TWI398405B - Process for preparing organically modified layered double hydroxide - Google Patents
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- TWI398405B TWI398405B TW095145444A TW95145444A TWI398405B TW I398405 B TWI398405 B TW I398405B TW 095145444 A TW095145444 A TW 095145444A TW 95145444 A TW95145444 A TW 95145444A TW I398405 B TWI398405 B TW I398405B
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Abstract
Description
本發明係關於製備經有機改質之層狀雙氫氧化物之方法。This invention relates to a process for the preparation of organically modified layered double hydroxides.
以下方法在此項技術中已知。The following methods are known in the art.
WO 99/35185揭示製備經有機改質之層狀雙氫氧化物(LDH)之方法，其中經由離子交換將有機陰離子引入LDH中。藉由將LDH懸浮於水中來進行離子交換，其後將懸浮液之pH值降低至小於4之值。接下來將有機陰離子添加至懸浮液中且將pH值調節至超過8之值。此方法相當複雜且一般提供含鹽廢液流。WO 99/35185 discloses a process for the preparation of organically modified layered double hydroxides (LDH) in which organic anions are introduced into the LDH via ion exchange. Ion exchange is carried out by suspending LDH in water, after which the pH of the suspension is lowered to a value less than 4. The organic anion is then added to the suspension and the pH is adjusted to a value above 8. This method is quite complex and generally provides a salty waste stream.
WO 00/09599描述包含有機陰離子作為***陰離子之LDH的製備。藉由使用二價及三價金屬離子之鹽(諸如鎂及鋁之氯化物鹽或鋁酸鈉)，可以各種方式製備此等經改質之LDH。WO 00/09599中所述之方法需要在廢液流中至少將部分終止之鹽，此並非所要的。應進一步注意，此等方法中所用之鹽相對昂貴。WO 00/09599 describes the preparation of LDH comprising an organic anion as an intercalating anion. Such modified LDHs can be prepared in a variety of ways by using salts of divalent and trivalent metal ions such as chloride or magnesium aluminate of magnesium and aluminum. The process described in WO 00/09599 requires at least a partially terminated salt in the waste stream, which is not desirable. It should be further noted that the salts used in such methods are relatively expensive.
總之，上述方法之經濟性顯現需要在經濟上更具吸引力且更為環保之方法。In summary, the economics of the above methods need to be economically more attractive and environmentally friendly.
因此，本發明之一目的在於提供一種製備經有機改質之層狀雙氫氧化物之更簡單且更環保的方法。Accordingly, it is an object of the present invention to provide a simpler and more environmentally friendly process for preparing organically modified layered double hydroxides.
該目的係由一種製備經有機改質之層狀雙氫氧化物之方法而達成，該層狀雙氫氧化物之個別層之間的距離大於1.5 nm且包含有機陰離子作為電荷平衡陰離子，該方法包含以下步驟：(a)製備包含二價金屬離子源及三價金屬離子源之前驅體懸浮液；(b)溶劑熱處理該前驅體懸浮液以獲得該層狀雙氫氧化物，其中在形成步驟(b)之層狀雙氫氧化物之前或期間或在形成該層狀雙氫氧化物之後添加有機陰離子，以便獲得經有機改質之層狀雙氫氧化物，其限制條件為去氧膽酸並非僅有的有機陰離子。The object is achieved by a method for preparing an organically modified layered double hydroxide having a distance between individual layers of greater than 1.5 nm and comprising an organic anion as a charge balancing anion. The method comprises the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source; (b) treating the precursor suspension with a solvent to obtain the layered double hydroxide, wherein the forming step Adding an organic anion before or during the layered double hydroxide or after forming the layered double hydroxide to obtain an organically modified layered double hydroxide, the restriction condition being deoxycholic acid Not the only organic anion.
該目的亦係由一種製備經有機改質之層狀雙氫氧化物之方法而達成，該層狀雙氫氧化物之個別層之間的距離大於1.5 nm且包含有機陰離子作為電荷平衡陰離子，該方法包含以下步驟：(a)製備包含二價金屬離子源及三價金屬離子源之前驅體懸浮液；(b)熱處理該前驅體懸浮液以獲得該層狀雙氫氧化物，其中在形成步驟(b)之層狀雙氫氧化物之前或期間或在形成層狀雙氫氧化物之後添加有機陰離子，以便獲得經有機改質之層狀雙氫氧化物，其限制條件為在步驟a)中，在添加二價金屬離子源之前，三價金屬離子源與有機陰離子在介於60℃與85℃之間的溫度下不反應歷時4至8小時，且隨後在90至95℃之溫度下進行步驟b)歷時4至8小時。The object is also achieved by a method for preparing an organically modified layered double hydroxide having a distance between individual layers of greater than 1.5 nm and comprising an organic anion as a charge balancing anion. The method comprises the steps of: (a) preparing a precursor suspension comprising a source of divalent metal ions and a source of trivalent metal ions; (b) thermally treating the precursor suspension to obtain the layered double hydroxide, wherein in the forming step Adding an organic anion before or during the layered double hydroxide or after forming the layered double hydroxide to obtain an organically modified layered double hydroxide, the restriction being in step a) Before the addition of the divalent metal ion source, the trivalent metal ion source and the organic anion do not react at a temperature between 60 ° C and 85 ° C for 4 to 8 hours, and then at a temperature of 90 to 95 ° C. Step b) lasts 4 to 8 hours.
本發明之方法中所用之二價金屬離子源及三價金屬離子源並非此等金屬離子之鹽，詳言之，此等源並非二價及三價金屬離子之氯化物或高氯酸鹽，或者若三價金屬離子為鋁，則此等源並非鋁酸鹽。應注意，此等源可部分溶解於懸浮介質中。The divalent metal ion source and the trivalent metal ion source used in the method of the present invention are not salts of such metal ions, and in particular, such sources are not chlorides or perchlorates of divalent and trivalent metal ions, Or if the trivalent metal ion is aluminum, then the source is not an aluminate. It should be noted that such sources may be partially soluble in the suspending medium.
二價及三價金屬離子源一般為二價或三價金屬離子之氧化物或氫氧化物。二價金屬離子之實例為Zn2＋ 、Mn2＋ 、Ni2＋ 、Co2＋ 、Fe2＋ 、Cu2＋ 、Sn2＋ 、Ba2＋ 、Ca2＋ 及Mg2＋ 。三價金屬離子之實例為Al3＋ 、Cr3＋ 、Fe3＋ 、Co3＋ 、Mn3＋ 、Ni3＋ 、Ce3＋ 及Ga3＋ 。本發明方法亦涵蓋在所製備之層狀雙氫氧化物中使用三種或三種以上的不同金屬離子。在此等金屬離子中，Mg2＋ 及/或Zn2＋ 與Al3＋ 之組合為較佳。合適鎂源之實例包括氧化鎂、氫氧化鎂、羥基碳酸鎂、碳酸氫鎂、白雲石及海泡石。氧化鎂為較佳。亦涵蓋兩種或兩種以上鎂源之組合。鋁源通常為鋁之氫氧化物或氧化物。鋁源之實例為三氫氧化鋁(諸如三水鋁石及三水鋁礦)、氧基氫氧化鋁(諸如軟水鋁石、水硬鋁石或針鐵礦)及過渡型氧化鋁，其均為熟習此項技術者所已知。The divalent and trivalent metal ion source is typically an oxide or hydroxide of a divalent or trivalent metal ion. Examples of divalent metal ions are Zn 2+ , Mn 2+ , Ni 2+ , Co 2+ , Fe 2+ , Cu 2+ , Sn 2+ , Ba 2+ , Ca 2+ , and Mg 2+ . Examples of trivalent metal ions are Al 3+ , Cr 3+ , Fe 3+ , Co 3+ , Mn 3+ , Ni 3+ , Ce 3+ , and Ga 3+ . The method of the present invention also encompasses the use of three or more different metal ions in the prepared layered double hydroxide. Among these metal ions, a combination of Mg 2+ and/or Zn 2+ and Al 3+ is preferred. Examples of suitable magnesium sources include magnesium oxide, magnesium hydroxide, magnesium hydroxycarbonate, magnesium hydrogencarbonate, dolomite and sepiolite. Magnesium oxide is preferred. Combinations of two or more sources of magnesium are also contemplated. The aluminum source is typically a hydroxide or oxide of aluminum. Examples of aluminum sources are aluminum trihydroxide (such as gibbsite and gibbsite), oxy aluminum hydroxide (such as boehmite, diaspore or goethite) and transition alumina, both of which are It is known to those skilled in the art.
在本發明方法中使用上述二價金屬離子源及三價金屬離子源提供一種更為環保之方法，因為即便在該方法所導致之廢液流中殘留鹽，但其量亦相當少。此外，二價及三價金屬離子源，且詳言之鎂源及鋁源，一般比生產層狀雙氫氧化物中通常所用之對應鹽便宜。另外，本發明方法一般較簡單，因為其需要較少步驟及/或無需廢液流之後續處理。此外，此等方法可在短得多的時間內進行，其又可導致與習知方法相比更高的經有機改質之層狀雙氫氧化物之生產速率。The use of the above-described divalent metal ion source and trivalent metal ion source in the process of the present invention provides a more environmentally friendly method because the amount of salt remains relatively small even in the waste stream resulting from the process. In addition, sources of divalent and trivalent metal ions, and in particular magnesium and aluminum sources, are generally less expensive than the corresponding salts typically used in the production of layered double hydroxides. Additionally, the process of the present invention is generally simpler because it requires fewer steps and/or does not require subsequent processing of the waste stream. Moreover, such processes can be carried out in much shorter times, which in turn can result in higher rates of organically modified layered double hydroxide production compared to conventional processes.
在本發明方法之一實施例中，將二價金屬離子源及/或三價金屬離子源活化，之後對包含兩種源之懸浮液進行熱處理或溶劑熱處理。術語"活化"係指活化二價及/或三價金屬離子源，因此增加其在該方法中之反應性；該活化例如可藉由乾式或濕式研磨及/或藉由酸處理來進行。活化金屬離子源之另一優勢在於在該方法期間形成顯著更少之雜質，諸如水鎂石或三水鋁礦)。以該方法獲得之產物中之該等雜質的減少或不存在具有以下額外優勢：在聚合基質中使用該產物可導致所得複合材料具有經改良之動力學及/或機械特性。In one embodiment of the method of the invention, the source of divalent metal ions and/or the source of trivalent metal ions is activated, followed by heat treatment or solvent heat treatment of the suspension comprising the two sources. The term "activation" refers to the activation of a source of divalent and/or trivalent metal ions, thus increasing its reactivity in the process; such activation can be carried out, for example, by dry or wet milling and/or by acid treatment. Another advantage of activating a source of metal ions is that significantly less impurities, such as brucite or gibbsite, are formed during the process. The reduction or absence of such impurities in the product obtained by this process has the additional advantage that the use of the product in a polymeric matrix can result in improved kinetic and/or mechanical properties of the resulting composite.
以本發明之方法製備之經有機改質之層狀雙氫氧化物的個別層之間的距離大於1.5 nm。此在該等經有機改質之層狀雙氫氧化物之使用中(例如若用於聚合基質中)具有優勢。在聚合基質中(例如在奈米複合材料或塗覆組合物中)，較大之層間距離使得在聚合基質中可易於處理本發明之層狀雙氫氧化物，且其進一步使得可易於使層狀雙氫氧化物分層及/或脫落，從而導致經改質之層狀雙氫氧化物與聚合物基質之混合物具有改良之物理特性。本發明LDH中之層間距離較佳為至少1.5 nm，更佳為至少1.6 nm，甚至更佳為至少1.8 nm且最佳為至少2 nm。如下文所述，可使用X光繞射及透射電子顯微法(TEM)測定個別層之間的距離。The distance between the individual layers of the organically modified layered double hydroxide prepared by the process of the invention is greater than 1.5 nm. This is advantageous in the use of such organically modified layered double hydroxides, for example in polymeric matrices. In a polymeric matrix (for example in a nanocomposite or coating composition), the greater interlayer distance allows easy handling of the layered double hydroxides of the invention in the polymeric matrix, and which further makes it easier to The double hydroxides are layered and/or detached, resulting in improved physical properties of the modified layered double hydroxide and polymer matrix mixture. The interlayer distance in the LDH of the present invention is preferably at least 1.5 nm, more preferably at least 1.6 nm, even more preferably at least 1.8 nm and most preferably at least 2 nm. X-ray diffraction and transmission electron microscopy (TEM) can be used to determine the distance between individual layers as described below.
在本發明之一較佳實施例中，在步驟(b)之前研磨或活化二價及/或三價金屬離子源且詳言之為鎂源及/或鋁源。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 μm之d50值及小於50 μm之d90值。較佳地，d50值小於15 μm且d90值小於40 μm，更佳地，d50值小於10 μm且d90值小於30 μm，甚至更佳地，d50值小於8 μm且d90值小於20 μm，且最佳地，d50值小於6 μm且d90值小於10 μm。可使用熟習此項技術者已知之方法(例如根據DIN 13320之雷射繞射法)測定粒度分佈。該研磨步驟使得層狀雙氫氧化物之形成可更快進行。若二價及三價金屬離子源為鎂源及鋁源，則可進一步減少雜質(諸如三水鋁礦或水鎂石)之量。In a preferred embodiment of the invention, the source of divalent and/or trivalent metal ions and, in particular, the source of magnesium and/or aluminum, is ground or activated prior to step (b). In the process of the invention, the source of divalent and/or trivalent metal ions generally has a d50 value of less than 20 μm and a d90 value of less than 50 μm. Preferably, the d50 value is less than 15 μm and the d90 value is less than 40 μm, more preferably, the d50 value is less than 10 μm and the d90 value is less than 30 μm, and even more preferably, the d50 value is less than 8 μm and the d90 value is less than 20 μm, and Most preferably, the d50 value is less than 6 μm and the d90 value is less than 10 μm. The particle size distribution can be determined using methods known to those skilled in the art, such as laser diffraction according to DIN 13320. This grinding step allows the formation of layered double hydroxide to proceed faster. If the divalent and trivalent metal ion sources are a magnesium source and an aluminum source, the amount of impurities such as gibbsite or brucite can be further reduced.
在本申請案之上下文中，術語"熱處理"及"熱"係指在30℃至前驅體懸浮液於大氣壓力下之沸點的溫度下處理前驅體懸浮液。若懸浮介質為水，則熱處理之溫度一般為30℃至100℃，較佳為40℃至95℃且最佳為50℃至90℃。In the context of this application, the terms "heat treatment" and "hot" refer to the treatment of a precursor suspension at a temperature from 30 ° C to the boiling point of the precursor suspension at atmospheric pressure. If the suspending medium is water, the heat treatment temperature is usually from 30 ° C to 100 ° C, preferably from 40 ° C to 95 ° C and most preferably from 50 ° C to 90 ° C.
另外，術語"溶劑熱處理"及"溶劑熱"係指在高於大氣壓力之壓力下及一般大於前驅體懸浮液在大氣壓力下之沸點的溫度下處理前驅體懸浮液。壓力一般為1巴至200巴，較佳為2巴至150巴且最佳為3巴至100巴。若懸浮介質為水，則溫度一般為100℃或更高，較佳為100℃至300℃，更佳為110℃至250℃且最佳為120℃至200℃。Additionally, the terms "solvent heat treatment" and "solvent heat" refer to the treatment of a precursor suspension at a pressure above atmospheric pressure and generally at a temperature greater than the boiling point of the precursor suspension at atmospheric pressure. The pressure is generally from 1 bar to 200 bar, preferably from 2 bar to 150 bar and most preferably from 3 bar to 100 bar. If the suspending medium is water, the temperature is generally 100 ° C or higher, preferably 100 ° C to 300 ° C, more preferably 110 ° C to 250 ° C and most preferably 120 ° C to 200 ° C.
適用於熱處理及溶劑熱處理之懸浮介質可為水、有機溶劑或其混合物。有機溶劑之合適實例包括醇類(諸如甲醇、乙醇、1－丙醇及異丙醇)及烷烴類(諸如戊烷、己烷及庚烷)及芳族烴類(諸如苯、甲苯及二甲苯)。用於本發明方法之尤其合適的溶劑為水。The suspending medium suitable for heat treatment and solvent heat treatment may be water, an organic solvent or a mixture thereof. Suitable examples of organic solvents include alcohols (such as methanol, ethanol, 1-propanol and isopropanol) and alkanes (such as pentane, hexane and heptane) and aromatic hydrocarbons (such as benzene, toluene and xylene). ). A particularly suitable solvent for use in the process of the invention is water.
本發明之方法可在前驅體懸浮液中無CO2 或任何碳酸鹽存在時進行，以便確認無碳酸鹽併入層狀雙氫氧化物中作為電荷平衡陰離子。此另外使得可將有機陰離子併入層狀雙氫氧化物中作為電荷平衡陰離子。For the methods of the invention may be any carbonate or CO 2 -free precursor in the presence of the suspension, to confirm carbonate-free layered double hydroxide is incorporated as a charge balancing anion. This additionally makes it possible to incorporate an organic anion into the layered double hydroxide as a charge balancing anion.
在本發明之一實施例中，在步驟(b)進行之前或同時將有機陰離子添加至前驅體懸浮液中。以此方式，一步製備經有機改質之層狀雙氫氧化物，此一般使得該方法更為簡單及快速，且因此更具經濟吸引力。In one embodiment of the invention, the organic anion is added to the precursor suspension prior to or simultaneously with step (b). In this way, the organically modified layered double hydroxide is prepared in one step, which generally makes the process simpler and faster, and therefore more economically attractive.
或者，在層狀雙氫氧化物形成之後添加有機陰離子，在該狀況下層狀雙氫氧化物主要包含羥基作為電荷平衡陰離子。作為電荷平衡陰離子之該羥基可易於由有機陰離子交換。Alternatively, an organic anion is added after the formation of the layered double hydroxide, and in this case, the layered double hydroxide mainly contains a hydroxyl group as a charge balance anion. The hydroxyl group as a charge balancing anion can be easily exchanged by an organic anion.
在本申請案之上下文中，術語"電荷平衡陰離子"係指補償結晶LDH薄片之靜電荷缺乏的陰離子。因為LDH通常具有層狀結構，所以電荷平衡陰離子可位於堆疊LDH層之夾層中、邊緣上或外表面上。位於堆疊LDH層之夾層中的該等陰離子係稱為***離子。In the context of this application, the term "charge-balancing anion" refers to an anion that compensates for the lack of static charge of crystalline LDH flakes. Since the LDH typically has a layered structure, the charge balancing anions can be located in the interlayer, on the edge or on the outer surface of the stacked LDH layer. The anions in the interlayer of the stacked LDH layer are referred to as intercalated ions.
例如，該堆疊LDH或有機黏土亦可在聚合基質中分層或脫落。在本說明書之上下文中，術語"分層"係定義為藉由使LDH結構至少部分脫層來降低LDH顆粒之平均堆疊度，藉此產生每體積含有顯著更多之個別LDH薄片的材料。術語"脫落"係定義為完全分層，亦即與LDH薄片垂直之方向上的週期性消失，導致個別層在介質中之隨機分散，藉此使得堆疊完全無次序。For example, the stacked LDH or organic clay may also delaminate or fall off in the polymeric matrix. In the context of this specification, the term "layering" is defined as reducing the average stacking of LDH particles by at least partially delaminating the LDH structure, thereby producing a material containing significantly more individual LDH flakes per volume. The term "shedding" is defined as complete delamination, i.e., periodic disappearance in the direction perpendicular to the LDH flakes, resulting in random dispersion of individual layers in the medium, thereby making the stack completely out of order.
可用X光繞射(XRD)觀測LDH之發脹或膨脹(亦稱為LDH之***)，因為底面反射(亦即d(001)反射)之位置表明層間距離，該距離在***時增加。X-ray diffraction (XRD) can be used to observe the swell or expansion of the LDH (also known as the insertion of LDH) because the position of the bottom reflection (i.e., d(001) reflection) indicates the interlayer distance, which increases at the time of insertion.
平均堆疊度之降低可觀察為XRD反射之拓寬(直至消失)或可由基底反射(001)之不對稱性增加而觀察到。The decrease in the average stacking degree can be observed as a broadening of the XRD reflection (until disappearing) or can be observed by an increase in the asymmetry of the substrate reflection (001).
對完全分層(亦即脫落)之表徵在分析上仍具挑戰性，但一般而言可根據自原始LDH之非(hk0)反射的完全消失來推斷。The characterization of complete stratification (ie, shedding) is still analytically challenging, but can generally be inferred from the complete disappearance of non-(hk0) reflections from the original LDH.
可進一步以透射電子顯微法(TEM)來觀測層之次序且因此獲得分層程度。The order of the layers can be further observed by transmission electron microscopy (TEM) and thus the degree of delamination is obtained.
本發明之LDH可為熟習此項技術者已知之任何LDH。此等LDH通常為可膨脹或發脹之礦物LDH。該等LDH具有包含帶電結晶薄片(亦稱為個別LDH層)之層狀結構，在該等薄片之間夾有電荷平衡陰離子。在本申請案上下文中之術語"膨脹"及"發脹"係指帶電結晶薄片之間距離的增加。可膨脹之LDH可在合適溶劑(例如水)中發脹，且可藉由以其他(有機)電荷平衡離子交換電荷平衡離子而進一步膨脹及改質，該改質在此項技術中亦稱為***。The LDH of the present invention can be any LDH known to those skilled in the art. These LDHs are typically mineral LDH that can swell or swell. The LDHs have a layered structure comprising charged crystalline flakes (also referred to as individual LDH layers) with charge balancing anions interposed therebetween. The terms "expansion" and "expansion" in the context of this application refer to an increase in the distance between charged crystalline sheets. The swellable LDH can swell in a suitable solvent, such as water, and can be further expanded and upgraded by ion exchange charge balancing ions with other (organic) charge balances, also known in the art. insert.
本發明之經有機改質之層狀雙氫氧化物具有對應於以下通式之層狀結構：
此項技術中已知之其他陰離子的實例包括氫氧根、碳酸根、碳酸氫根、硝酸根、氯離子、溴離子、磺酸根、硫酸根、硫酸氫根、釩酸根、鎢酸根、硼酸根、磷酸根、橋架化陰離子(諸如HVO4 －、V2 O7 4－ 、HV2 O12 4－ 、V3 O9 3－ 、V10 O28 6－ 、MO7 O24 6－ 、PW12 O40 3－ 、B(OH)4 － 、B4 O5 (OH)4 2－ 、[B3 O3 (OH)4 ]－ 、[B3 O3 (OH)5 ]2－ 、HBO4 2－ 、HGaO3 2－ 、CrO4 2－ 及Keggin離子)。Examples of other anions known in the art include hydroxide, carbonate, bicarbonate, nitrate, chloride, bromide, sulfonate, sulfate, hydrogen sulfate, vanadate, tungstate, borate, Phosphate, bridged anion (such as HVO 4 -, V 2 O 7 4- , HV 2 O 12 4- , V 3 O 9 3- , V 10 O 28 6- , MO 7 O 24 6- , PW 12 O 40 3- , B(OH) 4 - , B 4 O 5 (OH) 4 2- , [B 3 O 3 (OH) 4 ] - , [B 3 O 3 (OH) 5 ] 2- , HBO 4 2 - , HGaO 3 2- , CrO 4 2- and Keggin ions).
本發明之LDH包括水滑石及類水滑石陰離子性LDH。該等LDH之實例為水滑石及類水滑石材料、羥鎂鋁石、水鎂鋁石、菱水碳鐵鎂石、水碳鐵鎂石、菱水碳鉻鎂礦、水鎂鉻礦、水鋁鎳石、隕菱鐵鎳礦及水碳錳鎂石。較佳LDH為水滑石，其為具有對應於以下通式之層狀結構的LDH：
m/n較佳應具有2至4之值、更尤其為接近3之值。m/n should preferably have a value of 2 to 4, more particularly a value close to 3.
LDH可為此項技術中已知之任何晶體形式，諸如由Cavani等人(Catalysis Today,11(1991)，第173－301頁)或Bookin等人(LDHs and LDH Minerals,(1993)，第41(5)卷，第558－564頁)所述。若LDH為水滑石，則水滑石可為例如具有3H1 、3H2 、3R1 或3R2 堆疊之多型體。LDH can be in any crystal form known in the art, such as by Cavani et al. (Catalysis Today, 11 (1991), pp. 173-301) or by Bookin et al. (LDHs and LDH Minerals, (1993), pp. 41 ( 5) Volume, pp. 558-564). If the LDH is hydrotalcite, the hydrotalcite may be, for example, a polytype having a 3H 1 , 3H 2 , 3R 1 or 3R 2 stack.
本發明方法中所用之有機陰離子可為在***後提供本發明之經有機改質之層狀雙氫氧化物的任何有機陰離子。可適當用於本方法中之有機陰離子可衍生自有機陰離子之鹽或酸。使用諸如鹼金屬硬脂酸鹽之鹽來源有機陰離子可為有利的，此係歸因於其與對應酸來源有機陰離子相比在溶劑中之較高溶解性。或者，使用酸來源有機陰離子可為有利的，因為鹽離子將不引入廢液流中，使得廢液流無需額外處理以移除鹽離子，從而使該方法更為便宜且簡單。The organic anion used in the process of the invention may be any organic anion which provides the organically modified layered double hydroxide of the invention after insertion. The organic anion which may be suitably used in the process may be derived from a salt or an acid of an organic anion. It may be advantageous to use a salt-derived organic anion such as an alkali metal stearate due to its higher solubility in the solvent compared to the corresponding acid-derived organic anion. Alternatively, it may be advantageous to use an acid source organic anion because the salt ions will not be introduced into the waste stream so that the waste stream does not require additional processing to remove the salt ions, making the process less expensive and simpler.
適用於本發明方法中之有機陰離子一般包含8個或8個以上碳原子，其限制條件為作為電荷平衡陰離子存在之唯一有機陰離子並非對苯二甲酸根。具有至少8個碳原子之該等有機陰離子包括單、二或聚羧酸根、磺酸根、膦酸根及硫酸根。有機陰離子較佳包含至少10個碳原子、更佳為至少12個碳原子，且有機陰離子包含至多1,000個碳原子、較佳至多500個碳原子、更佳至多100個碳原子、甚至更佳至多50個碳原子且最佳至多20個碳原子。設想使用兩個或兩個以上有機陰離子(其中至少一者具有至少8個碳原子)，且所得LDH具有至少1.5 nm之層間距離，其他有機陰離子中之一者因此可具有少於8個碳原子。Organic anions suitable for use in the process of the invention generally comprise 8 or more carbon atoms, with the proviso that the only organic anion present as a charge balancing anion is not terephthalate. Such organic anions having at least 8 carbon atoms include mono-, di- or polycarboxylates, sulfonates, phosphonates and sulfates. The organic anion preferably comprises at least 10 carbon atoms, more preferably at least 12 carbon atoms, and the organic anion comprises up to 1,000 carbon atoms, preferably up to 500 carbon atoms, more preferably up to 100 carbon atoms, even more preferably up to 50 carbon atoms and optimally up to 20 carbon atoms. It is envisaged to use two or more organic anions (at least one of which has at least 8 carbon atoms) and the resulting LDH has an interlayer distance of at least 1.5 nm, one of the other organic anions may therefore have less than 8 carbon atoms .
僅包含1個選自由乙酸根、琥珀酸根、苯甲酸根及對苯二甲酸根組成之群之電荷平衡有機陰離子的經有機改質之LDH並非較佳，因為其具有小於1.5 nm之層間距離且一般不易於在聚合基質中脫落或分層，從而使得此等經改質LDH較不適用於(例如)奈米複合材料或塗覆組合物中。在US 5,728,366中給出該等經有機改質之LDH的實例。另外，具有去氧膽酸作為僅有的有機陰離子亦並非較佳，因為其過於昂貴。此外，去氧膽酸含有2個羥基，其可使得在聚合基質中之脫落或分層極為困難甚或不可能。咸信此係藉由一種橋架化行為所引起，該橋架化行為係歸因於兩種或兩種以上經***去氧膽酸陰離子之間的相互作用或歸因於與兩種不同黏土片層相互作用之單一去氧膽酸陰離子。在本發明之一實施例中，理想的是不使用去氧膽酸作為電荷平衡陰離子。An organically modified LDH comprising only one charge-balanced organic anion selected from the group consisting of acetate, succinate, benzoate and terephthalate is not preferred because it has a layer-to-layer distance of less than 1.5 nm and It is generally not easy to detach or delaminate in the polymeric matrix, making such modified LDH less suitable for use in, for example, nanocomposites or coating compositions. Examples of such organically modified LDHs are given in US 5,728,366. In addition, it is not preferred to have deoxycholic acid as the only organic anion because it is too expensive. In addition, deoxycholic acid contains two hydroxyl groups which can make detachment or delamination in the polymeric matrix extremely difficult or impossible. This is caused by a bridging behavior attributed to the interaction between two or more inserted deoxycholic acid anions or due to two different clay sheets. A single deoxycholate anion that interacts. In an embodiment of the invention, it is desirable not to use deoxycholic acid as the charge balancing anion.
進一步涵蓋電荷平衡有機陰離子包含一或多個諸如羥基、胺、羧酸及乙烯基之官能基。若在聚合基質中使用該等經有機改質之LDH，則此等官能基可與聚合物相互作用或反應。It is further contemplated that the charge balancing organic anion comprises one or more functional groups such as a hydroxyl group, an amine, a carboxylic acid, and a vinyl group. If such organically modified LDHs are used in a polymeric matrix, such functional groups can interact or react with the polymer.
本發明有機陰離子之合適實例為一元羧酸(諸如脂肪酸)及松香基離子。Suitable examples of organic anions of the invention are monocarboxylic acids (such as fatty acids) and rosin-based ions.
在一實施例中，有機陰離子為具有8至22個碳原子之脂肪酸或其鹽。該脂肪酸可為飽和或不飽和脂肪酸。該等脂肪酸之合適實例為辛酸、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。In one embodiment, the organic anion is a fatty acid having from 8 to 22 carbon atoms or a salt thereof. The fatty acid can be a saturated or unsaturated fatty acid. Suitable examples of such fatty acids are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, decenoic acid, palmitoleic acid, oleic acid, linoleic acid, linoleic acid and their mixture.
在本發明之另一實施例中，有機陰離子為松香或其鹽。松香係來源於天然來源，其易於獲得且與合成有機陰離子相比相對便宜。松香之天然來源的典型實例為松香膠、木松香及高油松香。松香通常為通常含有約20個碳原子之一元羧酸三環松香酸的多種不同異構體的懸浮液。各種松香酸之三環結構的主要差別在於雙鍵之位置。松香通常為包含左松脂酸(levopimaric acid)、新松香酸(neoabietic acid)、長葉松酸(palustric acid)、松香酸(abietic acid)、去氫松香酸(dehydroabietic acid)、二級去氫松香酸(seco－dehydroabietic acid)、四氫松香酸(tetrahydroabietic acid)、二氫松香酸、松脂酸(pimaric acid)及異松脂酸之物質的懸浮液。來源於天然來源之松香亦包括藉由聚合、異構化、歧化、氫化及與丙烯酸、丙烯酸酐及丙烯酸酯進行迪爾－阿德反應(Diels－Alder reaction)而經顯著改質之松香、亦即松香懸浮液。以此等方法所獲得之產物稱為經改質松香。天然松香亦可由此項技術中已知之任何方法加以化學改變，諸如使松香上之羧基與金屬氧化物、金屬氫氧化物或鹽反應以形成松香皂或鹽(所謂樹脂酸鹽)。該等經化學改變之松香稱為松香衍生物。In another embodiment of the invention, the organic anion is rosin or a salt thereof. Rosin is derived from natural sources and is readily available and relatively inexpensive compared to synthetic organic anions. Typical examples of natural sources of rosin are rosin gum, wood rosin and high oil rosin. The rosin is typically a suspension of a plurality of different isomers of a monocarboxylic acid tricyclic rosin acid, typically containing about 20 carbon atoms. The main difference between the various tricyclic structures of rosin acids is the position of the double bonds. Rosin usually contains levopimaric acid, neoabietic acid, palustric acid, abietic acid, dehydroabietic acid, secondary dehydroabietic rosin A suspension of a substance of seco-dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, pimaric acid, and isostearic acid. Rosin derived from natural sources also includes rosin which has been significantly modified by polymerization, isomerization, disproportionation, hydrogenation and Diels-Alder reaction with acrylic acid, acrylic anhydride and acrylate. This is the rosin suspension. The product obtained by such methods is referred to as modified rosin. Natural rosin can also be chemically altered by any method known in the art, such as reacting a carboxyl group on the rosin with a metal oxide, metal hydroxide or salt to form a rosin soap or salt (so-called resinate). These chemically altered rosins are referred to as rosin derivatives.
可藉由引入有機基團、陰離子基團或陽離子基團來對該松香進行改質或化學改變。有機基團可為具有1至40個碳原子之經取代或未經取代之脂族或芳族烴。陰離子基團可為熟習此項技術者已知之任何陰離子基團，諸如羧酸根或磺酸根。The rosin may be modified or chemically altered by introducing an organic group, an anionic group or a cationic group. The organic group may be a substituted or unsubstituted aliphatic or aromatic hydrocarbon having 1 to 40 carbon atoms. The anionic group can be any anionic group known to those skilled in the art, such as a carboxylate or sulfonate.
此等以松香為主之材料的其他細節可自D.F.Zinkel及J.Russell(在Naval Stores,production－chemistry－utilization,1989,New York，第II節，第9章中)及J.B.Class("Resins,Natural,"第1章："Rosin and Modified Rosins,"Kirk－Othmer Encyclopedia of Chemical Technology，線上公佈日期：2000年12月4日)收集。Additional details of such rosin-based materials are available from DFZinkel and J. Russell (in Naval Stores, production-chemistry-utilization, 1989, New York, Section II, Chapter 9) and JBClass ("Resins , Natural, "Chapter 1: "Rosin and Modified Rosins, "Kirk-Othmer Encyclopedia of Chemical Technology, online publication date: December 4, 2000).
亦涵蓋使用包含一或多種有機陰離子之本發明的LDH。在一實施例中，***陰離子為脂肪酸與松香之混合物。The use of the LDH of the invention comprising one or more organic anions is also contemplated. In one embodiment, the insertion anion is a mixture of fatty acid and rosin.
在本發明之LDH類型中，***離子總量之至少10%一般為有機陰離子，***離子總量之較佳至少30%、更佳至少60%且最佳至少90%為有機陰離子。在一較佳實施例中，***陰離子總量之至少10%為脂肪酸來源或以松香為主之陰離子或兩種陰離子之懸浮液，***離子總量之較佳至少30%、更佳至少60%且最佳至少90%為脂肪酸來源或以松香為主之陰離子或兩種陰離子之混合物。In the LDH type of the invention, at least 10% of the total amount of intercalated ions is typically an organic anion, preferably at least 30%, more preferably at least 60% and most preferably at least 90% of the total amount of intercalated ions are organic anions. In a preferred embodiment, at least 10% of the total amount of intercalated anions is a fatty acid source or a suspension of rosin-based anions or two anions, preferably at least 30%, more preferably at least 60% of the total amount of intercalated ions. Preferably, at least 90% is a source of fatty acids or an anion based on rosin or a mixture of two anions.
在以下實例中進一步說明本發明。The invention is further illustrated in the following examples.
市售脂肪酸依原樣使用。KortacidPH05(棕櫚酸與硬脂酸之摻合物)係由Oleochemicals GmbH(一家Akzo Nobel Chemicals公司)供應。Commercially available fatty acids are used as they are. Kortacid PH05 (a blend of palmitic acid and stearic acid) is supplied by Oleochemicals GmbH (a company of Akzo Nobel Chemicals).
將50公克氧化鎂(Zolitho40,ex Martin Marietta Magnesia Specialties LLC)及39公克三氫氧化鋁(Alumill F505)在648公克脫礦質水中混合且研磨至2.5 μm之平均粒度(d50 )。將漿液饋入配備有高速攪拌器之油加熱式高壓釜中並加熱至80℃。接著經15分鐘之時期將102公克KortacidPH05添加至高壓釜中。在添加之前，將脂肪酸摻合物加熱至80℃。在酸添加之後，關閉高壓釜且加熱至170℃並保持1小時。接著將高壓釜冷卻至約40℃且移除所得漿液。接著在2,000 rpm下離心漿液約10分鐘。傾析液體且在80℃下於烘箱中將固體真空乾燥隔夜。Will be 50 grams of magnesium oxide (Zolitho 40, ex Martin Marietta Magnesia Specialties LLC) and 39 g of aluminum hydride (Alumill F505) were mixed in 648 g of demineralized water and ground to an average particle size (d 50 ) of 2.5 μm. The slurry was fed into an oil-heated autoclave equipped with a high-speed stirrer and heated to 80 °C. Then 102 grams of Kortacid will be passed over a period of 15 minutes. PH05 was added to the autoclave. The fatty acid blend was heated to 80 °C prior to addition. After the acid addition, the autoclave was closed and heated to 170 ° C for 1 hour. The autoclave was then cooled to about 40 ° C and the resulting slurry was removed. The slurry was then centrifuged at 2,000 rpm for about 10 minutes. The liquid was decanted and the solid was vacuum dried overnight in an oven at 80 °C.
用X光繞射法分析包含脂肪酸摻合物之所得水滑石樣黏土以確定層間間距或d間距。如上文製備之水滑石樣黏土之XRD圖案顯示少量與水滑石相關之非(hk0)反射，此表明陰離子黏土之***。***物呈現29之特徵性d(001)值。The resulting hydrotalcite-like clay containing the fatty acid blend was analyzed by X-ray diffraction to determine the interlayer spacing or d-spacing. The XRD pattern of the hydrotalcite-like clay prepared as above showed a small amount of non-(hk0) reflection associated with hydrotalcite, indicating the insertion of an anionic clay. Insert presentation 29 Characteristic d(001) value.
藉由熔融中國松香膠(Chinese gum rosin)且將其加熱至235℃而於室內生產穩定松香。在熔融期間，添加以松香計3.5重量%之Vultac－2(Arkema Inc.)。將熔融松香在235℃下攪拌15小時，此後冷卻樹脂且備用。Stable rosin is produced indoors by melting Chinese gum rosin and heating it to 235 °C. During the melting, 3.5% by weight of Vultac was added in terms of rosin -2 (Arkema Inc.). The molten rosin was stirred at 235 ° C for 15 hours, after which the resin was cooled and set aside.
將50公克氧化鎂(Zolitho40,ex Martin Marietta Magnesia Specialties LLC)及39公克三氫氧化鋁(Alumill F505)在648公克脫礦質水中混合且研磨至2.5 μm之平均粒度(d50 )。將漿液饋入配備有高速攪拌器之油加熱式高壓釜中且在關閉後將其加熱至120℃。接著經30分鐘之時期將115公克如上製備之穩定松香添加至高壓釜中。在添加之前，亦將松香摻合物加熱至120℃。在酸添加之後，將高壓釜加熱至170℃並保持1小時。接著將高壓釜冷卻至約40℃且移除所得漿液。接著在2,000 rpm下離心漿液約10分鐘。傾析液體且在80℃下於烘箱中將固體真空乾燥隔夜。Will be 50 grams of magnesium oxide (Zolitho 40, ex Martin Marietta Magnesia Specialties LLC) and 39 g of aluminum hydride (Alumill F505) were mixed in 648 g of demineralized water and ground to an average particle size (d 50 ) of 2.5 μm. The slurry was fed into an oil-heated autoclave equipped with a high-speed stirrer and heated to 120 ° C after shutdown. Next, 115 g of the stabilized rosin prepared as above was added to the autoclave over a period of 30 minutes. The rosin blend was also heated to 120 °C prior to addition. After the acid addition, the autoclave was heated to 170 ° C and held for 1 hour. The autoclave was then cooled to about 40 ° C and the resulting slurry was removed. The slurry was then centrifuged at 2,000 rpm for about 10 minutes. The liquid was decanted and the solid was vacuum dried overnight in an oven at 80 °C.
用X光繞射法分析包含脂肪酸摻合物之所得水滑石樣黏土以確定層間間距或d間距。如上製備之水滑石樣黏土之XRD圖案顯示少量與水滑石相關之非(hk0)反射，此表明陰離子黏土之***。***物呈現23之特徵性d(001)值。The resulting hydrotalcite-like clay containing the fatty acid blend was analyzed by X-ray diffraction to determine the interlayer spacing or d-spacing. The XRD pattern of the hydrotalcite-like clay prepared as above showed a small amount of non-(hk0) reflection associated with hydrotalcite, indicating the insertion of an anionic clay. Insert presentation 23 Characteristic d(001) value.
將252公克氧化鎂(Zolitho40,ex Martin Marietta Magnesia Specialties LLC)及240公克三氫氧化鋁(Alumill F505)在3,513公克脫礦質水中混合且研磨至2.4 μm之平均粒度(d50 )。將部分此漿液(704公克)饋入配備有攪拌器、氮流及回流冷卻器之玻璃反應器中。將漿液加熱至90℃。接著經90分鐘之時期將147公克熔融Kortacid PH05(T＝90℃)添加至玻璃反應器中。將反應混合物在90℃下另外保持19小時且接著冷卻至低於50℃。接著在2,000 rpm下離心所得漿液約10分鐘。傾析液體且在80℃下於烘箱中將固體真空乾燥隔夜。Will be 252 grams of magnesium oxide (Zolitho 40, ex Martin Marietta Magnesia Specialties LLC) and 240 g of aluminum hydride (Alumill F505) were mixed in 3,513 g of demineralized water and ground to an average particle size (d 50 ) of 2.4 μm. A portion of this slurry (704 grams) was fed into a glass reactor equipped with a stirrer, a nitrogen stream, and a reflux cooler. The slurry was heated to 90 °C. 147 grams of molten Kortacid PH05 (T = 90 °C) was then added to the glass reactor over a period of 90 minutes. The reaction mixture was held at 90 ° C for an additional 19 hours and then cooled to below 50 °C. The resulting slurry was then centrifuged at 2,000 rpm for about 10 minutes. The liquid was decanted and the solid was vacuum dried overnight in an oven at 80 °C.
用X光繞射法分析包含脂肪酸摻合物之所得水滑石樣黏土以確定層間間距或d間距。如上製備之水滑石樣黏土之XRD圖案顯示少量與水滑石相關之非(hk0)反射，此表明陰離子黏土之***。***物呈現28之特徵性d(001)值。The resulting hydrotalcite-like clay containing the fatty acid blend was analyzed by X-ray diffraction to determine the interlayer spacing or d-spacing. The XRD pattern of the hydrotalcite-like clay prepared as above showed a small amount of non-(hk0) reflection associated with hydrotalcite, indicating the insertion of an anionic clay. Insert presentation 28 Characteristic d(001) value.
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| CN102030944B (en) * | 2009-09-25 | 2012-07-18 | 中国石油化工股份有限公司 | Scratch-resistant polypropylene composition and preparation method thereof |
| CN102030943B (en) * | 2009-09-25 | 2012-07-18 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| KR101130282B1 (en) * | 2009-10-26 | 2012-03-26 | 이화여자대학교 산학협력단 | Sepiocite Compound derived from Layered Double Hydroxide and Method for Preparing the Same |
| CN102009959A (en) * | 2010-09-10 | 2011-04-13 | 北京理工大学 | Preparation method of organic acid anion intercalation hydrotalcite |
| US9410031B2 (en) * | 2011-06-28 | 2016-08-09 | Flow Polymers, Llc | Organic functionalization of layered double hydroxides |
| JP6313751B2 (en) * | 2012-05-15 | 2018-04-18 | 株式会社ブリヂストン | Halogenated diene rubber for tires |
| ITUD20130030A1 (en) * | 2013-03-01 | 2014-09-02 | Sumeet Kumar | HYBRID COMPOSITE NANOMATERIALS |
| CN103359792B (en) * | 2013-07-22 | 2015-01-14 | 中国科学院青海盐湖研究所 | MgFe binary hydrotalcite-like compound with high iron content and preparation method thereof |
| EP2933300A1 (en) * | 2014-04-16 | 2015-10-21 | BASF Coatings GmbH | Composition based on layered hydroxides and polyesters, method for preparing the composition and its use |
| CN104192810B (en) * | 2014-08-15 | 2015-10-28 | 浙江大学 | A kind of preparation method of layered double-hydroxide of large interlamellar spacing |
| EP3245258B1 (en) * | 2015-01-06 | 2019-09-11 | Scg Chemicals Co. Ltd. | Sio2-layered double hydroxide microspheres and methods of making them |
| GB201502832D0 (en) * | 2015-02-19 | 2015-04-08 | Scg Chemicals Co Ltd And Scg Cement Co Ltd | Process for preparing small size layered double hydroxide particles |
| CN108430948B (en) * | 2015-12-18 | 2021-08-27 | 圣戈班石膏板公司 | Gypsum product composition, gypsum product and method of using compound in gypsum board |
| WO2018091894A1 (en) | 2016-11-15 | 2018-05-24 | Scg Chemicals Co., Ltd. | Surface modified layered double hydroxide |
| GB201703558D0 (en) * | 2017-03-06 | 2017-04-19 | Univ Oxford Innovation Ltd | catalysts |
| US10745606B2 (en) * | 2017-08-15 | 2020-08-18 | Saudi Arabian Oil Company | Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers |
| CN108948749A (en) * | 2018-07-06 | 2018-12-07 | 佛山市高明区爪和新材料科技有限公司 | A kind of bullet O-shaped rubber seal and preparation method thereof |
| CN110641118B (en) * | 2019-10-17 | 2021-07-27 | 厦门长塑实业有限公司 | High-barrier scratch-resistant biaxially oriented polyamide film and preparation method thereof |
| CN110639366B (en) * | 2019-10-26 | 2021-06-18 | 北京工业大学 | Method for preparing Fe-cage intercalated layered double hydroxide nanofiltration membrane |
| CN113493225B (en) * | 2021-08-11 | 2023-11-10 | 洛阳理工学院 | Preparation method and application of Co/Fe layered double hydroxide nanosheets |
| CN116162304A (en) * | 2023-03-02 | 2023-05-26 | 江苏馨德高分子材料股份有限公司 | Polyethylene sheath material prepared from modified montmorillonite and preparation method thereof |
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