏土層由於層間之穩定正負電荷吸引， 使得雖然插層劑已經進入黏土夾層中但仍無足夠能量將居 間距撐的很大。一直到插層劑的量等於CEC值時，才得·” 本紙張尺度適用中國國家標準（CNS ) A4現格（210X2974(楚）/P -------. (請先閱讀背面之注意事項再填寫本頁)550246 A7 B7 V. Description of the invention (Z) ^ --- (Please read the precautions on the back before filling this page) In addition, it is very difficult to make the layered silicate flakes uniformly dispersed in other resins. For example, homogeneous dispersion of highly hydrophilic layered silicates in non-polar polyethylene or polypropylene is very difficult. In order to solve this problem, it is described in Japanese Laid-Open Patent No. 8-53572 that the organic layer ion (Onium 丨 ⑽) is used to enter the intercalation reaction to expand the interlayer distance of the layered silicate and then melt the polyolefin resin. Mix so that the layered silicate flakes have a uniformly dispersed structure in the resin. Although organic ions can expand the interlayer distance of layered silicates, olefin resins are easy to be continuously inserted between interlayers, but because of the organic intercalating agent and the dilute: ^ Shuyue Yue's affinity is not enough, so the layered stone Infinite swelling is extremely difficult. In addition, Japanese Patent Publication No. 10_1 82892 describes that organic layered chopper salts can be melt-kneaded with olefin oligomers and polyfluorinated resins containing hydrogen bonding functional groups to make layered silicates. Unlimited swelling in resin. This is due to the strong affinity of the intercalating agent with hydrogen-bonding-containing olefin polymers (such as polyamide polymers). However, in order for the layered silicate to be uniformly dispersed, a sufficient amount of oligomers must be present. However, a large amount of oligomers in the resin may reduce the mechanical properties of the resin, especially the impact resistance. [Summary of the invention] Therefore, 'The purpose of the present invention is to provide a modified silica-layered inorganic clay using polyetheramine as an intercalating agent, so that its lipophilicity is compatible with the polymer, and the distance between layers is increased to 50 ~ 92A, helps the polymer enter the clay interlayer, so that the clay reaches nanoscale dispersion in the polymer 'to obtain a new type of organic / inorganic polymer composite. This stable compound has both a polar hydrophilic structure and non-polarity. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 ^ < 297 ?, Canton) > ^ '550246 A7 Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed 5. Description of the invention GJ) The lipophilic structure, so it has excellent surfactant effectiveness, can be applied to oily surfactants such as film release agents in PVC reactors. At the same time, it can also be used as a polymer reinforcement / agent to improve the mechanical properties of the polymer such as heat resistance, gas barrier properties, rigidity, tensile resistance, and reversibility. Conventional intercalating agents, including 12-ami no 1 auric acid, hexadecylamine, fatty amine, and bis (2-ethylethyl) fluorenyl tallow Ammonium or ammonium salts such as bis (2-hydroxyethyl) methyl tallow alkyl ammonium chloride and stearylamine. The polar group of such low molecular type intercalating agents can form polar valence bonds with the charged inorganic layered molecules, and change the hydrophilicity of the clay into an organic solvent-friendly property. In other words, it enhances the affinity of clay for organic monomers or polymers to facilitate the next delamination reaction. However, through intensive research, the inventors found that the molecular weight of the intercalating agent is closely related to the intercalating effect. The larger the molecular weight of the intercalating agent, the greater the height of the clay interlayer, and the height of the interlayer plate. The molecular weight of the intercalating agent has a linear relationship, that is, the better the intercalating effect. That is, when the height of the clay moxibustion layer is larger, it is more helpful for the polymer to enter the clay interlayer to disperse the clay-like oxygen layered structure 'and the nanometer-scale dispersion. Therefore, in the present invention, polyoxy-alkylene amine with a molecular weight of 18,000 or more is used as an intercalating agent, and polyoxypropylene diamine is used as a good product Jeffamine D2000 [Polypropylene i Paper size is applicable to China Standard (CNS) Eighty-fourth Secret (21〇 > < 297 / Bile) 'This substance is commercial diol bis (2-aminopropyl (please read the precautions on the back before filling this page) Line UF. 550246 A7 Disaster printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ______B7 _V. Description of the Invention (Order) Poly (propyleneglycol) bis (2-aminopropyl ether), Mw 2000], D4000 [Polypropylene glycol Bis (2-aminopropyl ether) (poly (propyleneglycol) bis (2-aminopropyl ether)), Mw 4000], etc., among which Jeffamine D2000 is the best (the structural formula of the Jeffamine series is shown below); others such as T3000 [tri- functi na 1 poly (propyleneglycol) 2-aminopropyl ether), Mw 3000], T5000 [tri-functional polyglycol 2-aminopropyl ether (tri-functional poly (propylene glycol) 2-aminopropyl ether), Mw 5 0 0 0] and the like. h2nchch2 (och2ch) nh2 ch3 ch3 X = 2-3 (Approx. Mw = 230; Jeffamine® D-230) X = 5-6 (Approx. Mw = 400; Jeffamine® D-400) X = 33 (Approx. Mw = 2000; Jeffamine® D-2000) X = 68 (Approx. Mw-4000; Jeffamine® D-4000) In addition, T. J. Pinnavaia (Michigan State University) found diglycidyl ether with double S fraction A bis of BPA, epoxy resin Epon828) can be intercalated by CH3 (CH2) n-NH3 + and montmorillonite. The paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm)! il? (Please read the back first (Note ¾ then fill out this page), \ '* u line A7 550246 V. Description of the invention (Even) The soil polymerizes into nano-grade polyether-clay composite materials. The structural formula of the intercalating agent is different, and the interlayer distance can reach 1 8 A, and then it can be polymerized by itself at 75 ° C into 3 4 · 1 A epoxy resin / clay material, and its heat distortion temperature (heat distortion temperature), the regularity of the intercalating agent can be from a single layer (m ο η ο 1 ayer) to a double bi layer (please read the precautions on the back before filling this page) to a three-layer structure (pseudo tTimolecular ), The interlayer distance is between i3.8 ~ 18〇A. Intercalation at this height allows the epoxy resin to enter the polymerization and further disperse the layered inorganics to achieve the application effect of nanomaterials. Inorganic / organic nanocomposites are materials with two different phases, and have a nanoscale regime dispersion to the phase. In a uniform blade regime, that is, in a state of high surface to volume ratio, the mechanical properties are increased. Therefore, a good composite structure is determined by the two-phase valley of organic and inorganic matter ('raw montmorillonite structure has an average 10 layers of lamel lae), about 10 nm (L e ·, 100A The size of the layer diameter exists, and the distance between the layers is only about 12A, which is the smallest pr imary structure of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Its hydrophilic silicate (3 丨1 ία. 'It becomes a secondary structure by its own fine agglomeration, which has a low affinity for organic polymers. Improving the compatibility of the two requires the exchange of ions and organic quaternary ammonium salts between clay layers. Ability to introduce this organic quaternary ammonium salt to increase interlayer distance by intercalation, usually up to 20A force + alpha stone, and generate non-conjugated valence with ionic chains. Nature. The state of intercalation (i nterca i at i on) is the layer of the panel screen eve ri day ------- ', said < between a fixed distance from the paper scale and suitable for financial and family (CNS) A4 · ( 21GX297 minus) / ^ ------ 550246 A7 B7 V. Description of the invention (G) (Please read the note on the back first Please fill in this page again.) The separated crystal forms exist separately. However, each single layer of dispersed delamination (e X f 〇 丨 iat 丨 ◦ n) exists at an irregular distance and direction. This is a delamination process, usually You need to go through the layering of your clay and south molecules and go further; montmorillonite (MMT) is a hydrophilic alumino-si 1 icate clay with a two-layer structure Tetrahedral silicon dioxide (tetrahedral silicate) and delaminated octahedral alumina (octahedral alumina). Electron microscope observation is 0.1 ~ 10μ size aggregate (aggregate), and structural units (strutural units) are 16 planes (Planes) or 8 layers (lamellae), each layer thickness is 9.6-10A. Therefore, the primary particle has a height of 80-1〇A, and a radius of 300 A. The wisdom of the Ministry of Economics Employees' Cooperative of the Property Bureau of India printed the siliceous layered inorganic clay used in the present invention is selected from montmorillonite, kaolin, mica and talc, and its cation exchange equivalent is 50 ~ 200 me q / 100g is better. When the cation exchange equivalent is less than 50meci / 100g, the organicization achieved through ion exchange is insufficient, and the swelling of the clay is not easy; when the cation exchange equivalent is higher than 200 meq / 100g, the interlayer bonding force Too high will also make clay swelling very difficult. The manufacturing method of the siliceous layered inorganic clay / polyetheramine composite of the present invention is to acidify a polyetheramine having a molecular weight of 1800 or more with an inorganic acid, and then mix the water-swelled siliceous layered inorganic clay. The mixture was stirred vigorously at 60 ° to 80 ° C to perform a cation exchange reaction to obtain a siloxane layered inorganic clay / polyetheramine composite. The paper size of this issue applies to the Chinese National Standard (CNS) A4 specification (210X297 centimeters) 7 A7 550246 B7 V. Description of the invention (7) An important finding in the Ming is that the polyetheramine with a molecular weight lower than 1 800 does not reach the upper level The effect of the distance from the intercalation layer, and the polyetheramine must be a diamine (diamine), if it is a monoamine (m ο η oamine), it can not achieve satisfactory results. (Please read the precautions on the back before filling this page.) Among them, if the intercalating agent is not acidified, most intercalating agents will not be able to enter the interlayer of clay during the intercalation reaction, making the intercalation effect ineffective. good. Useful inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid. And the most suitable condition for acid treatment is that -N H 2 / Η + has the best effect at a molar ratio of 2: 1, that is, when the degree of acidification of the amine is half, the molecular arrangement is the best when the state is b i 1 a y e r. In addition, when the amount of the intercalating agent is less than the cation exchange capacity of the layered inorganic clay (CEC: cation exchange capacity of c 1 ay), the clay layer is attracted by the stable positive and negative charges between the layers, so that the intercalating agent has entered the clay interlayer. Medium but still not enough energy to extend the distance between layers. Therefore, the mole number of the intercalating agent polyetheramine used in the present invention is at least the cation exchange equivalent of the siliceous layered inorganic clay. The interlayer distance of the silicon-oxygen layered inorganic clay / polyetheramine composite prepared in this manner was 50 to 9 2 A. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs! «-The natural clay surface is hydrophilic, so it can be evenly dispersed in water. However, it is incompatible with most polymers, so phase separation will be formed during melt-kneading, and micro-fine dispersion cannot be achieved. The modified clay is partially non-polar or organic due to the introduction of organic molecules, which can increase the degree of compatibility with polymers. Therefore, the complex obtained after the foregoing reaction can be filtered to obtain a white fluffy solid, which can be blended with the polymer to ‘modify the polymer. The paper size obtained after drying is applicable to Chinese National Standard (CNS) A4 specification (21 × 297 mm) & 550246 at B7 V. Description of the invention (") (Please read the precautions on the back before filling this page) Earth color Viscous solid, stable dispersion in toluene. Whether it is dry or not can be selected depending on the application. It can be blended with the compound of the present invention to modify the South molecule such as epoxy resin (e ρ ο X yresi η), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), syndiotactic polystyrene (SPS), polyurethane (PU), Nylon, and styrene-acrylonitrile copolymer (san). [Detailed description of the preferred embodiment] In order to explain the present invention in more detail, the preferred embodiments are given below. When the scope of the present invention cannot be limited by this, that is, what is generally done according to the scope of the patent application and the content of the invention specification Simple equivalent changes and modifications should still fall within the scope of the invention patent. [Example 6 and Comparative Examples 1 to 5] A silicon-oxygen layered inorganic clay composite modified by an intercalating agent was manufactured according to the following steps. 1 · Swelling steps of siliceous layered inorganic clay: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾. Sodium cation-exchange montmorillonite Kunipia F (Na + -MMT) with cation exchange equivalent CEC = 115 meq / 100 g Disperse in hot water at 1000 m 1 80 ° C and stir vigorously for 4 hours to make the aqueous solution a stable and uniform dispersion of earth color. 2. Acidification treatment steps of the intercalating agent: Dissolve the intercalating agent in 100 m 1 hexanol, add hydrochloric acid (HC1) of equal molar number, and acidify at room temperature for 3 ◦ minutes. This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm ¾ full size). 鎏 鎏 鎏 肖 费 泎 泎 泎 printed 550 246 A7 __ B7 V. Description of the invention (9) 3. Intercalation reaction Steps: The acidified intercalation solution is poured into the dispersion of step 1 and stirred vigorously at 60 to 70 ° C for hrs for a cation exchange reaction. The reaction solution is left to stand to separate the layers. Filter and use water Wash several times with ethanol to remove unreacted intercalating agent and montmorillonite. The obtained product was dried in a vacuum oven for 24 hours, to remove water and ethanol to obtain a layer of silica modified by the intercalating agent. Inorganic clay composites, and by SEM images, the metal Na + is no longer present in the sample. The intercalating agents used in Examples 1 to 4 and Comparative Example 3, and the specific weight of the intercalating agent and montmorillonite The results are shown in Table 1. The obtained composites were analyzed by X-ray diffraction, and the interlayer distance was measured. The results are shown in Table 1. According to the data in Table 1, the molecular weight and intercalation The effect is closely related. The larger the molecular weight of the intercalating agent, the greater the distance between clay layers. In Examples 1, 5, 6 and Comparative Examples 4 and 5, D200 00 was used as an intercalating agent, and the weight ratio of the compound to montmorillonite is shown in Table 2. The obtained composite was diffracted by calendering ( X-ray di f fraction) analysis, measured the interlayer distance, and the results are shown in Table 2. According to the data in Table 1, 'When the amount of intercalating agent is less than the maximum cation exchange equivalent (CEC), the clay layer is Stable positive and negative charge attraction, so that even though the intercalating agent has entered the clay interlayer, there is not enough energy to support the interstitial distance. It is only obtained when the amount of intercalating agent is equal to the CEC value. ”This paper standard applies to China Standard (CNS) A4 is now available (210X2974 (Chu) / P -------. (Please read the precautions on the back before filling this page)
550246 at B7 五、發明説明（丨ϋ 將夾層距離打開到5 8 Α。此時增加插層劑的量，也無法 再增加層間距。此乃因夾層中之D2 0 0 0已形成良好排列， 且黏土外之D2000亦無法再借陽離子交換而導入黏土夾層 〇 經濟部智慧財產局員工消費合作社印製 【其他圖表說明】 圖一 以X光繞射（x —ray di f fraction)分析，層間距 離與插層劑之分子量成線性關係。 圖二就插層劑D2000而言，黏土之層間距離由12. 4 A 增加到58 A，且黏土層間形成規則之棑列，在χ 光繞射中達到η = 5之結晶繞射峰，此表現出極規 則之結構。 圖三 由於晶格缺陷使黏土表面帶負電，而插層劑在經 酸化後則形成帶正電之四級銨鹽，在高濃度時 (>15 wt % )由於正負電荷之吸弓丨導致擬交聯狀 態之生成。MMT-D20 0 0在甲苯中，當滚度大於3訂 %時，其黏度明顯上升。 天然黏土表面為親水性，因此能均勻分散於水中， 與絕大部分之有機溶劑不相容。改質後之黏土由 於有機分子之導入’而帶部份非極性，可與有機 溶劑相容。將改質後之黏土經超音波震盪後，觀 察其分散之穩定性。 由聚丙基鍵雙胺插層無機黏土所製備得之有機/無 f尾+ # ’ φ & mu^水結構與非極性 表三 圖四 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297也釐）f / (請先閱讀背面之注意事項再填寫本頁) A7 550246 ^___B7 五、發明説明（丨丨） 親油結構，因此，展現極佳之界面混合能力。就 D2 0 0 0插層無機黏土之改質黏土（MMT_D2〇〇〇)而 言’可使甲苯（Tolubne)與水之界面張力由365 dyne/cm下降至1. 5 dyne/cm，並顯現濃度甚低之 臨界微胞濃度在1 0 p p m附近。此特殊之界面現象 將有助無機黏土在兩分子中之均句分散，並達奈 米（nanometer)尺度。由圖四可看出，題T-D2000 及MMT-D4000與市面上非離子型界面活性劑Span 20 [山梨糖單月桂酸酯（sorbitan monolaurate)， 分子量346 ]比較，可更有效降低曱苯/水相之界 面張力。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印^ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297必楚）/厶 550246 表一插層效果（層間距離）及複合物之組成 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 插層劑 D2000 D4000 T3000 T5000 D230 D400 分子量 2000 4000 3000 5000 230 400 插層劑/ 黏土 重量比 (w/w %) 63/37 72/18 76/24 84/13 0/100 23/77 35/65 層間距 離（A ) 58. 0 92. 0 62. 6 >92. 0 12· 4 · 15. 0 19. 4 D2000: poly(propylene glycol) bis(2-aminopropy1 ether) at 〜2000 Mw D4000: poly(propylene glycol) bis(2-aminopropy1 ether) at 〜4000 Mw T3000 : tri-functional poly(propylene glycol)2-aminopropy1 ether at 3000 Mw T5000 : tri-functional poly(propylene glycol)2-aminopropy1 ether at 5000 Mw D230: poly(propylene glycol) bis(2-aminopropy1 ether) at -230 Mw D400: polyCpropylene glycol) bis(2-aminopropyl ether) at -400 Mw w/w :插層劑與黏 土之比例乃由Thermal Gravimelric Analysis (T G A) 儀器準確測出。 15 550246 表二插層劑對C E C之比例與複合物組成及層間距之影響* 實施例1 實施例5 實施例6 比較例4 比較例5 D2000莫耳數/ 黏土 CEC 1:1 3:2 2:1 1:5 1:2 插層劑/黏土 重量比（w/w %) 63/37 64/36 65/35 35/65 52/48 層間距離（人） 58 58 59 19 19550246 at B7 V. Description of the invention (丨 ϋ Open the interlayer distance to 5 8 Α. At this time, increasing the amount of intercalating agent can not increase the interlayer distance. This is because D2 0 0 0 in the interlayer has formed a good arrangement. Moreover, D2000 outside the clay can no longer be introduced into the clay interlayer by cation exchange. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Other chart description] Figure 1 Analysis by X-ray diffraction (x-ray di f fraction), the distance between layers It has a linear relationship with the molecular weight of the intercalating agent. Figure 2 As far as the intercalating agent D2000 is concerned, the interlayer distance of the clay increases from 12. 4 A to 58 A, and a regular queue is formed between the clay layers, which is reached in χ light diffraction. The crystalline diffraction peak of η = 5, which shows a very regular structure. Figure 3. The clay surface is negatively charged due to lattice defects, and the intercalating agent forms a positively charged quaternary ammonium salt after acidification. At the concentration (> 15 wt%), the pseudo-crosslinking state is generated due to the suction bow of the positive and negative charges. MMT-D2 0 0 0 In toluene, when the roll is greater than 3%, its viscosity increases significantly. The surface of natural clay It is hydrophilic so it can be dispersed evenly In water, it is incompatible with most organic solvents. The modified clay is partially non-polar due to the introduction of organic molecules and is compatible with organic solvents. After the modified clay is subjected to ultrasonic vibration, Observe the stability of dispersion. Organic / f-tail-free + # 'φ & mu ^ water structure and non-polarity prepared from polypropyl-bonded bisamine intercalated inorganic clay. (CNS) A4 specifications (210X297 also centimeters) f / (Please read the precautions on the back before filling this page) A7 550246 ^ ___ B7 V. Description of the invention (丨 丨) Oil-wet structure, therefore, it shows excellent interfacial mixing ability As far as the modified clay (MMT_D2000) of D2 0 0 0 intercalated inorganic clay is concerned, the interfacial tension between toluene (Tolubne) and water can be reduced from 365 dyne / cm to 1.5 dyne / cm, and appears The critical cell concentration of very low concentration is around 10 ppm. This special interface phenomenon will help the inorganic clay to be dispersed in both molecules and reach the nanometer scale. As can be seen from Figure 4, the problem T-D2000 and MMT-D4000 and non-ionic boundary on the market Compared with the surfactant Span 20 [sorbitan monolaurate, molecular weight 346], it can effectively reduce the interfacial tension of the toluene / water phase. (Please read the precautions on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives ^ This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 must be Chu) / 厶 550246 Table 1 Interlayer effect (distance between layers) and composition of the compound Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Intercalating agent D2000 D4000 T3000 T5000 D230 D400 Molecular weight 2000 4000 3000 5000 230 400 Intercalating agent / clay weight ratio (w / w%) 63/37 72/18 76 / 24 84/13 0/100 23/77 35/65 Interlayer distance (A) 58. 0 92. 0 62. 6 > 92. 0 12 · 4 · 15. 0 19. 4 D2000: poly (propylene glycol) bis (2-aminopropy1 ether) at ～ 2000 Mw D4000: poly (propylene glycol) bis (2-aminopropy1 ether) at ～ 4000 Mw T3000: tri-functional poly (propylene glycol) 2-aminopropy1 ether at 3000 Mw T5000: tri-functional poly (propylene glycol) 2-aminopropy1 ether at 5000 Mw D230 : poly (propylene glycol) bis (2-aminopropy1 ether) at -230 Mw D400: polyCpropylene glycol) bis (2-aminopropyl ether) at -400 Mw w / w: The ratio of intercalating agent to clay is determined by Thermal Gravimelric Analysis ( TGA) instrument to accurately measure. 15 550246 Table 2 Effect of intercalation agent on CEC ratio, composite composition and interlayer distance * Example 1 Example 5 Example 6 Comparative Example 4 Comparative Example 5 D2000 Molar Number / CEC 1: 1 3: 2 2 : 1 1: 5 1: 2 Intercalation agent / clay weight ratio (w / w%) 63/37 64/36 65/35 35/65 52/48 Distance between layers (person) 58 58 59 19 19
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