200946455 九、發明說明： 【發明所屬之技術領域】 本發明係關於製備有機修飾之層狀雙氫氧化物之方法。 其即：包含作為電荷-平衡陰離子之有機陰離子之層狀雙 氫氧化物。 【先前技術】 製備該有機修飾之層狀雙氫氧化物之方法一般係已知的 且一般係在水中進行。有機修飾，即電荷平衡陰離子一般 係從脂肪酸或其鹽中獲得。 該等方法中水的使用導致最終乾燥産物具有大量水且當 再分散於水中時形成鹼性懸浮液。傳統製備之層狀雙氫氧 化物當被摻雜於聚合基質時，其中大量水及鹼度可（例如） 藉由造成解聚合而改變所得材料之機械與物理性質。 脂肪酸之使用導致形成包含脂肪酸黏聚物之非均質懸浮 液。此係因為脂肪酸於水中之溶解度受限制且隨pH而降低 之事實且因為在製備層狀雙氫氧化物期間pH降低，因此該 製程期間脂肪酸之溶解度降低而導致脂肪酸黏聚且沉積在 反應器中。 為降低有機修飾之層狀雙氫氧化物中水之量及鹼度， WO 2007/065877在可與水互溶且可溶解至少5 g/Ι電荷平衡 陰離子前驅物之有機溶劑存在下製備層狀雙氫氧化物。然 而，水與有機溶劑之組合使用需要附加分離及純化步驟， 其使該方法相對複雜且經濟上吸引力較小。 【發明内容】 136674.doc 200946455 本發明之一目的係提供一種製備具有較低鹼度之 有機修飾之層狀雙氫氧化物之新穎方法，其係簡單且經濟 n 的另—目的係提供降低或甚至阻止黏聚物形成 、本發明之附加目的係進一步增加嵌入層狀雙氫氧 化物層間之有機陰離子之量。 5 的可以製備包含作為電荷平衡陰離子之有機陰離 子之有機修飾之層狀雙氫氧化物（LDH)之方法達成，該方 法包括下列步驟： ⑷製備包含二價金屬離子源、三價金屬離子源及水之水 性懸浮液或溶液及 w在m懸浮液或溶液中令該二價金屬離子源與該三 價金屬離子源反應以獲得層狀雙氫氧化物， 、、中在v驟⑻之别、期間或之後’於水性懸浮液或溶 液中添加有機酸及非離子界面活性劑，且其中非離子界面 活生劑之量係、基於有機酸與非離子界面活性劑總重量之 0.1至10重量〇/0。200946455 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for preparing an organically modified layered double hydroxide. That is, a layered double hydroxide containing an organic anion as a charge-balance anion. [Prior Art] The method of preparing the organically modified layered double hydroxide is generally known and generally carried out in water. Organic modifications, i.e., charge balancing anions, are generally obtained from fatty acids or salts thereof. The use of water in such processes results in a final dried product having a large amount of water and forming an alkaline suspension when redispersed in water. The conventionally prepared layered dihydrogen oxides, when doped into a polymeric matrix, wherein a large amount of water and alkalinity can change the mechanical and physical properties of the resulting material, for example, by causing depolymerization. The use of fatty acids results in the formation of a heterogeneous suspension comprising fatty acid cohesives. This is due to the fact that the solubility of fatty acids in water is limited and decreases with pH and because the pH is lowered during the preparation of the layered double hydroxide, the solubility of the fatty acid during the process is reduced to cause the fatty acid to coagulate and deposit in the reactor. . In order to reduce the amount of water and the alkalinity of the organically modified layered double hydroxide, WO 2007/065877 prepares a layered double in the presence of an organic solvent which is miscible with water and can dissolve at least 5 g/Ι charge-balance anion precursor. hydroxide. However, the combined use of water and organic solvents requires additional separation and purification steps which make the process relatively complex and less economically attractive. SUMMARY OF THE INVENTION 136674.doc 200946455 One object of the present invention is to provide a novel method for preparing an organically modified layered double hydroxide having a lower alkalinity, which is simple and economical. Even the formation of agglomerates is prevented, and an additional object of the present invention is to further increase the amount of organic anions intercalated between the layered double hydroxide layers. 5 can be prepared by a method comprising preparing an organically modified layered double hydroxide (LDH) as an organic anion of a charge-balanced anion, the method comprising the steps of: (4) preparing a source comprising a divalent metal ion, a source of a trivalent metal ion, and An aqueous suspension or solution of water and w in a m suspension or solution to react the source of divalent metal ions with the source of the trivalent metal ion to obtain a layered double hydroxide, wherein, in v (8), Adding an organic acid and a nonionic surfactant to the aqueous suspension or solution during or after, and wherein the amount of the nonionic interfacial surfactant is 0.1 to 10 weight based on the total weight of the organic acid and the nonionic surfactant. /0.
At在本發明之方法中使用有機酸與非離子界面活性劑組合 能製造出具有較低鹼度之層狀雙氫氧化物。即：當再溶解 於水中時’其等具有較低PH。此外，此方法較少遭受有機 酸黏聚且因此可獲得較高嵌入度。 在本發明之方法中，可同時或在不同階段分別添加有機 酸及非離子界面活性劑。在一實施例中，在添加有機酸之 前’將非離子界面活性劑加入懸浮液或溶液中。在另一實 施例中，同時添加非離子界面活性劑與有機酸之混合物。 136674.doc 200946455 在本發明之一實施例φ + ^ 在步驟（b)進行之前或， 於懸洋液或溶液中添加有機 ^ 以此方法，以一步驟製成有機修飾之層劑 -般使該方法更簡單且更快虱軋化物’其 亦設想在步驟（b)之前戋期門 人0 子只而壬“ 加部分有機酸及/或非離 子界面活性劑，且在形成層 户雕 分。層狀雙風氧化物之後添加剩餘部 進-步設想在步驟(b)之後添加有機酸及非離子界面活 =齊卜在此例中，將有機酸及非離子界面活 至 .在添加有機醆及非離子界面活 ，劑之别’此已製成之層狀雙氫氧化物較 虱氧化物、硝酸鹽、氣化物選自匕括 ^ ^ 化物磷酸鹽、膦酸鹽、 蟥酸鹽、硫酸鹽、硫酸氫 祕齡2 其合物之群之無機電荷平 衡陰離子，較佳係氫氧化物 其混人物m ^ f 1氣化物、溴化物及 丹此〇物’最佳係氫氧化物。 因此’本發明亦係關於製備包含作 有機㈣+ 十衡陰離子之 包括下列步驟·· 日狀雙氫氧化物之方法，該方法 0)製備水與包含選自包 Μ ^ 祜焱基硝酸鹽、磷酸鹽、膦酸 n酸鹽、硫酸鹽、硫酸氫鹽及南 電荷平衡陰離子之層狀雙氯氧化物之懸浮液及 (b)rr洋液中添加有機酸及非離子界面活性劑，界面活 十劑之量為基於有機酸與非離子界面活性劑總重量之 〇.1至10重量％。 J36674.doc 200946455 /離子界面活性劑係由非極性疏水部分連接於極性親水 p刀、及成之兩性分子。本發明之方法中所使用之非離子界 面活性劑中之疏水部分較佳係包含9_24，更佳係，最 佳係12-20個碳原子之直鏈或支鏈烴鏈。 適宜非離子界面活性劑之實例包括乙氧基化醇、乙氧基 化烷基酚、乙氧基化脂肪酸、山梨糖醇酯及其等之乙氧基 化衍生物、乙氧基化脂及油、乙氧基化胺、氧化乙烯-氧 耱 &丙烯共聚物、源自單·及多糖諸如统基聚葡萄糖普及甘 油S旨之界面活性劑。 較佳係乙氧基化界面活性劑，而乙氧基化醇係用於本發 明之方法中之最佳非離子界面活性劑。適宜乙氧基化非離 子界面活性劑較佳包含至少6個氧化乙烯部分，更佳係ι〇_ 25個氧化乙烯部分，最佳係15_25個氧化乙烯部分。 非離子界面活性劑一般係根據其等之hlb值分類。 HLB(親水·親脂平衡）值提供親水與親脂基團之相對比例之 ❿ 量度且係疋義為親水部分之重量％除以5，其等於下列方 程式： HLB=2〇xMhp/MW，其中Mhp係親水部分之重量且mw為 整個分子之分子重量。對於乙氧基化非離子界面活性劑， Mhp等於氧化乙烯部分之數量乘以其等分子量（44 g/m〇1)。 本發明之方法中欲使用之界面活性劑的HLB值較佳係至 少10 ’更佳係至少12，最佳係至少14。 本發明之方法中所使用之非離子界面活性劑之量係基於 有機酸與界面活性劑總重量之〇· 1至1 〇重量％(wt%) ^此量 136674.doc -9 - 200946455 較佳係至少0.2重景 〇 量Λ，更佳係至少〇.3重量％且最佳係至少 最祛/ 〇且車父佳係至多8重量％’更佳係至多5重量％且 最佳係至多4重量％。 隹離子界面活性射單獨或與其它非離子界面活性劑组 口或與離子界面活性劑諸如陰離子界面活性餘合使用、。 ，雖…、所有有機酸均可在本發明之方法中使用，但有機酸 較佳包含至少2個碳原子，更佳係至少8個碳原子，甚至更 佳係至v 1〇個兔原子且最佳係至少⑽礙原子。有機酸較 佳匕3至多1，〇〇〇個碳原子，更佳係至多5〇〇個碳原子甚 至更佳係至多1 〇〇個碳原子且最佳係至多5〇個碳原子。 尤其適且有機酸之實例係單羧酸諸如脂肪酸及松香基 酸。 在一實施例中，有機酸係具有8至22個碳原子之脂肪 酸該知肪酸可為飽和或不飽和。適宜脂肪酸之實例係辛 酉文、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、花生 酸、癸烯酸、棕櫚油酸、油酸、亞麻油酸、次亞麻油酸及 其混合物。 在本發明之另一實施例中，有機酸係松香基酸。松香係 源自天然源、易獲得且舆合成有機酸相比相對廉價。松香 天然源之普通實例係膠松香、木松香及松油松香。松香常 為各種不同常含有約20個碳原子之單羧酸三環松香酸之異 構物之懸浮液。各種松香酸之三環結構主要不同處係在於 雙鍵位置。通常而言，松香為包含左旋海松酸、新松脂 酸、長葉松酸、松脂酸、去氫松脂酸、角化·去氫松脂 136674.doc -10· 200946455 «At the combination of an organic acid and a nonionic surfactant in the process of the present invention, a layered double hydroxide having a lower alkalinity can be produced. That is, when it is redissolved in water, it has a lower pH. Moreover, this method is less subject to organic acid cohesion and thus a higher degree of embedding. In the process of the present invention, the organic acid and the nonionic surfactant may be added simultaneously or at different stages. In one embodiment, the nonionic surfactant is added to the suspension or solution prior to the addition of the organic acid. In another embodiment, a mixture of a nonionic surfactant and an organic acid is added simultaneously. 136674.doc 200946455 In an embodiment of the invention φ + ^ before the step (b) or in the suspension or the addition of organic liquid in the solution, in this way, in one step to make an organically modified layering agent - This method is simpler and faster to roll the product's. It is also envisaged that before step (b), the doorman will only add a portion of the organic acid and/or nonionic surfactant and form a layered engraving. After adding the remaining part of the layered double-wind oxide, it is assumed that the organic acid and the non-ionic interface are added after the step (b). In this example, the organic acid and the non-ionic interface are activated. And non-ionic interface activity, the difference between the agent's layered double hydroxide is more than the cerium oxide, nitrate, gasification selected from the group consisting of phosphate, phosphonate, citrate, sulfuric acid Salt, hydrogen sulphate, age 2, inorganic charge-balanced anion of the group of compounds, preferably hydroxides mixed with the character m ^ f 1 vapor, bromide and danthene's best hydroxide. 'The invention also relates to the preparation of an organic (tetra) + ten-balance anion The method comprises the following steps: a daily double hydroxide, the method 0) preparing water and comprising a selected from the group consisting of a ruthenium nitrate, a phosphate, a phosphonic acid n-acid salt, a sulfate salt, a hydrogen sulfate salt, and a south a layered double oxychloride suspension of a charge-balanced anion and an organic acid and a non-ionic surfactant added to the (b) rr aqueous solution, and the amount of interfacial activity is based on the total weight of the organic acid and the nonionic surfactant. 11 to 10% by weight J36674.doc 200946455 / Ionic surfactant is a non-polar hydrophobic moiety attached to a polar hydrophilic p-knife, and amphoteric molecule. Among the nonionic surfactants used in the method of the present invention Preferably, the hydrophobic portion comprises 9-24, more preferably a straight or branched hydrocarbon chain of 12-20 carbon atoms. Examples of suitable nonionic surfactants include ethoxylated alcohols, ethoxylated. Alkyl phenols, ethoxylated fatty acids, sorbitan esters and the like, ethoxylated derivatives, ethoxylated fats and oils, ethoxylated amines, ethylene oxide-oxonium oxides, propylene copolymers, From mono- and polysaccharides such as GTP The surfactant is preferably an ethoxylated surfactant, and the ethoxylated alcohol is the best nonionic surfactant used in the method of the invention. Suitable ethoxylated nonionic interfacial activity Preferably, the agent comprises at least 6 ethylene oxide moieties, more preferably ι _ 25 ethylene oxide moieties, preferably 15-25 oxyethylene moieties. Nonionic surfactants are generally classified according to their hlb values. The lipophilic balance value provides a relative ratio of hydrophilic to lipophilic groups and is expressed as the weight percent of the hydrophilic portion divided by 5, which is equal to the following equation: HLB = 2 〇 x Mhp / MW, where Mhp is hydrophilic Part of the weight and mw is the molecular weight of the entire molecule. For ethoxylated nonionic surfactants, Mhp is equal to the amount of ethylene oxide fraction multiplied by its molecular weight (44 g/m 〇 1). The surfactant used in the method of the present invention preferably has an HLB value of at least 10 Å, more preferably at least 12, and most preferably at least 14. The amount of the nonionic surfactant used in the method of the present invention is based on the total weight of the organic acid and the surfactant: 1 to 1% by weight (wt%) ^ This amount is preferably 136674.doc -9 - 200946455 At least 0.2 〇 〇 Λ, preferably at least 3 3% by weight and optimally at least 祛 / 〇 and the car is up to 8% by weight 'better 5% up to 5% by weight and optimally up to 4 weight%. The ruthenium ion interface is used alone or in combination with other nonionic surfactant groups or with an ionic surfactant such as an anionic interface. Although all organic acids can be used in the process of the invention, the organic acid preferably comprises at least 2 carbon atoms, more preferably at least 8 carbon atoms, even more preferably to v 1 兔 rabbit atoms and The best system is at least (10) hindering atoms. The organic acid is preferably 3 to more than 1, preferably one carbon atom, more preferably up to 5 carbon atoms or even more preferably up to 1 carbon atom and most preferably up to 5 carbon atoms. Examples of particularly suitable organic acids are monocarboxylic acids such as fatty acids and rosin acids. In one embodiment, the organic acid is a fatty acid having from 8 to 22 carbon atoms which may be saturated or unsaturated. Examples of suitable fatty acids are octanoic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, decenoic acid, palmitoleic acid, oleic acid, linoleic acid, linoleic acid, and mixtures thereof. In another embodiment of the invention, the organic acid is a rosin acid. Rosin is derived from natural sources, is readily available, and is relatively inexpensive compared to synthetic organic acids. Rosin Natural examples of natural sources are gum rosin, wood rosin and pine oil rosin. Rosin is often a suspension of various isomeric structures of monocarboxylic acid tricyclic rosin acids which often contain about 20 carbon atoms. The main difference between the various tricyclic structures of rosin acids lies in the double bond position. In general, rosin contains L-conic acid, neo-rosin, long-leafed acid, rosin acid, dehydroabietic acid, keratinized dehydrogenated rosin 136674.doc -10· 200946455 «
酸、四氫松脂酸、海松酸及異海松酸之物質之懸浮液。源 自天然源之松香亦包括松香，即尤其藉由聚合、異構化、 歧化 '氫化及與丙烯酸、酸酐及丙烯酸酯進行狄（耳士阿 (德爾）反應（Diels-Alder reactions)修飾之松香懸浮液。松香 亦可藉由引入有機基團、陰離子基團或陽離子基團而修飾 或化學改性。有機基團可為具有丄至仂個碳原子之經取代 或未經取代之脂族或芳香族烴。陰離子基團可為任何為熟 習此項技術者所知之陰離子基團，諸如羧酸鹽或磺酸鹽。 在一實施例中’有機酸為脂肪酸與松香之混合物。 本發明之方法中所使用之二價金屬離子源及三價金屬離 子源可為任何為熟習此項技術者所知之源。該等源包括二 價及/或三價金屬離子之可溶性鹽及不可溶或部分不可溶 之二價及三價金屬離子源或其混合物。 在本專利說明書之上下文中，「可溶性鹽（s〇lubie alts)」意扎在室溫下可完全溶解於水中且形成澄清溶液 之一價及二價金屬離子源。在本專利說明書中，術語「不 π 、或口P刀不可〉谷金屬離子源QI> parHaiiy insoluble metal 1〇n _rces)」意指在室溫下不能完全溶液 於水中而形成懸浮液之源。 金屬離子源之可溶性鹽之實例係硝酸鹽、氯化物、過氣 酸皿及鋁酸鹽。不可溶或部分不可溶二價及三價金屬離子 ^之實例係氧化物、氫氧化物及碳酸鹽。該等源較佳係不 可'合或。卩分可溶。二價及三價金屬離子源最佳係氧化物或 氫氧化物。 136674.d〇( 200946455 二價金屬離子之實例係Zn2+、Mn2+、Ni2+、Cq2+、A suspension of the acid, tetrahydroabietic acid, pimaric acid and isopimaric acid. Rosin derived from natural sources also includes rosin, i.e., by polymerization, isomerization, disproportionation, hydrogenation, and rosin modified with Diels-Alder reactions with acrylic acid, acid anhydride, and acrylate. Suspension. Rosin may also be modified or chemically modified by the introduction of an organic group, an anionic group or a cationic group. The organic group may be a substituted or unsubstituted aliphatic group having from 丄 to one carbon atom or The aromatic group may be any anionic group known to those skilled in the art, such as a carboxylate or a sulfonate. In one embodiment, the 'organic acid is a mixture of a fatty acid and a rosin. The divalent metal ion source and the trivalent metal ion source used in the method may be any source known to those skilled in the art. These sources include soluble salts of divalent and/or trivalent metal ions and are insoluble or Partially insoluble bivalent and trivalent metal ion source or mixtures thereof. In the context of this patent specification, "soluble salts (s〇lubie alts)" are completely soluble in water at room temperature and are shaped Clarifying one of the valence and the source of the divalent metal ion. In this patent specification, the term "no π, or a P-knife is not available", a grain metal ion source QI> parHaiiy insoluble metal 1〇n _rces) means at room temperature The solution cannot be completely formed in water to form a source of suspension. Examples of soluble salts of metal ion sources are nitrates, chlorides, peroxyacids, and aluminates. Examples of insoluble or partially insoluble divalent and trivalent metal ions are oxides, hydroxides and carbonates. Preferably, the sources are not capable of being combined. The mash is soluble. The divalent and trivalent metal ion sources are preferably oxides or hydroxides. 136674.d〇( 200946455 Examples of divalent metal ions are Zn2+, Mn2+, Ni2+, Cq2+,
Fe2+、Cu2+、Sn2+、Ba2+、rn2+s λ/Γ 2+ 3+ Ba Ca及叫。三價金屬離子之實Fe2+, Cu2+, Sn2+, Ba2+, rn2+s λ/Γ 2+ 3+ Ba Ca and called. Trivalent metal ion
例係 Al3、Cr3+、Fe3+ Γλ3+ μ 3+ ， X k、C〇、Mn、Ni3+、Ce3iGa3+。 在上述金屬離子中，較佳係Mg2+與A13+之組合。 不可溶或部分不可溶之適宜鎮源之實例係氧化鎖、氫氧 化鎮碳酸氫氧鎂、碳酸氫鎮、白雲石（dolomite)及海泡 石（sepiolite)。亦考量兩種或多種鎂源之組合。 不可办或。卩刀不可溶之鋁源通常係鋁的氫氧化物或氧化 物。此18源之實例係三氫氧化料如轉土（g—叫及三 Jc，石（bayerite)，偏氫氧化銘諸如水銘礦水銘石或針鐵 礦及為熟習此項技術者所知之過渡氧化鋁。 上述不可溶或部分可溶二價及三價金祕子源之使用比 鹽之使用更環境友好，因為其不會産生鹽性碎屑流。此 外，不可溶或部分可溶二價及三價金屬離子源（尤其係鎂 與鋁源）一般比對應鹽廉價。 在本發明之較佳實施例中’不可溶或部分可溶二價及/ 或二價金屬離子源（尤其係鎂及/或鋁源）係在步驟（b)之前 經過碾磨。在本發明之方法中，二價及/或三價金屬離子 源一般具有小於20 μπι之d50值及小於50 4111之(19〇值。較佳 係d50值小於15 μηι且d90值小於40 μιη，更佳係d5〇值小於 10 μιη且d90值小於30 μιη，甚至更佳係d50值小於8 μηι且 d90值小於20 μιη’最佳係d50值小於6 μιη且d90值小於1〇 μιη。利用熟習此項技術者所知之方法，例如根據 DIN 13320之雷射繞射測定粒徑分佈。此碾磨步驟使層狀雙 136674.doc 12- 200946455 氫氧化物的形成更快。若二價及三價金屬離子源係鎮及紹 源’其進一步可降低所得層狀雙氫氧化物中之雜質諸如水 馨土或水鎖石之量。 懸浮液或溶液中二價金屬離子源與三價金屬離子源之間 的反應可在約30°C至大氣壓力下懸浮液或溶液之彿點間之 溫度下進行。溫度一般係從40至120。(：，較佳係5〇至 l〇〇°C，最佳係60至90°C *然而，反應亦可在高於大氣壓 力之壓力及一般高於大氣壓力下懸浮液或溶液之沸點之溫 度下進行。壓力一般係從1 bar至200 bar，較佳係從2 bar 至150 bar，最佳係從3 bar至100 bar。在如此高壓下，可 使用100°C或更高’較佳係從1〇〇。〇至300°C，更佳從i10°c 至250°C ’最佳係從120°C至200°C之溫度。若使用高於正 常彿點之溫度，則施加的塵力一般係自生的。 懸浮液或溶液中二價金屬離子源與三價金屬離子源之間 的反應之所需時間係取決於溫度、壓力及使用金屬源，但 一般需約3 0分鐘至24小時，較佳係1 _6小時且最佳係2_4小 時。 若於已成形之LDH中添加有機酸及非離子界面活性劑， 則LDH、有機酸、非離子界面活性劑較佳係在約3 至大 氣壓力下懸浮液或溶液之沸點間之溫度下接觸。溫度一般 係從40至150°c ’較佳係50至120°C，最佳係從60至90°C。 壓力一般係從1 bar至ό bar，較佳係1至3 bar，且最佳係1 至2 bar。在高於！ bar之壓力下，可使用i〇(rc或更高，較 佳係100 C至150。〇，更佳係11〇。〇至i4〇°c，且最佳係 136674.doc 13 200946455 120°C至130°C之溫度。 加的壓力一般係自生的 若使用高於正 常沸點之溫度 則施 DH與有機酸及非離子界面活性 ._ _ 饮啊之所需時間#敢 決於溫度及壓力，但一般需约 ’、 八链吐I 飯需約2〇刀鐘至6小時，較佳係40 刀鐘至3小時且最佳係1 _2小時。 ^發明之方法可在缺少C〇2或碳酸醋之前驅物懸浮液中Examples are Al3, Cr3+, Fe3+ Γλ3+ μ 3+ , X k, C〇, Mn, Ni3+, Ce3iGa3+. Among the above metal ions, a combination of Mg2+ and A13+ is preferred. Examples of suitable town sources that are insoluble or partially insoluble are oxidative locks, hydroxide towns of magnesium hydrogencarbonate, hydrogencarbonate towns, dolomites and sepiolites. A combination of two or more magnesium sources is also contemplated. Do not do or. The aluminum source in which the file is insoluble is usually a hydroxide or oxide of aluminum. Examples of such 18 sources are tri-metal hydroxides such as soil transfer (g-called and three Jc, bayerite, partial hydrogen hydroxide such as Shui Ming Mine water Mingshi or goethite and known to those skilled in the art) Transitional alumina. The use of the above insoluble or partially soluble divalent and trivalent gold secret sources is more environmentally friendly than the use of salts because it does not produce a salty debris flow. In addition, it is insoluble or partially soluble. Divalent and trivalent metal ion sources (especially magnesium and aluminum sources) are generally less expensive than the corresponding salts. In the preferred embodiment of the invention 'insoluble or partially soluble divalent and/or divalent metal ion sources (especially The magnesium and/or aluminum source is milled prior to step (b). In the method of the invention, the source of divalent and/or trivalent metal ions generally has a d50 value of less than 20 μπι and less than 50 4111 ( 19 〇 value. Preferably, the d50 value is less than 15 μηι and the d90 value is less than 40 μηη, and the better d5 小于 value is less than 10 μηη and the d90 value is less than 30 μηη, even better, the d50 value is less than 8 μηι and the d90 value is less than 20 μιη 'The best system d50 value is less than 6 μιηη and the d90 value is less than 1〇μιη. Methods known to the skilled person, for example to determine the particle size distribution according to laser diffraction according to DIN 13320. This milling step makes the formation of the layered double 136674.doc 12-200946455 hydroxide faster. If bivalent and trivalent metals The ion source system and the Shaoyuan' further reduce the amount of impurities such as acacia or water-locked stone in the obtained layered double hydroxide. The source of the divalent metal ion and the source of the trivalent metal ion in the suspension or solution The reaction can be carried out at a temperature between about 30 ° C and atmospheric pressure at the point of suspension or solution. The temperature is generally from 40 to 120. (:, preferably from 5 〇 to l 〇〇 ° C, most Preferably, the reaction is carried out at a temperature above atmospheric pressure and at a temperature generally above the boiling point of the suspension or solution at atmospheric pressure. The pressure is generally from 1 bar to 200 bar, preferably. From 2 bar to 150 bar, the best is from 3 bar to 100 bar. Under such high pressure, it can be used at 100 ° C or higher 'best from 1 〇〇 to ° to 300 ° C, better from i10 °c to 250 °C 'The best temperature is from 120 ° C to 200 ° C. If using a temperature higher than the normal point, then The added dust is generally self-generated. The time required for the reaction between the divalent metal ion source and the trivalent metal ion source in the suspension or solution depends on the temperature, pressure and metal source used, but generally requires about 30. From minute to 24 hours, preferably 1 to 6 hours and optimal for 2 to 4 hours. If organic acid and nonionic surfactant are added to the formed LDH, LDH, organic acid, and nonionic surfactant are preferably attached. Contact at a temperature between about 3 and about the boiling point of the suspension at atmospheric pressure. The temperature is generally from 40 to 150 ° C 'preferably from 50 to 120 ° C, preferably from 60 to 90 ° C. The pressure is generally from 1 bar to ό bar, preferably from 1 to 3 bar, and the optimum is from 1 to 2 bar. Above! Under the pressure of bar, i 〇 (rc or higher, preferably 100 C to 150 is preferred, 〇, more preferably 11 〇. 〇 to i4 〇 °c, and the best system 136674.doc 13 200946455 120 ° C The temperature is up to 130 ° C. The applied pressure is generally self-generated. If the temperature above the normal boiling point is used, the DH and organic acid and non-ionic surfactants are applied. _ _ The time required for drinking # 敢 depends on temperature and pressure, However, it is generally required to have a 'eight-chain spit I meal for about 2 knives to 6 hours, preferably 40 knives to 3 hours and the best system is 1 _2 hours. ^The method of invention can be in the absence of C〇2 or carbonated Vinegar precursor suspension
進仃以確保無碳酸鹽併入層狀雙氫氧化物中作 陰離子。 W 由本發明之方法所得之有機修飾之層狀雙氫氧化物包含 作為電荷平衡陰離子之有機陰離子。在本中請案之上下文 中術》口電街平衡陰離子（charge-balancing anion)」係 指彌補晶狀LDH板之靜電荷不足之陰離子。由於LDH通常 具有層狀結構，所以電荷平衡陰離子可處於層間、層疊 LDH層之邊緣或外表面上。此處於層疊[DU層間之陰離子 係稱為嵌入離子。 由本發明之方法所得之有機修飾之層狀雙氫氧化物具有 對應通式： k+M^(〇H)2m+2n]x.-.bH2〇 ⑴ 之層狀結構 其中M2+為二價金屬離子諸如Zn2+、Mn2+、Ni2+、Co2+、 Fe2 、Cu2+、Sn2+、Ba2+ ' Ca2+、Mg2+，且最佳係 Mg2+， M係三價金屬離子諸如Al3+、Cr3+、Fe3+、Co3+ ' Mn3+ ' Nl 、Ce3+及Ga3+，且最佳係Al3+，m/n=l至10，較佳係1 136674.doc 200946455 至6’更佳係2至4，最佳係接近3’ b值在〇至l〇範圍内，一 般係2至6之值’常為約4之值，且χζ-係電荷平衡陰離子， 其至少部分源自有機酸。 一般而言’嵌入陰離子之總量之至少丨〇%，較佳係至 少30°/。’更佳係至少6〇% ’最佳係至少9〇%係源自有機酸 之有機酸。在較佳實施例中，嵌入陰離子χΖ·之總量之至 少10%，更佳係至少3〇%，甚至更佳係至少6〇%，最佳係 至少90%係源自脂肪酸或松香。 LDH可為此項技術中已知之任何晶形。若LDH為水滑 石’則水滑石可為（例如）具有3%、3h2、3Ri43r2層疊之 多型。 藉由本發明之方法所得之有機修飾之層狀雙氫氧化物係 尤其適宜在聚合基質中使用。在此聚合基質内，有機修飾 之層狀雙風氧化物可經脫層（deiaminated)或剝離 (exfolmted) »在本申請案之上下文中，術語「脫層 φ (delamination)」係定義為藉由ldh結構至少部分去層而降 低LDH顆粒之平均層疊度，藉此產生每體積包含明顯更多 個别LDH板之材料。術語「剝離（^化1丨以〇11)」係定義為完 全脫層，即垂直於LDH板方向中周期性消失，導致個別層 隨機分散在介質中，藉此導致層疊無序。 藉由觀察基質之位置及不對稱性-即d(001)-反射，由X-射線繞射（XRD)可觀察到脫層及層疊度。完全脫層（即剝 離）之特徵仍有分析性挑戰，但通常可由原LDH之非_(hk〇) 反射完全消失推斷出。 136674.doc -15· 200946455 該等層之次序及脫層程度可進一步以透射電子顯微術 (TEM)而形象化。 尤其當在聚合基質（例如，納米複合材料或塗層組合物） 中使用時，最好由本發明之方法製備之有機修飾之層狀雙 氫氧化物具有高於丨.5 nm之個別層間距。此使層狀雙氫氧 化物易於在聚合基質中操作，且其進一步可使層狀雙氫氧 化物易脫層及/或剝離，導致具有較佳物理性質之有機修 飾之層狀雙氫氧化物與聚合基質之混合物。層間距較佳係 至少1.5 nm，更佳係至少丨6 nm，甚至更佳係至少i 8 nm，最佳係至少2 ηπ^個別層間距可利用χ_射線繞射及 如上所述之透射電子顯微術（ΤΕΜ)測得。個別層間距包括 個別層之一板厚度。 【實施方式】 實例 普通程序1 在3,684克去礦物質水中混合626 8克氧化鎂（2〇出11〇4〇, 購自 Martin Marietta Magnesia Specialties LLC)及 485 3 克 氫氧化銘（AlumillF505，購自 Nyalc〇byAmsterdam)且碾 磨成平均粒徑（dw)小於2.5 μηΐβ將800克水置入配備有高 速授拌器之以油加熱之高壓鍋中。隨後將該高壓鍋加熱至 85 C，然後於反應器中置入8〇〇克經碾磨之漿液。關閉反 應器後，將混合物加熱至901 4小時以形成層狀雙氫氧化 物。 冷卻高壓鍋後，將250克去礦物質水及25〇克層狀雙氫氧 136674.doc -16 - 200946455 化物加入1升燒瓶中且在80-95°C下加熱且攪拌1.5小時。在 此溫度下，加入界面活性劑且於漿液置入劑量為65克之 Kortacid®PH05-(由 Oleon GmbH Germany供應之棕櫊酸與 硬脂酸之摻雜物）且再在80-95°C下攪拌漿液2小時。所得産 物係經離心且在80°C下隔夜乾燥。 上述程序步驟均在氮氣氛圍下進行。 普通程序2 在5,000克去礦物質水中混合678.0克氧化鎂（Zolitho 40, 購自 Martin Marietta Magnesia Specialties LLC)及 5 14.0克 氫氧化銘（Alumill F505，購自 Nyalco by Amsterdam)且碾 磨成平均粒徑（d5Q)小於2.5 μιη。將400克水置入配備有高 速攪拌器之以油加熱之高壓鍋中。隨後將該高壓鍋加熱至 90°C，然後於反應器中置入333克經碾磨之漿液。關閉反 應器後，將漿液加熱至120°C且於反應器中置入劑量包含 100克Kortacid®PH05及界面活性劑之混合物。在120°C下 攪拌漿液1.5小時。所得產物係經離心且在80°C下隔夜乾 燥。 上述程序步驟均在氮氣氛圍下進行。 實例1 在普通程序1之後，利用下列界面活性劑製備有機修飾 之層狀雙氫氧化物： 136674.doc •17- 200946455 界面活性劑 類型 HLB 十二基硫酸鈉 陰離子 Cl4-16烯磺酸鈉 陰離子 十二基苯磺酸鈉 陰離子 十三醇6 E01 非離子 11.3 癸醇3 EO 非離子 9.1 十六醇23 EO 非離子 16.1 硬脂醇16 EO 非離子 14.5 十六醇20 EO 非離子 15.7 硬脂醇20 EO 非離子 15.3 油醇10 EO 非離子 12.4 1具有6個氧化乙烯（EO)部分之乙氧基化物 普通程序1係利用基於脂肪酸與界面活性劑總重量之〇.5 至16重量％之量之彼等界面活性劑進行。已發現使用陰離 子界面活性劑會導致脂肪酸黏聚。用陰離子界面活性劑之 最佳結果係由Cw,6烯磺酸鈉獲得，但該等懸浮液仍包含 脂肪酸黏聚物且懸浮液之最終pH係高於8。 使用陰離子界面活性劑（(：14_16缔續酸納）與非離子界面活〇 性劑（十三醇6 EO)之組合可在黏聚程度上獲得一些改進， 但仍有黏聚存在。僅使用至多1〇重量％之非離子界面活性 劑導致進-步改進，尤其係當❹则值高於^非離子 界面活性劑時。此獲得絲聚物之均質懸浮液及pH在7與8 使用大於10重量％(基於脂 两s文與界面活性劑之總重量） 之量之非離子界面活性劑會導致發泡。 136674.doc •18- 200946455 實例2 普通程序2係利用硬脂醇16 EO作為界面活性劑而進行。 界面活性劑係以基於脂肪酸與界面活性劑總重量之2.5重 量％之量使用。獲得pH為8之均質LDH漿液。The enthalpy is introduced to ensure that no carbonate is incorporated into the layered double hydroxide as an anion. W The organically modified layered double hydroxide obtained by the process of the present invention comprises an organic anion as a charge-balancing anion. In the context of this case, "charge-balancing anion" refers to an anion that compensates for the lack of static charge in a crystalline LDH plate. Since LDH typically has a layered structure, the charge balancing anions can be on the edge or on the outer surface of the interlayer, laminated LDH layer. This is in the stack [the anion between the DU layers is called an intercalating ion. The organically modified layered double hydroxide obtained by the method of the present invention has a layered structure corresponding to the formula: k+M^(〇H)2m+2n]x.-.bH2〇(1) wherein M2+ is a divalent metal ion Such as Zn2+, Mn2+, Ni2+, Co2+, Fe2, Cu2+, Sn2+, Ba2+ 'Ca2+, Mg2+, and the best system Mg2+, M system trivalent metal ions such as Al3+, Cr3+, Fe3+, Co3+ 'Mn3+ 'Nl, Ce3+ and Ga3+, And the best is Al3+, m/n=l to 10, preferably 1 136674.doc 200946455 to 6' is better 2 to 4, the best system is close to 3' b value in the range of 〇 to l〇, generally A value of 2 to 6 'usually a value of about 4, and a χζ-series charge-balanced anion, which is at least partially derived from an organic acid. Generally, at least 丨〇% of the total amount of embedded anions is preferably at least 30°/. More preferably, at least 6% of the optimum is at least 9% by weight of an organic acid derived from an organic acid. In a preferred embodiment, at least 10%, more preferably at least 3%, even more preferably at least 6%, based on the total amount of the anionic oxime, is derived from the fatty acid or rosin. LDH can be any crystal form known in the art. If the LDH is hydrotalcite, then the hydrotalcite may be, for example, a polytype having a 3%, 3h2, 3Ri43r2 stack. The organically modified layered double hydroxide system obtained by the process of the invention is especially suitable for use in polymeric matrices. Within this polymeric matrix, the organically modified layered double wind oxide can be deionated or exfommed. » In the context of the present application, the term "delamination" is defined by The ldh structure is at least partially de-layered to reduce the average lamination of the LDH particles, thereby producing a material comprising significantly more individual LDH plates per volume. The term "peeling" is defined as complete delamination, i.e., periodically disappearing perpendicularly to the direction of the LDH plate, resulting in random dispersion of individual layers in the medium, thereby causing lamination disorder. The delamination and lamination were observed by X-ray diffraction (XRD) by observing the position and asymmetry of the substrate - d(001)-reflection. The feature of complete delamination (ie, stripping) still has analytical challenges, but is usually inferred from the complete disappearance of the non-(hk〇) reflection of the original LDH. 136674.doc -15· 200946455 The order of these layers and the degree of delamination can be further visualized by transmission electron microscopy (TEM). Particularly when used in a polymeric matrix (e.g., a nanocomposite or coating composition), the organically modified layered double hydroxides preferably prepared by the process of the present invention have individual layer spacings above 丨.5 nm. This facilitates the operation of the layered double hydroxide in the polymeric matrix, and further allows the layered double hydroxide to be easily delaminated and/or exfoliated, resulting in an organically modified layered double hydroxide having better physical properties. Mixture with a polymeric matrix. Preferably, the layer spacing is at least 1.5 nm, more preferably at least 丨6 nm, even more preferably at least i 8 nm, and preferably at least 2 ηπ^ individual layer spacing can utilize χ-ray diffraction and transmission electrons as described above Microscopy (ΤΕΜ) measured. The individual layer spacing includes the thickness of one of the individual layers. [Examples] Example General Procedure 1 Mix 626 8 g of magnesium oxide (2 〇 11 〇 4 〇, purchased from Martin Marietta Magnesia Specialties LLC) and 485 3 g KOH (Alumill F505, purchased from 3,684 g of demineralized water). Nyalc〇byAmsterdam) and milled to an average particle size (dw) of less than 2.5 μηΐβ. 800 g of water was placed in an oil-heated autoclave equipped with a high-speed agitator. The autoclave was then heated to 85 C and then 8 g of the milled slurry was placed in the reactor. After the reactor was closed, the mixture was heated to 901 4 hours to form a layered double hydroxide. After cooling the autoclave, 250 g of demineralized water and 25 g of layered dihydrogen 136674.doc -16 - 200946455 were added to a 1 liter flask and heated at 80-95 ° C and stirred for 1.5 hours. At this temperature, a surfactant was added and Kortacid® PH05- (a mixture of palmitic acid and stearic acid supplied by Oleon GmbH Germany) was placed in the slurry at a temperature of 80-95 ° C. The slurry was stirred for 2 hours. The resulting product was centrifuged and dried overnight at 80 °C. The above procedure was carried out under a nitrogen atmosphere. General Procedure 2 In a 5,000 gram demineralized water, 678.0 grams of magnesium oxide (Zolitho 40, available from Martin Marietta Magnesia Specialties LLC) and 5 14.0 grams of Hydroxide (Alumill F505, available from Nyalco by Amsterdam) were mixed and ground into average granules. The diameter (d5Q) is less than 2.5 μηη. 400 grams of water was placed in an oil-heated pressure cooker equipped with a high speed agitator. The autoclave was then heated to 90 ° C and then 333 grams of milled slurry was placed in the reactor. After the reactor was turned off, the slurry was heated to 120 ° C and a mixture containing 100 g of Kortacid® PH05 and a surfactant was placed in the reactor. The slurry was stirred at 120 ° C for 1.5 hours. The resulting product was centrifuged and dried overnight at 80 °C. The above procedure was carried out under a nitrogen atmosphere. Example 1 After the ordinary procedure 1, an organically modified layered double hydroxide was prepared using the following surfactant: 136674.doc • 17- 200946455 surfactant type HLB sodium dodecyl sulfate anion Cl4-16 sulfonate anion Sodium dodecyl benzene sulfonate anionic tridecyl alcohol 6 E01 Nonionic 11.3 sterol 3 EO Nonionic 9.1 Cetyl alcohol 23 EO Nonionic 16.1 Stearyl alcohol 16 EO Nonionic 14.5 Cetyl alcohol 20 EO Nonionic 15.7 Stearyl alcohol 20 EO Nonionic 15.3 Oleic Alcohol 10 EO Nonionic 12.4 1 Ethoxylate with 6 ethylene oxide (EO) fractions General Procedure 1 is based on the total weight of fatty acids and surfactants. 5 to 16% by weight These surfactants are carried out. The use of anionic surfactants has been found to cause fatty acid cohesion. The best results with anionic surfactants were obtained from sodium Cw,6 ene sulfonate, but the suspensions still contained fatty acid cohesives and the final pH of the suspension was above 8. The use of an anionic surfactant ((: 14_16 contiguous sodium) and a nonionic interfacial active agent (tridecyl alcohol 6 EO) can achieve some improvement in the degree of cohesion, but there is still cohesion. Use only Up to 1% by weight of the nonionic surfactant results in a further improvement, especially when the enthalpy is higher than the nonionic surfactant. This results in a homogenous suspension of the silk polymer and a pH greater than 7 and 8 used. A nonionic surfactant in an amount of 10% by weight (based on the total weight of the lipid and the surfactant) causes foaming. 136674.doc • 18- 200946455 Example 2 General procedure 2 uses stearyl alcohol 16 EO as The surfactant was used in an amount of 2.5% by weight based on the total weight of the fatty acid and the surfactant. A homogeneous LDH slurry having a pH of 8 was obtained.
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