TW200734275A - Process for preparing organically modified layered double hydroxide - Google Patents

Abstract

The invention relates to a process for preparing an organically modified layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising an organic anion as charge-balancing anion, the process comprising the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source;(b) solvothermally treating the precursor suspension to obtain the layered double hydroxide, wherein an organic anion is added before or during the formation of the layered double hydroxide of step (b), or following the formation of the layered double hydroxide, so as to obtain the organically modified layered double hydroxide, with the proviso that deoxycholic acid is not the sole organic anion.; The invention further pertains to a process for preparing an organically modified layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising an organic anion as charge-balancing anion, the process comprising the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source; (b) thermally treating the precursor suspension to obtain the layered double hydroxide, wherein an organic anion is added before or during the formation of the layered double hydroxide of step (b), or following the formation of the layered double hydroxide, so as to obtain the organically modified layered double hydroxide, with the proviso that in step a) the trivalent metal ion source is not reacted with the organic anion at a temperature of between 60 and 85 DEG C for 4 to 8 hours prior to the addition of the divalent metal ion source and step b) is subsequently carried out at a temperature of 90 to 95 DEG C for 4 to 8 hours.

Description

200734275 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for preparing a layered double hydroxide. [Prior Art] These methods are known in the art. Cavani et al. (Catalysis Today, 11 (1991), pp. 173-301) report various preparation methods for producing layered dihydrogen oxides. The exemplified preparation methods are all carried out in water.

Carlino (5WM / (10) /, 98 (1997), pp. 73-84) describes various preparation methods for mainly using an aqueous solution to insert a slow acid into a layered double hydroxide. Most of the methods used to prepare the layered double hydroxide are carried out in water, resulting in a final dried product containing a large amount of water. Moreover, an alkaline suspension is usually formed when a layered double hydroxide having a hydroxyl group or an organic anion as a charge balancing ion is redispersed in water. When a layered double hydroxide is incorporated into a polymeric matrix, the large amount of water and the degree of formation of the layered double hydroxide prepared by conventional methods may alter the mechanical and physical properties of the resulting composite, for example, blending may Lead to depolymerization. SUMMARY OF THE INVENTION [The present invention] It is an object of the present invention to provide a novel method for preparing layered double gas oxidation, whereby the degree of verification and/or water content in the final product can be reduced. The purpose of the further step is to provide a novel layered double hydroxide. This object is achieved by a process for preparing a layered dihydrogen emulsion comprising a charge-balancing anion comprising the steps of: (4) preparing a precursor suspension or solution '丨 comprising a divalent metal ion 116965.doc 200734275 a source, a source of trivalent metal ions, water, and a solvent miscible with water and capable of dissolving at least 5 g/l of charge-balanced anion precursor; (8) treating the precursor suspension or solution to obtain the layered dichloro-oxidation And the charge-balanced anion precursor is added to the suspension or solution before, during or after step (b), and wherein if the charge balance ion is an organic anion, then the charge balances the anion before (four) ^, the charge balance of less than 50% by weight is separated from the ~ sub-driver is a salt, the limitation is that the balance of the charge is not carbonate. A solvent in the process of the invention is relatively more capable of producing a relatively low di-containing: double hydroxide. The layered double hydroxide typically has improved thermal stability. The process of the invention is particularly suitable for the preparation of layered double hydroxides containing organic anions as charge balancing anions. The organically modified layered double hydroxides have a reduced alkalinity, and the 'swelling cone is known to be /, prepared in a self-conceived manner, ΓηΓ minus, #redistributed in (feed) water will have Compared with: depreciation. A higher degree of organic anion insertion can be achieved using the process of the invention: In general, a layered double gas oxide (and especially a = double hydroxide) will have an improvement with the polymer it is pushed into. In the process of the invention, the solvent may be miscible with water. And any solution in which at least 5 charge-correction anion precursors can be dissolved can be used. The water can be used depending on, the solubility of the e AA ° anion precursor, the pH of the substance, and/or Or temperature. In the process of the invention, 116965.doc 200734275 is selected such that, for example, at the reaction temperature, at least 5 g/1 of charge-balance anion is driven. Examples of such solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol; alkanol polyterpenes such as ethylene glycol 'propylene glycol and glycerol; Ethers such as dimethyl ether, diethyl ether or dibutyl ether; diethers of alkane polyols, dimercaptoethanol monoethyl glycol, dimercapto propylene glycol and diethyl propylene glycol; An alkoxylated alcohol of the formula

VIII RACVCs alkyl or phenyl, & hydrogen or methyl and up to the number; amines, such as triethylamine; nonionic polymerization solvent, such as polyethylene, polyacrylonitrile, lauryl Alcohol; ionic liquid; '• bite type; dimethyl sulfoxide; and pyrrolidone, such as η-methylpyrrolidone. In one embodiment, the solvent is a solvent that forms an azeotrope with water. The use of an azeotrope in the process of the invention makes it easier to remove the solvent and remove the water more efficiently. The solvent preferably has a leaven of _田#^& Examples of such alcohols are monoalcohols such as methanol, ethanol, n-propanol, 5%, n-butanol, isobutanol and tributyl, and alkoxylated alcohols as described above. In one embodiment of the invention, the fluorenyl hydrazinyl alcohol. Examples of such alkanoicated alcohols are ethanol 1~ lingsyl ether, ethylene glycol monoethyl ether, ethyl ketone to early n-propyl ether, ethyl bromide, isopropyl isopropyl ether, ethylene Alcohol monobutyl ether, 116965.doc 200734275 ethylene glycol mono-tert-butyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol 2-ethylhexyl ether, diethylene glycol single Methyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-isopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol single Ethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-telebutyl ether, propylene glycol monohexyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl ether, dipropylene glycol mono φ n-propyl ether, dipropylene glycol monoisopropyl ether and dipropylene glycol monobutyl ether. Among such alcohols, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether are less preferred because they are deformed and may cause health problems. The most preferred alkoxylated alcohols are propylene glycol monomethyl ether and propylene glycol monoethyl scale. Solvents are commercially available, for example, from Shell (0xitol/Pr〇xit® and D〇w (D_n〇1) and Union Carbide (Carbit〇l/Cell〇s〇lve). It is also envisaged to use two or more solvents. In the process of the invention, it is further contemplated to use another φ organic solvent which is immiscible with water and/or which can dissolve less than 5 g/1 of charge-balance anion precursor. Suitable examples of such organic solvents include alkanes such as pentane. , hexane and heptane; ketones such as decyl amyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; unsaturated acrylate Such as butyl acrylate, decyl methacrylate, hexamethylene propyl propylene and dimethyl propyl triacrylate; and aromatic hydrocarbons such as benzene, toluene and xylene. The amount of water and solvent used in the process of the invention may vary within wide limits. In one embodiment of the invention, less than 50% by weight, preferably less than 40% by weight, based on the total mass of water and solvent, And the best is less than 3 〇 weight 116965.doc 200734275 quantity % 0 the divalent gold used in the method of the invention The source of ions and the source of trivalent metal ions may be any source known to those skilled in the art. These sources include soluble salts of monovalent and/or divalent metal ions and insoluble or partially insoluble divalent and trivalent metal ion sources or Mixtures of the metal ion source include nitrates, gas salts, perchloric acid _ and methacrylates. Insoluble or partially insoluble divalent and trivalent metal ion sources generally include oxidation of divalent or trivalent metal ions. Or a hydroxide or a carbonate. The sources are preferably insoluble or partially soluble. Preferably, the source of one, one, and two metal ions is an oxide or hydroxide. In the context of the present application, "Soluble salt" means a source of divalent and trivalent metal ions that completely dissolves at room temperature and forms a clear solution. In the context of this application, the term 'insoluble salt or partially insoluble salt' means at room temperature It does not completely dissolve and forms a source of suspension. Examples of divalent metal ions are Zn2+, Mn2+, Ni2+, Cq2+, _Fe2+, Cy, Sn2+, Ba2+, Ca2+, and Mg2+. Examples are A1, Cr3+, Fe3+, Co3+, Mn3+, Ni3+, ce3+, and Ga3+. It is also contemplated to use three or more different metal ions in the layered double hydroxide prepared by the method of the present invention. Preferred combinations of Mg2+ and Al3+. Examples of suitable magnesium sources for insoluble or partially insoluble include magnesium oxide, magnesium hydroxide, magnesium hydroxycarbonate, magnesium hydrogencarbonate, dolomite (d〇1〇mite) and sepiolite. It is also expected to combine two or more kinds of magnesium sources. The insoluble or partially insoluble aluminum source is usually aluminum hydroxide or oxidized 116965.doc -10- 200734275 The example of this source is dijing Ming (such as Sanbi Mingshi (gibbsite) and three $bayerite, aiuininiurn 〇x〇hydroxide (such as boehmite, diasp〇re or goethite) Goethite)) and transition alumina, which are known to those skilled in the art.

The use of the above insoluble or partially soluble divalent metal ions and trivalent metal ions from the process of the present invention provides a more environmentally friendly process because less salt, if any, remains in the waste stream from the process. Moreover, divalent and divalent metal ion sources, and especially magnesium sources and aluminum sources, are generally less expensive than the corresponding salts commonly used in the preparation of layered double hydroxides. Moreover, the process of the present invention is generally simpler because it requires fewer steps and/or does not require post treatment of the waste stream. Moreover, compared to conventional methods, such methods can be carried out in a much shorter period of time, which in turn leads to higher yields of organically modified layered double hydroxides. In a preferred embodiment of the invention, the insoluble or partially soluble divalent and/or divalent metal ion source and especially the magnesium source and/or aluminum source are ground prior to step 卬). 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 value of less than 50 pm2d9. Preferably, the d50 value is less than 15 pmad90 value is less than 40 μηη, more preferably, the d5〇 value is less than 10 μηι and the d90 value is less than 30 μηη, and preferably, the (four) value is less than 8 _ and the _ value is less than 20 μηι, and the best Ground, the d50 value is less than 6 μηη and the d9〇 value is less than ι〇μπι. The particle size distribution can be determined according to DIN 13320 using methods known to those skilled in the art, such as laser diffraction. This grinding step allows the formation of the layered double hydroxide to proceed more quickly. If the divalent and trivalent metal ion source is a magnesium source and an aluminum source, this step can further reduce the impurity content such as gibbsite or brucite 116965.doc 200734275 (brucite).

In the context of this application, the terms 'process' and 'processed', as in the treatment of step (b), refer to the treatment of the suspension at elevated temperatures. This treatment can be a heat treatment or a solvothermal treatment. In the context of this application, the terms "heat treatment" and "thermal method" refer to the treatment of a precursor suspension or solution at atmospheric pressure at a temperature between it and the precursor suspension or the boiling point of the solution. The temperature is usually 4 (rc to 12 (rc, preferably 5 〇. 〇 to 100 ° C and most preferably 60 ° C to 90 ° C. Again, the term "solvent heat treatment " &" with solvent heat "Method" means treating a precursor suspension or solution at a pressure above atmospheric pressure and at a temperature above the boiling point of the precursor suspension or solution at atmospheric pressure. The pressure is usually from 1 bar to 200 bar, preferably It is from 2 bar to 15 bar, and most preferably from 3 bar to _ bar. The temperature is usually loot or higher, preferably 1 〇〇. (: to 3 〇〇. 〇, more preferably litre to 25 ( TC, and most preferably 120. 〇 to 200. (: The process of the invention can be carried out in the presence of no c〇2 or any carbonate in the precursor suspension to ensure that no carbonate is incorporated into the layered double hydroxide The substance is equilibrated as an anion. ' ' The method of the invention is also suitable for preparing an organic anion as an electrolayered dichloride The layered bis(oxychloride) is referred to as "layered double hydroxide" or "organic clay (.rgan〇c(4)". In an embodiment, the organic anion is in the step (8) Simultaneous addition to the precursor suspension or solution. The organically modified layered double hydroxide is prepared in a step-by-step manner, which makes the method i simple and faster. Therefore more economical. 116965.doc 12 200734275

The electric Hehengheng yin and the dynasty may be the salt or acid or a mixture thereof of the metal or soil metal H and/or trivalent metal ion. In the present invention, a small (four) weight percent of the charge-balancing anion is introduced into the suspension in the form of a salt based on the total mass of the charge-balanced anion precursor. In order to reduce the amount of salt in the waste & it is preferred to use an organic anionic acid and a mixture of a divalent and/or trivalent 2 genus ion with an organic anion salt or an organic anion acid. The above description is based on the total mass of the charge-balanced anion precursor. The charge-balance anion of the weight % is used in the form of a salt, preferably less than 3% by weight. The charge-balance anion is a salt, and more preferably less than 1 〇% by weight of the charge is equal to the salt. It is also envisaged that no salt of charge-balanced anions will be present in the process of the invention to reduce the amount of salt in the waste stream and/or even in the final product. In one embodiment of the invention, the charge balancing anion is an organic anion. The organic anion precursor may be an alkali metal or alkaline earth metal salt or a salt or acid of a divalent and/or trivalent metal ion or a mixture thereof. The organic anion can be used in the above amounts. Suitable examples of the acid of the organic anion include acetic acid, succinic acid, terephthalic acid, benzoic acid, octanoic acid, citric acid, lauric acid, myristic acid, chlorpyrifos, sulphuric acid, citric acid, Decenoic acid, palmitoleic acid, oleic acid, lin〇leic acid, iin〇ienic acid, and rosin. It is also contemplated to add a portion of the organic anion before or during step (b) and to add the remainder after forming the layered double hydroxide. Or 'adding an organic anion after the formation of the layered double hydroxide, in which case the layered double hydroxide comprises a charge-balanced anion selected from the group 116965.doc • 13 - 200734275: hydroxide , nitrate, wrapper, bromide, phosphate, phosphonate, sulfonate, sulfate, sulfur & The present invention relates to the method as described above, and the one-step comprises the following steps: (〇 preparing a suspension medium and a layered double hydroxide suspension, a liquid, the layered double hydroxide comprising selected from the following a charge-balance anion of the composition of the eight yiyi: hydroxide, nitrate, phosphate, phosphonate, sulfonate, | sulfate, hydrogen sulfate and halide; (d) treating the suspension to obtain organic a modified layered double hydroxide, wherein the organic anion precursor is added during step (c) or (d). Preferably, the charge-balance anion of the layered double hydroxide used in step (C) It is selected from the group consisting of hydroxide, nitrate, gas ion, bromide ion or a mixture thereof. The charge-balancing anion can be easily exchanged with an organic anion. Compared to water used in a similar method, the exchange system By Φ is advantageously improved by the use of the solvent of the invention. Alternatively, the invention relates to a process for preparing a layered double hydroxide comprising an organic anion as a charge-balancing anion, the method comprising The following steps: (a) preparing a layered double hydroxide, a solvent and optionally a suspension of water, the layered double hydroxide comprising an electrohepatic anion selected from the group consisting of: hydroxide, Nitrate, phosphate, phosphonate, rhein, sulfate, hydrogen sulfate and halide; (b) treatment of the precursor suspension or solution to obtain layered double hydroxide H6965.doc -14- 200734275 Wherein 'the organic hypomixed 1 π sub-driver is attached to the step (hooking in the suspension, and wherein #, the goods < (added to, during the month, the sorghum / gluten can be miscible with water and gM organic Anionic precursor. The layered double hydroxide u flat milk used in at least 5 of Bailing solution is prepared according to the square double hydroxide of the present invention or the layer method prepared by the sound system. square

If the method of the present invention comprises the step of "equalizing anions and organics, from the early stage, and what matter" after the formation of the layered double gas oxide, the step of the formation and the exchange step may be performed by a thermal method or a solvothermal method, or The formation step can be used for the side, the sleeve, the financial method, and the exchange step is performed by the hydrothermal method, and vice versa. In the context of this application, the term "charge balance anion" An anion with insufficient static charge of the sheet. Since it usually has a layered structure', the charge-balanced anion can be located in the layer, on the edge or on the outer surface of the stacked ldh layer. The anion located in the interlayer of the stacked ldh layer is called an insertion. Ion. β Stacked LDH comprising organic anions or organic clays may also be layered or stripped, for example, in a polymeric matrix. In the context of this specification, the term, layered is defined as the at least partial delamination of the LDH structure. The reduction in the average stacking of the lDH particles results in a material containing significantly more individual LDH flakes per volume. Terminology, stripping &quot The system is defined as a complete stratification, that is, a periodic disappearance perpendicular to the direction of the LDH sheet, resulting in a random dispersion of the individual layers in the medium, thereby completely losing the stacking order. 116965.doc -15· 200734275 Swelling or swelling of LDH • Also known as the insertion of ldh - can be observed by Xenon diffraction (XRD) because the position of the bottom reflection (ie, d(〇〇1) reflection) indicates the distance between the layers, which increases at the time of insertion. The decrease can be observed as the broadening of the XRD reflection until it disappears or is observed by the increasing asymmetry of the bottom reflection (〇〇1). The characterization of the complete layering (ie, stripping) remains to be analyzed, but in general It can be performed according to the complete disappearance of the non-(hkO) reflection of the original LDH. The ordering of the φ layer and thus the stratification range can be further visualized by a transmission electron microscope (TEM). The LDH of the present invention can be familiar with this item. Any ldh known to the skilled artisan may only have different morphological and physicochemical properties. Typically, _ldh is a mineral LDH that can swell or swell. These LDHs contain charged crystalline flakes (also known as individual LDH layers) and a layered structure of charge-balanced anions entrained therein. The terms "expansion" and "swell up" are in the context of the present application an increase in the distance between the privately-charged crystalline sheets. The swell can be adapted to the solvent (eg water) The medium melts up and can be further expanded and modified by exchanging charge balancing ions with other (organic) charge balancing ions, which is also referred to as insertion in the art. The invention further relates to the method obtained by the method of the invention Layered double hydroxide. The layered double hydroxide of the present month and especially the organically modified layered double hydroxide have a lower ratio than the layered double hydroxide prepared in water. Water content, reduced degree of inspection and improved thermal stability. The invention has improved compatibility with polymers and can be used in a wide range of polymers, especially when LDH is incorporated. 116965.doc • 16 · 200734275 ^ 6 Used in. In such cases, the resulting polymer will generally have a lower degree of depolymerization, a lower degree of discoloration, and/or a reduced degree of degradation of the antioxidant. Due to the lower alkalinity of the resulting organically modified layered double hydroxide, when applied to a sulfur condensation (slllfur-con (ienzation) rubber compound, compared to the unmodified layered double hydroxide, The effect of the focus time is reduced.

In one embodiment of the invention, an LDH having a morphology different from that of the conventional LDH can be prepared. The ratio of the average length to the diameter of the individual lamellae in the LDH or organically modified LDH (L/D ratio) may exceed 2 〇〇, preferably L/D ratio to 夕300, more preferably at least 5 〇〇, and even Good for at least 丨〇〇〇. The ratio can be determined using an electron microscope such as a scanning electron microscope (sem) and/or TEM. The length is the maximum size of the platelets in the direction perpendicular to the stacking direction, and the diameter refers to the thickness of the clay particles in the stacking direction. If the clay is layered and/or peeled off, the diameter can be as large as the thickness of one layer. The layered double hydroxide of the present invention has a layered structure corresponding to the following formula, [M; Mn3 + (〇H) 2m + 2n JXn /; - bH20 (|) wherein M2+ is such as Zn2+, Mn2+, Ni2+, a divalent metal ion of c〇2+, Fe2+, Sn2+, Ba2+, Ca2+, Mg2+, m3+ is a trivalent metal ion such as ai3+, \N~e3 + w + , m and η have such a ^^丨 to (7) The value, and b has a value in the range of 〇 to 1〇. X is a charge balancing anion known to those skilled in the art. The charge balancing anion can be an organic anion or an inorganic anion. It is envisaged to use one or 116965.doc • 17- 200734275 multiple organic anions and/or one or more inorganic anions. Examples of inorganic anions known in the art include: hydroxide, carbonate, bicarbonate, nitrate, chloride, bromide, sulfonate, sulfate, hydrogen sulfate, vanadate, tungstate, borate Phosphate; = pillaring anion, such as HV〇4-, V2〇74-, HV2〇i24-, V3, V1〇〇286-, Μ〇7〇2Λ, PWl2(V-, Β(〇Η)4·, B4〇5_429

[B3〇3(〇H)4]-, [B3〇3(OH)5]2·, _?·, HGa〇32_, (10) broad; and Kegghl ion. Preferably, the inorganic anion is selected from the group consisting of the following four substances: oxime, carbonate, hydrogencarbonate, lithothate, chloride, ion, % acid, sulfate, hydrogen sulfate or a mixture thereof . The organic anions used in the process of the invention are known to those skilled in the art: what organic anions. The organic anion which is suitable for use in the process of the invention can be derived from a salt or acid of an organic anion. The use of an organic anion derived from a salt of a metal salt such as stearic acid may be advantageous because it is more stable than the corresponding acid-derived organic anion in a solvent. Alternatively, the use of salt ions will not be introduced into the waste stream = the waste stream does not require additional treatment to remove salt ions, making the process cheaper and simpler. 'The organic anions include ···, di- or poly-repulsive, acid, phosphonic acid and sulfuric acid. Preferably, the organic anion comprises at least 2 carbon atoms, more preferably at least 10 carbon atoms, and preferably at least 12 anatomical atoms' and the organic anion comprises up to a plurality of carbon atoms, preferably at most 5 〇0 More than 1 GG carbon atoms, and most preferably up to 50 carbons 116965.doc 200734275 The organically modified layered double hydroxide prepared by the method of the present invention preferably has a single layer of 1.5 nm or more. distance. This is advantageous in the use of such layered double hydroxides which have been organically modified X, for example if they are used in a polymeric matrix. In a polymeric matrix (e.g., in a nanocomposite or coating composition), the greater interlayer distance allows the layered dihydrogen oxyhydroxides of the present invention to be readily processed in a polymeric matrix' and which further renders layered dihydrogen The oxide is susceptible to delamination and/or exfoliation, resulting in improved physical properties of the modified layered double hydroxide and φ polymer matrix mixture. Preferably, the interlayer distance of the LDH of the present invention is at least 丨.5 nm, more preferably at least -6 nm, very preferably at least 1.8 nm, and most preferably at least 2 nm. The distance between the individual layers can be determined using a ray diffraction and a transmission electron microscope (TEM), as outlined above. It is further contemplated that the charge-balanced organic anion comprises one or more functional groups such as a trans-base, an amine, a citric acid, and an ethylene group. If such organically modified LDH is used in a polymeric matrix, the functional groups can interact or react with the polymer. A suitable example of an organic anion of Benbenming is a monobasic acid, such as a fatty acid, and a rosin-based ion. In one embodiment, the organic anion has from 8 to 22 carbon atoms to a fatty acid or a salt thereof. The fatty acid or a salt thereof may be a saturated or unsaturated fatty acid. Suitable examples of such fatty acids or salts thereof are derived from octanoic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, decenoic acid, palmitoleic acid, oleic acid, linoleic acid, sub- Linoleic acid and its mixtures. In another embodiment of the invention, the organic anion is rosin or a salt thereof. Rosin is obtained from natural sources and is readily available and relatively inexpensive compared to synthetic organic anions 116965.doc -19- 200734275. 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 mono-acid tricyclic rosin acid generally having about 2 carbon atoms. The three ring structure of various rosin acids differ mainly in the position of the double bond. Usually, the rosin contains lev〇pimaric acid, neoabietic acid, palustric acid, abietic acid, dehydr〇abietic acid, Dehydro-hydrogen pyridine rosinic acid (seco-dehydroabietic add), tetrahydroabietic acid, dihydr〇abietic acid, pharic acid and is〇pimaric acid a suspension of the substance. Rosin derived from natural sources also includes rosin, that is, a rosin suspension, which is especially by polymerization, isomerization, disproportionation, nitriding and Deer_Ade with acrylic acid, acid anhydride and acrylate ( Diels_Alder) The reaction was modified. The product obtained by these methods is called modified rosin. Natural rosin can also be chemically altered by any method known to those skilled in the art, such as the rosin group on rosin reacting with a metal oxide, metal hydroxide or salt to form a rosin soap or salt (so-called Resinate. These chemically modified rosins are called rosin derivatives. Rosin can be modified or chemically altered by introducing an organic group, an anionic group or a cationic group. The substituted or unsubstituted aliphatic or aromatic hydrocarbon is a hydrazine having a working carbon atom. The anionic group may be any anionic group known to those skilled in the art, such as a tallow or a sulphate.

Other details of the /equal scent-based materials can be found in ^^(10)^ and L 116965.doc -20- 200734275

Russe\\ (Naval Stores, production-chemistry-utilization, 1989, New York, Section II, Chapter 9) and J_B. Class(''Resins,Natural,''Chapter 1:''Rosin and Modified Rosins, '' 〇 / C/zemka/, online publication date: December 4, 2000). In one embodiment, the intercalated anion is a mixture of fatty acid and rosin. In general, at least 10% of the total amount of intercalated ions in the LDH type of the invention is an organic anion, preferably at least 30%, more preferably at least 60%, and most preferably at least 90%. In a preferred embodiment, at least 10% of the total amount of intercalated anions is a suspension of a fatty acid-derived anion or a rosin-based anion or both, preferably at least 30%, more preferably at least 60%, and most preferably at least 90% 0 The molar ratio of the charge-balance anion to aluminum contained in the LDH used in the preparation of the organically modified LDH may be any desired value. This ratio may range from 10:1 to 1:10, preferably from 5:1 to 1:5, and most preferably from 2:1 to 1:2. It is expected to use a ratio of 1. The LDH of the present invention includes hydrotalcite and hydrotalcite-like anionic LDH. Examples of such LDHs are hydrotalcite and hydrotalcite-like materials, meixnerite, manasseite, pyroaurite, sj6grenite, carbon magnesium chrome Sthottite, barbertonite, takovite, reevesite, and desautelsite. Preferably, the LDH is hydrotalcite, which is an LDH having a layered structure corresponding to the following general formula, 116965.doc -21 - 200734275 (II) [Mg^Aln3+(OH) 2m+2n K2/; -bH20 wherein m And n has a value such that 111/11 = 1 to 1 Torr (preferably, working to (eight), and 1^ has a value in the range of 0 to 10, usually a value of 2 to 6, and often a value of about 4. X is a charge balancing ion as described above. Preferred m/n should have a value of 2 to 4, more particularly a value close to 3. LDH can be any crystal form known to those skilled in the art, such as Cavani et al. (Catalysis Today, 11 (1991), pp. 173_3〇1) or B〇〇kir^A (LDHS and LDHMinerals, (1993) i4g(5), pp. 558-564). If LDH is hydrotalcite, the water The talc may be a polytype having, for example, a 3 Η, 3H2, 3R! or 3R2 stack. The LDH of the present invention can be used as a component in a coating composition, a (printing) ink formulation, and a binder viscosifying agent. Agent, resin-based composition, rubber composition, cleaning formulation, iron well fluid and cement, paste preparation, non-woven fabric, fiber, material body 1, oriented plastic fastener (10) (4) ㈣t), (former) study ceramic materials, and hybrid organic-inorganic composite material _, Ji Naimi as polymer composites. The LDH of the present invention can be further used in a polymerization reaction such as solution polymerization, emulsion polymerization, and suspension polymerization. Organic clay can be further used as a crystallization aid in semi-crystalline polymers such as polypropylene. The LDH of the present invention can be further used in applications where LDH and organic anions of separate functions can be combined, as in the papermaking process or detergent industry: and the LDH of the present invention can be used for pharmaceuticals, bombicides and/or Or a controlled release application of fertilizers' and can be used as an adsorbent for organic compounds (eg, stains, colorants, etc.). 116965.doc -22- 200734275 入天月$纟 relates to the nano-particles containing the polymer and the LDH of the present invention, wherein the LDH comprises an organic anion having at least 8 broken atoms and an organically modified coffee. The content of LDH with a relatively high degree of peeling or delamination' and micron-sized modification is generally lower

Or even zero. The fully exfoliated and/or layered LDH in the nanocomposite allows the material to be visible to light, and thus makes it suitable for optical applications. 0 Terminology "Nanocomposite" means at least one of these components A composite comprising an inorganic phase having at least one dimension in the range of from 1 to 1 GG nanometer is particularly suitable for use in the nanocomposite comprising a charge-balanced organic anion in the nanocomposite of the invention chemically altered A charge-balanced organic anion mixture that is more compatible or more reactive with the polymer matrix. This improves the interaction between the LDH and the polymer group f, resulting in improved mechanical properties and/or viscoelastic properties. More compatible organic anions may contain substituted or unsubstituted aliphatic or aromatic hydrocarbons having one carbon atom. Alternatively or additionally, at least one of the organic anions may comprise a reactive group selected from the group consisting of acrylate, methacrylate, thiol, gas ion, amine, epoxide, thiol, Ethylene, disulfide and polysulfide, carbamate, ammonium, sulfonate, sulfinate, sparse, scale (Ph〇Sph〇nium), phosphonate, isocyanate, sulfhydryl, phenyl , hydride, ethoxylated and anhydride. The polymer which can be suitably used in the nanocomposite of the present invention can be any polymer matrix known to those skilled in the art. In the present specification, the term 116965.doc -23 - 200734275 π polymer" means that the scorpion has at least two building blocks (ie, monomers), and thus includes the contact of the contactor, the copolymerization Body and polymeric resin. Suitable for use in the matrix of the human body. The & 曰 曰 曰 为 为 为 为 为 为 为 为 为 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Preferably, the polymeric matrix has a degree of polymerization of 丨, 20, and more preferably at least 50. In this relationship, for the definition of degree of polymerization, see PJ ^ • Fl〇ry5 Principles of Polymer Chemistry^ New

York, 1953. Examples of suitable polymers are: polyolefins, such as polyethylene or polypropylene; vinyl polymers, #polystyrene, polymethyl methacrylate, polyethylene ethylene, ethylene oxide or polyethylene Difluoroethylene; saturated polyesters, such as polyethylene terephthalate, polylactic acid or poly(ε_hexine vinegar); unsaturated polyester resin, acrylic vinegar resin, methacrylic resin Classes, polyimines, epoxy resins, aged phthalic acid resins, urea formic acid resins, melamine formaldehyde resins, polyurethane resins, polycarbonates, polyaryl saponins, polythioethers , polyamines, polyether oximines, polyether vinegars, polyether ketones, polyether ketones, polyoxyalkylenes, polyamines, polyepoxides, and two or a blend of two or more polymers. Preferred are polyolefins, vinyl polymers, polyesters, polycarbonates, polyamines, polyurethanes or polyepoxides. The organic clay of the present invention is especially suitable for use in thermoplastic polymers such as polyethylene, polypropylene, polystyrene or acetal (co)polymers (such as polyoxymethylene 'ΡΟΜ); and rubber such as natural rubber (NR), styrene-butadiene rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), polyisobutylene rubber (IIR), halogenated polyisobutylene rubber 116965.doc -24 - 200734275 Glue, nitrile rubber (NBR), halogenated nitrile rubber (HNBR), styrene-isoprene-styrene rubber (SIS) and similar styrenic block copolymers, poly(gas alcohol) rubber ( CO, ECO, GPO), polyoxyxene rubber (Q), chloroprene rubber (CR), ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), polysulfide rubber (T), fluororubber ( FKM), ethylene vinyl acetate rubber (EVA), polyacrylate rubber (ACM), polynorbornene (PNR), polyurethane rubber (AU/EU), and polyester/ether thermoplastic elastomer. Particularly preferred are polymers or copolymers obtained by polymerizing at least one ethylenically unsaturated monomer. Examples of such polymers are polyolefins and modified polyolefins, which are known to those skilled in the art. The polyolefin or modified polyolefin can be a homopolymer or a copolymer. Suitable examples of such (modified) polyolefins are: polyethylene, polypropylene, polybutene, polystyrene, polyethylene oxide, polyvinylidene chloride, and ethylene-propylene rubber, propylene-butene copolymer , ethylene-gas ethylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-acrylate-styrene copolymer (AAS), methyl methacrylate - Butadiene-styrene copolymer (MBS), chlorinated polyethylene, chlorinated polypropylene, ethylene-acrylate copolymer, ethylene-propylene copolymer, and mixtures thereof. Very good polymers are polyethylene, polypropylene, polystyrene and polyethylene. Specific examples of the polyethylene are high density polyethylene, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, and ultra high molecular weight polyethylene. Examples of vinyl polymers are ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid methyl ketone 116965.doc -25- 200734275 copolymer (EMA) and Ethylene-acrylic acid copolymer (Eaa). The best t compound is polypropylene. Any polypropylene known in the art will be suitable for use in the present invention. Examples of polypropylenes are found in R b.

Liebe Yman (Kirk_Othmer Encyclopedia of Chemical Technology, online publication: December 4, 2000) "P〇lypropyiene,, Chapter j_", "Properties". One of the special types of polypropylene of the present invention is called Thermoplastic polyolefin (TPO) is formed, which includes a blend of polypropylene and rubber or a reactor grade. The nanocomposite of the present invention may further comprise additives commonly used in the art. Examples of such additives are Pigments, dyes, UV stabilizers, heat stabilizers, antioxidants, fillers (such as talc, chalk, lime, hydroxyapatite, vermiculite, carbon black, glass fiber, natural and synthetic polymeric fibers and other (organic) inorganic fillers ), flame retardant, nucleating agent, impact modified (4) plasticizer, rheology modifier, crosslinker, coupling agent and deaerator. The optional additives and their corresponding amounts can be as needed Preferably, the amount of LDH in the nanocomposite is preferably from 0.01 to 75% by weight, more preferably from 5 to 5 % by weight, even more preferably from 3 to 5% by weight, or less, based on the total weight of the mixture. Preferred 1 -1% by weight, more preferably 5% by weight of LM is particularly advantageous for the preparation of polymer based nanocomposites, that is to say. There is a boring layer - up to the stripping - organically modified LDH of the present invention The composition of the human body. The mouth is more than 1 〇 〇 〇 ❶ 更 更 更 更 更 更 更 更 尤 尤 尤 尤 尤 尤 尤 尤 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 116 .doc -26- 200734275 Premixes. Although the clay in these masterbatches is generally not fully layered and/or stripped, the masterbatch and other polymers are blended to obtain the true polymer base. In the case of a composite, further delamination and/or exfoliation may be achieved at a later stage. The nanocomposite of the present invention may be prepared according to any method known to those skilled in the art. Those skilled in the art may, for example, The polymer matrix is intimately mixed with the organic clay of the present invention by using a melt blending technique. This method is preferred because it is simple, cost effective, and easy to apply to existing equipment. Also contemplated as monomers and/or polymerizers. Before polymerization, to form a polymer matrix, simultaneously or The clay of the invention is then prepared in the presence of a polymer matrix or in the presence of monomers and/or oligomers. Additional details of the preparation and processing of the polypropylene can be found in RB Lieberman Wd-OAma 〇/C/zewka/仏(10)/%;;, published online: December 4, 2000) in ''Polypropylene'' Chapter 2 ''Manufacture''. The nanocomposite of the present invention can be used in the conventional use of such composite For any application of materials, nanocomposites can be suitably used in carpets, automotive parts, container closures, lunch boxes, covers, medical devices, household goods, food containers, dishwashers, outdoor furniture, blow molded bottles, Discarded non-woven fabrics, cables and wires, and packaging. Additional details on polypropylene can be found in RB· Lieberman (Kirk-Othmer Encyclopedia of Chemical Technology, online publication date: December 4, 2000) in "Polypropylene" Chapter 5 - ''Uses' and Basell titled ''Polypropylene: Textile, Rigid Packaging, Consumer, Film, Automotive, Electrical/Electronics and Home Appliances, pp. -27-116965.doc 200734275 booklet 022 PPe 10/01. Rubber-containing nanocomposites can be suitably used in tire manufacturing, such as green tires, truck tires, tractor tires, roads for construction machinery, tires and aircraft tires, for winter tires (wint^ hook; used for Latex products, including gloves, condoms, balloons, catheters, latex, foam, carpet backing and rubberized coir and hair, used in footwear, for civil engineering products, such as bridge support, Rubber·Metal_Laminated support; used in straps and hoses; used in non-tire automotive applications, including engine mounts, rubber supports, gaskets, grommet, gaskets and shields; used in wires and cables; And for pipe seals, medical closures, rollers, small solid tires, mounts for household and commercial appliances, rubber balls and tubular materials, milkers and other agricultural applications. If the rubber is polyoxyxene rubber and The modified layered double hydroxide is a modified layered double hydroxide according to the present invention, and the nano composite materials can be suitably used in coating products, including pressure sensitive adhesives, plastic hard coatings. And waterproof coating; used in fiber processing applications (including textiles) and hair care applications, sealants, adhesives, sealants, and solar cells. [Embodiment] The present invention is further illustrated by the following examples. Chemicals:

Kortacid® PH05 · a blend of palmitic acid and stearic acid supplied by Oleochemicals GmbH (a company of Akzo Nobel Chemicals).

Kortacid® PKGH: a blend of C12 to C22 fatty acids, from 116965.doc -28- 200734275

Oleochemicals GmbH (a company of Akzo Nobel Chemicals) is available. Dehydrogenated rosin: purchased from Hexion Specialty Products Hydrogenated rosin: Foral® AX-E, available from Eastman Chemical Prifac® 7990: Modified fatty acid (purchased from Uniqema) The following solvents were used: Isopropanol (bet from Acros)

Ethyl proxitol® : Ethoxypropan-2-ol (purchased from Shell)

Dowanol® DPNP: propoxy 2-methylethoxypropan-2-ol (purchased from Dow)

Chemicals)

Dowanol DPM: Dipropylene glycol methyl ether (available from Dow Chemicals)

Dowanol PMA: propylene glycol methyl ether acetate 酉I (available from Dow Chemicals)

Dowanol PPh · Propylene Glycol Phenyl Ether (available from Dow Chemicals)

Butyl Carbi to 1 : Diethylene glycol monobutyl ether (available from Acros) Example 1 20% by weight of hydrotalcite layered double hydroxide according to formula II having a Mg/Al ratio of 2 and a hydroxyl group as a charge-balance anion 250 g of the aqueous suspension and 250 g of isopropyl alcohol (available from Acros) were broken into a 1 liter glass reaction vessel equipped with a high speed stirrer and heated to 80 °C. Next, 90 grams of Kortacid® PH05 in 250 grams of isopropanol was added to the reaction vessel over 45 minutes. The fatty acid blend was heated to 80 °C prior to addition. After the acid addition, the reaction vessel was kept at 80 ° C for another 3 hours. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then centrifuged at 4000 rpm for about 20 minutes. The liquid was decanted and the solid was dried overnight at 80 ° C in a 116965.doc -29-200734275 oven under vacuum. The resulting hydrotalcite clay containing fatty acid blends was analyzed by X-ray diffraction to determine the inter-gallery spacing of 4 d-spacing. The xrd pattern of hydrotalcite clay prepared as described above shows a secondary hydrotalcite-related non-(hk0) reflection indicating the insertion of an anionic clay. The insert exhibits a characteristic d(〇〇l) value of 2Θ=1·72. The thermal decomposition starting point of the organically modified layered double hydroxide was 270 ° C as measured by thermogravimetric analysis (TGA). $ Example 2 20% by weight of a hydrotalcite layered double hydroxide of a hydrotalcite layered double hydroxide having a ratio of Mg/Al of 2 and a hydroxyl group as a charge-balanced anion, and 200 g of ethyl proxit〇 l (purchased from SheU) was broken into a 500 ml glass reaction vessel equipped with a high speed stirrer and heated to 8 〇t. This was then added to the reaction vessel at 7 g of K 〇rtaci # 1 > 11 〇 5 in 10 g of ethyl proxitol. The fatty acid blend is heated to 80 prior to addition. . . After the acid addition, the reaction vessel was heated while distilling off the hydrated pr〇xito1 azeotrope until it reached 130. The temperature of 〇. The reaction vessel was then cooled to about 5 Torr and the resulting slurry was removed. Then concentrate the material under 2,5 〇〇 willows for about ίο minutes. The liquid was decanted and the solid was dried in an oven at 8 Torr for 3 hours under vacuum. The resulting hydrotalcite clay containing fatty acid blends was analyzed by calender diffraction to determine the tunnel pitch or lattice spacing. The XRD pattern of the hydrotalcite clay prepared as described above shows the secondary hydrotalcite-related non-tank reflection, indicating that the anionic clay is inserted into the m-characteristic display 46^ characteristic d (howling 116965.doc -30· 200734275 example 3 20% by weight of a 34.5 gram aqueous suspension of hydrotalcite layered double hydroxide according to formula II, having a Mg/Al ratio of 2 and a hydroxyl group as a charge-balanced anion, and 200 gram of Dowanol DPNP broken into a high-speed stirrer 5 00 ml glass reaction vessel and heated to 80 ° C. Then add 7.5 g of Kortacid® PH05 in 10 g Dowanol DPNP to the reaction vessel over 15 minutes. Add the fatty acid blend to 80 before adding. After the acid addition, the reaction vessel was heated while distilling off the water/Dowanol DPNP mixture at a temperature of 130 ° C. The dry product was cooled to room temperature and the solid was dried in an oven at 80 ° C for 3 hours under vacuum. The XRD pattern of the hydrotalcite clay prepared above shows a minor hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. The insert exhibits a characteristic d(001) value of 47.0 A. Example 4 The amount % has a Mg/Al ratio of 2 and the hydroxyl group as a charge-balanced anion. 3 1.25 g of an aqueous suspension of hydrotalcite layered double hydroxide according to formula II and 200 g of Dowanol DPM broken into a high-speed stirrer 00 ml glass reaction vessel and heated to 80 ° C. Then 6.0 g of Kortacid® PKGH was heated to 80 ° C and added to the reaction vessel. After acid addition, the reaction vessel was heated while distilling off water at 130 ° C /Dowanol DPM mixture. The dry product was cooled to room temperature and the solid was dried in an oven at 80 ° C for 3 hours under vacuum. The XRD pattern of the hydrotalcite clay as described above shows the minor hydrotalcite-related non-(hkO Reflection, indicating the insertion of an anionic clay. The insert 116965.doc 31 200734275 shows the characteristic d(001) value of 32 A. Example 5 The basis of 20% by weight of a Mg/Al ratio of 2 and a hydroxyl group as a charge balancing anion 3 1.25 g of aqueous suspension of hydrotalcite layered double hydroxide and 200 g of Dowanol PMA were broken into a 500 00 glass reaction vessel equipped with a high-speed stirrer and heated to 80 ° C. Then 6.0 g Kortacid® PKGH was added to the reaction vessel. Prior to the addition, the fatty acid blend was heated to 80° C. After the acid addition, the reaction vessel was heated while distilling off the water/Dowanol PMA mixture at a temperature of 130° C. The reaction vessel was then Cool to about 50 ° C and remove the resulting slurry. The slurry was then centrifuged at 2,500 rpm for about 10 minutes. The liquid was decanted and the solid was dried in an oven at 80 ° C for 3 hours under vacuum. The XRD pattern of a hydrotalcite clay such as that described above shows a secondary hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. The insert shows a characteristic d(001) value of 48A. Example 6 3 1.25 g of an aqueous suspension of a hydrotalcite layered double hydroxide having a ratio of 2% by weight of Mg/Al and a hydroxyl group as a charge-balanced anion, and 200 g of Dowanol PPh were equipped with a high speed. The stirrer was placed in a 500 ml glass reaction vessel and heated to 80 °C. Next, 6.0 grams of Kortacid® PKGH was added to the reaction vessel. The fatty acid blend was heated to 80 °C prior to addition. After the acid addition, the reaction vessel was heated while distilling off the water/Dowanol PPh mixture at a temperature of 130 °C. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then centrifuged at about 4,000 116965.doc -32 - 200734275 rpm for about 10 minutes. The clear liquid was removed and the solid (slurry top) and gel (slurry bottom) were washed with acetone and under vacuum at 8 Torr. Dry in an oven for 3 hours. The XRD pattern of a hydrotalcite clay such as that described above shows a secondary hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. This insert shows the characteristic d(001) value of 29A. Example 7 0: 20% by weight of a hydrotalcite layered double hydroxide of a hydrotalcite layered double hydroxide having a ratio of Mg/Al of 2 and a hydroxyl group as a charge-balance anion; and a 200 gram of Butyl Carbitol It was placed in a 5 〇〇 ml glass reaction vessel equipped with a high speed stirrer and heated to 80 °C. Next, 0.000 grams of Kortacid® PKGH was added to the reaction vessel. The fatty acid blend was heated to 80 °C prior to addition. After the acid addition, the reaction vessel was heated while distilling off the water/Butyl Carbitol mixture at 12 (rc temperature. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then applied to 4, 〇〇〇 Centrifuge at rpm for about 1 〇 ^ minutes. Remove the clear liquid and solid (slurry top layer) and wash the gel (slurry bottom layer) with acetone and dry in an oven at 80 ° C for 3 hours under vacuum. The XRD pattern of a hydrotalcite-like clay shows a secondary hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. The insert exhibits a characteristic d(001) value of 30 A. Example 8 20% by weight with 2 The Mg/A1 ratio and the base as a charge-balanced anion are 3 丨·25 g of an aqueous suspension of a hydrotalcite layered double hydroxide such as Formula II and 200 g of Dowanol PPh are broken into a 116965.doc equipped with a high-speed stirrer. -33- 200734275 5 00 ml glass reaction vessel and heated to 8 (rc. Then add 9.75 grams of dehydrogenated rosin to the reaction vessel. Before adding, heat the rosin to 80 ° C. After acid addition, heat Reaction vessel, while at 13 〇 it warms The steam/Dowanol PPh mixture was steamed down. The reaction vessel was then cooled to about 50 C' and the resulting slurry was removed. The slurry was then centrifuged at 4, rpm for about 10 minutes. The clear liquid was removed and the gel was removed. (Slurry bottom layer) was washed with acetone and dried in an oven at 80 ° C for 3 hours under vacuum. φ XRD pattern of hydrotalcite clay prepared as described above showed secondary hydrotalcite-related non-(hkO) reflection, indicating anion Insertion of a clay. The insert exhibits a characteristic d(〇〇l) value of 25 A. Example 9 20% by weight of a hydrotalcite layer having a ratio of Mg/Al of 2 and a hydroxyl group as a charge-balanced anion according to formula π 62 5 g of an aqueous suspension of double hydroxide and 150 g of ethyl proxit® (purchased from Shell) were broken into a 500 ml glass reaction vessel equipped with a high-speed stirrer and heated to 85 〇. Then 4 • 06 g of Kwtaci # PKGH and 12.1 g of hydrogenated rosin were added to the reaction vessel. Before the addition, the fatty acid/rosin blend was heated to 85. In addition, 50 g of ethyl proxit〇i was added. After the admixture was added , heating the reaction bar, while The distillate/ethyi proxit〇i azeotrope was reached until the temperature reached 12. The reaction vessel was then cooled to about 5 〇〇c, 1 gram of ethyl proxito was added and the resulting slurry was removed. The mixture was centrifuged for about 10 minutes, and the liquid was decanted, and the solid was washed with acetone and dried in an oven at 80 ° C under vacuum overnight. The XRD pattern of the hydrotalcite clay prepared as described above shows the minor hydrotalcite 116965.doc -34- 200734275 correlated non-(hkO) reflection, indicating the insertion of an anionic clay. This insert shows the characteristic d(001) value of 29A. Example 10 20 wt% of an aqueous suspension of hydrotalcite layered double hydroxide having a ratio of Mg/Al of 2 and a hydroxyl group as a charge-balance anion according to formula II and 150 g of ethyl proxitol (purchased from Shell) ) Crush into a 500 ml glass reaction vessel equipped with a high speed stirrer and heat to 85. Hey. Next, 12.15 g of Kortacid 8 PKGH and 100 g of ethyl proxitol were added to the reaction vessel. The fatty acid blend was heated to 85 prior to addition. After the addition of the fatty acid admixture /ethyl proxitol, the reaction vessel was heated while distilling off the water/ethyl proxitol azeotrope until it reached 12 Torr. (: Temperature. An additional 100 grams of ethyl proxitol was added to the slurry. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then centrifuged at 2,5 rpm for about 10 minutes. The liquid was decanted, and the solid was washed with acetone and dried in an oven at 8 ° C for 6 hours under vacuum. The XRD pattern of the hydrotalcite clay prepared as described above shows the minor hydrotalcite-related non-(hkO) reflection. , indicating the insertion of an anionic clay. The insert exhibits a characteristic d(001) value of 28 A. Example 11 20% by weight of a hydrotalcite according to formula II having a Mg/Al ratio of 2 and a radical as a charge-balancing anion 62 5 g of an aqueous suspension of layered double hydroxide and 150 ml of 2-(2-ethylhexyloxy)ethanol were broken into a 500 ml glass reaction vessel equipped with a high-speed stirrer and heated to 85 Torr. Add ι215 grams of Kortacid® PKGH to the reaction vessel. Prior to addition, the fat 116965.doc -35- 200734275 fatty acid blend is heated to 85. After the fatty acid blend is added, the reaction vessel is heated while distilling off the water. /2_(2-ethylhexyloxy)ethanol The boiler is allowed to reach a temperature of 125 C. The reaction vessel is then cooled to about 5 Torr and the transferred slurry is removed. The slurry is then centrifuged at 4 Torr for about 1 Torr. The liquid is decanted. The solid was washed with acetone and dried under vacuum for 8 hours. The mixture was dried in an oven for 5 hours. The XRD pattern of the hydrotalcite clay prepared as described above showed a minor hydrotalcite φ related non-(hk0) reflection, indicating anionic Insertion of clay. The insert exhibits a characteristic d(〇〇i) value of 30 A. Example 12 A hydrotalcite layer according to formula II with 20 weights/〇 having a Mg/Al ratio of 2 and a hydroxyl group as a charge balancing anion 3 1.25 g of aqueous suspension of double hydroxide and 200 g of ethyi pr〇xit〇1 (purchased from SheU) were broken into a 500 ml glass reaction vessel equipped with a high-speed stirrer and heated to 85. 接着. Then 5.78 Ktacid Kortacid® PKGH and 0·28 gram of aminododecanoic acid were added to the reaction vessel. The fatty acid/aminododecanoic acid blend was heated to 85 ° C before addition. After the admixture was added , heating the reaction vessel while distilling out water/ethyl proxitol azeotrope Up to 12 〇. The temperature of 〇. Add 1 gram of ethyl proxitol to the slurry. Then cool the reaction vessel to about 50 ° C ' and remove the resulting slurry. Then the slurry is at 4, 〇〇〇rpjn Centrifugation for about 10 minutes. The liquid was decanted, and the solid was washed with acetone and dried overnight in an oven at 80 ° C under vacuum. The XRD pattern of the hydrotalcite clay prepared as described above shows that the secondary hydrotalcite is not _( Hk0) reflection, indicating the insertion of an anionic clay. The insert 116965.doc -36- 200734275 shows the characteristic d(001) value of 25A. Example 13 2 1.25 g of an aqueous suspension of hydrotalcite layered double hydroxide according to formula II having 20% by weight of a Mg/Al ratio and a hydroxyl group as a charge-balanced anion, and 200 g of ethyl proxitol were equipped with a high speed The mixer was placed in a 500 00 glass reaction vessel and heated to 85 °C. Next, 3.75 grams of Kortacid® PH05 and 4.87 grams of dehydrogenated rosin were added to the reaction vessel. The fatty acid/rosin blend was heated to 85 ° C prior to addition. After the addition of the blend, 1 50 grams of ethyl proxitol was added and the reaction vessel was heated while distilling off the water/ethyl proxitol azeotrope until a temperature of 120 °C was reached. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then centrifuged at 4,000 rpm for about 10 minutes. The liquid was decanted and the solid was dried in an oven at 80 ° C for 5 hours under vacuum. The XRD pattern of a hydrotalcite clay such as that described above shows a secondary hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. This insert shows the characteristic d(001) value of 29A. Example 14 20 g of an aqueous suspension of hydrotalcite layered double hydroxide according to formula II having 20% by weight of a Mg/Al ratio of 2 and a hydroxyl group as a charge balancing anion and 1 50 g of ethyl proxitol (purchased from Shell) It was broken into a 500 ml glass reaction vessel equipped with a high-speed agitator and heated to 85 °C. Then, 6.3 g of Kortacid® PKGH and 6.3 g of hydrogenated rosin in 50 g of ethyl proxitol were added to the reaction vessel over a period of 15 minutes. The fatty acid/rosin exchange was heated to 85 ° C before addition. After the admixture is added, the reaction volume is heated 116965.doc -37- 200734275' while steaming the effluent/ethyl proxitol azeotrope until the temperature of i2 〇 °C is reached. The reaction vessel was then cooled to about 5 (rc, 1 gram of ethyl proxitol' was added and the resulting slurry was removed. The slurry was then centrifuged at 2,5 rpm for about 10 minutes. The liquid was decanted and the solid was used. The acetone was washed and dried overnight in an oven at 80 ° C under vacuum. The XRD pattern of the hydrotalcite clay prepared as described above shows a minor hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. The characteristic d(〇〇i) value of 29A is shown. Example 15 1% of a hydrotalcite layered double hydroxide according to formula II having 20% by weight of a Mg/Al ratio and a hydroxyl group as a charge balancing anion The gram aqueous suspension and 21 g of ethyl proxit〇l (purchased from Shell) were broken into a 500 ml glass reaction vessel equipped with a high-speed stirrer and heated to 85 ° C. Then dissolved

25.16 g of Kortacid® PKGH in 21.85 g of ethyl proxitol was added to the reaction vessel over 30 minutes. The fatty acid blend was heated to 85 C before the addition. The resulting mixture was stirred for 3 hours. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then centrifuged at 4, rpm for about 10 minutes. The liquid was decanted and the solid was washed with water and dried in an oven at 80 ° C overnight under vacuum. The XRD pattern of a hydrotalcite clay such as that described above shows a secondary hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. The insert exhibits a characteristic d(001) value of 37.7A. Example 16 20% by weight of a Mg/Al ratio and a hydroxyl group as a charge balance anion 116965.doc -38- 200734275 according to the formula π, such as a hydrotalcite layered double hydroxide And 12.5 grams of ethyl proxitol (purchased from the shell) was broken into a 500 ml glass reaction vessel equipped with a high speed stirrer and heated to 85. Hey. Will dissolve

Solution to 12.5 grams of 12.5 grams of ethyl proxitol Kortacid® PKGH was added to the reaction vessel over 30 minutes. The fatty acid blend was heated to 85 °C prior to addition. The resulting mixture was stirred for 3 hours. The reaction vessel was then cooled to about 50 ° C and the resulting slurry was removed. The slurry was then centrifuged at 4 Torr rpm for approximately 10 minutes. The liquid was decanted and the solid was washed with water and dried overnight at 80 ° C in vacuo. The XRD pattern of a hydrotalcite clay such as that described above shows a secondary hydrotalcite-related non-(hkO) reflection indicating the insertion of an anionic clay. The insert exhibits a characteristic d(001) value of 38·4Α. Example 17 1,995 g of magnesium oxide (Zolith, 4 〇, available from Martin Marieua Magnesia Specialties LLC) and mg gram of aluminum hydroxide (Alumiu φ F505) were mixed in 7,500 g of demineralized water and ground to an average of 1.5 μm Particle size do). A portion of the slurry was diluted with demineralized water to 8% by weight solids. The 1.3 6 kg diluted slurry was broken into an oil-heated autoclave equipped with a high-speed stirrer and heated to 80 °C. Before the slurry was added, the high pressure dad was broken into 1.25 kg of 2-ethoxypropanol and heated to 8 (rc. The autoclave was then heated to 120 ° C, and 354 g of Kortacid® PH05 and Prifac 7990 were added over 15 minutes. 50/50 (by weight) mixture. Before the addition, the fatty acid blend was heated to 120 C. After the acid was added, the autoclave was heated to 17 (: (and kept for hours) and then the autoclave was cooled to about 4 ° ° C, and the resulting slurry was removed. Filtration 116965.doc • 39- 200734275 Aggregate and washed with acetone over a large area. The resulting material f was dried under vacuum in (9) c. overnight in a tank. Hydrotalcite-like clay is analyzed by calendering to determine the channel spacing or lattice spacing. The XRD pattern of the hydrotalcite clay such as the above-mentioned injury shows the secondary hydrotalcite-related non-(hk〇) reflection, indicating an anion. Insertion of clay. XRD shows 52A and 3 (^d((10)U values. In addition, SEM analysis of the washed powder shows the extremely high aspect ratio (L/D> l〇, 〇〇〇) of the resulting rectangular platelets. 18 from Martin Marietta will be 665 grams of magnesium oxide (z〇lith〇® 4〇

Magnesia Specialties LLC) and 576 grams of aluminum hydroxide (μ (10) Hill F505) were mixed in 2,500 grams of demineralized water and ground to an average of 丨$_, 5 . ). A portion of the slurry was diluted with demineralized water to a solids content of 96% by weight. 229 g of the diluted slurry was crushed into an oil equipped with a high-speed stirrer, and the door was heated to 9 〇 c. Before the dressing is added, the high waste dad will be broken into

2〇\ g 2-ethoxypropanol and heated to ah. Then heat the Gaoqing dad to 120C ’ X for about 15 minutes. The high pressure dad was then heated to "regeneration" for 1 hour. After the reaction, the autoclave was cooled to 6 (rc below, and the resulting polymer was removed. The slurry was filtered and washed extensively with acetone. The resulting material was at 80 ° under vacuum. C is dried overnight in an oven. / & Fluorescence analysis of hydrotalcite clay such as hushui to determine the pitch of the tunnel or the spacing of the grid. The XRD pattern of the hydrotalcite clay prepared as described above shows the typical hydrotalcite structure. _) and _) reflections and corresponding to the water lock stone - some secondary signals. 116965.doc

Claims (1)

200734275 X. Patent Application Scope 1. A method for preparing a layered double hydroxide comprising a charge-balancing anion. The method comprises the following steps: (4) preparing a precursor suspension or solution comprising two sources a solvent of a trivalent metal ion, water, and a solvent miscible with water and capable of dissolving at least 5 g/l of charge-balanced anion precursor; (7) treating the precursor suspension or solution to obtain the layered double hydrogenate, Milk wherein the charge-balanced anion precursor is added to the suspension or solution before, during or after step (b), and wherein if the charge: the anion is an organic anion, the charge-anion anion precursor The total weight, less than 5% by weight of the charge-balanced anion precursor is a salt limiting condition such that the charge-balancing anion is not carbonate. 2. The method of claim 1, wherein the solvent is an alcohol having a transbasic group, and the sterol is preferably selected from the group consisting of ethanol, n-propanol, isopropanol, butanol, and the following formula Alkoxylated alcohol, , OH /, medium, R! is CVC8 alkyl or phenyl, R2 is hydrogen or methyl, and an integer of n 5 . The method of claim 1 or 2, wherein the charge-balancing anion is an organic anion ·4, wherein the organic anion comprises 8 or more 116965.doc 200734275 carbon atoms, It preferably has from 10 to 40 carbon atoms. The method of claim 1 wherein the organic anion is carried out in step (b) and added to the ruthenium suspension or solution. The method of claim 3 wherein the organic anion is added after the layered dihydrogen is formed by a charge-balanced anion selected from the group consisting of roots and two species: hydroxide, A method of claim 1, wherein the divalent valent metal ion is W, a nitrate ion, a phosphonate, a root, a sulfate, a hydrogen sulfate, and a method according to claim 1. The method of claim 1, which further comprises the following steps: c-shaped =: a medium and a suspension of the layered bis-amine oxide, the layer of halide comprising a substance selected from the following The charge of the group consisting of: ions: hydroxide, nitrate, phosphate, phosphonate, ruthenium, sulfate, hydrogen sulfate and _ ions; (d) treating the suspension to obtain a packet anion as a charge The layered double hydroxide of the anion is added, and the second: anion::T_ is added during the step (4) or (4). Miscible and wherein the suspension medium comprises water and/or can be hydrated and wherein at least 5 g/l of the right μ-agent can be dissolved. The solution of the anion precursor is the same as the method of claim 8 or 9, wherein the suspension medium of the suspension is the same. And a method for preparing a layer comprising an organic anion as a charge-balancing anion in the step (4). 6. 7. 8. 8, 9 965 965.doc 200734275 A method for forming a double hydroxide, the method comprising the steps of: (4) preparing a layer a double hydroxide, a solvent and optionally a suspension of water, the layered double hydroxide comprising a charge balancing anion selected from the group consisting of: hydroxide, root, dish, lin, stone (6) treating the precursor suspension or solution to obtain the layered double compound, wherein the organic anion precursor is added to the step (4) or (b) In the suspension liquid and wherein the solvent is miscible with water and wherein at least 5 g/Ι of the organic anion precursor is soluble. A layered double hydroxide containing a charge-balanced negative material obtained by the method of any one of items 1 to 11. 13. = f The layered double hydroxide of item 12, wherein the charge balance anion = organic anion and the distance between the individual layers of the layered double hydroxide is 1 · 5 nm or more. 14· A nanocomposite, 1 layered double hydroxide. The amount of the layered double hydroxide, the total weight of the material and the total weight of the layered dihydrogen of the claim 12 or 13 and the layered dihydrogen of the claim 10 or 13 70% by weight, and the amount of polymer is 30% by weight to 9% by weight. 116965.doc 200734275 VII. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) A brief description of the component symbol: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 116965.doc