RU2426688C2 - Method of obtaining layered double hydroxide modified with organic compounds - Google Patents

Abstract

FIELD: chemistry. ^ SUBSTANCE: invention relates to a method of producing a layered double hydroxide containing a charge-compensating anion, comprising a step for obtaining a precursor suspension or solution containing a source of divalent or trivalent metal ions, water and a water-miscible solvent, in which at least 5 g/l precursor can be dissolved. The precursor suspension or solution is then treated to obtain layered double hydroxides, in which a charge-compensating anion precursor is added to the suspension or solution before, during or after treatment. If the charge-compensating anion is an organic anion, less than 50 wt % of the charge-compensating anion precursors per total weight of the charge-compensating anion precursors is a salt, if the charge-compensating anion is not a carbonate. The invention also relates to a layered double hydroxide obtained using the described method. ^ EFFECT: invention enables to lower alkalinity and amount of water in the layered double hydroxide. ^ 8 cl, 18 ex

Description

The invention relates to a method for producing layered double hydroxides.

Such methods are known to those skilled in the art. Cavani et al. ( Catalysis Today , 11 (1991), p. 173-301) have described various methods for preparing layered double hydroxides. All considered methods are carried out in water. Carlino ( Solid State Ionics , 98 (1997), p. 73-84) provides various preparative methods for the intercalation of carboxylic acids into the structure of layered double hydroxides, mainly using aqueous solutions.

Most methods for producing layered double hydroxides are carried out in water, as a result of which the final dried product contains a significant amount of water. In addition, layered double hydroxides containing hydroxides or organic anions as charge-compensating ions usually form alkaline suspensions when redispersed in water. A significant amount of water and the alkaline reaction of traditionally obtained layered double hydroxides can change the mechanical and physical properties of the resulting composite materials when they are mixed with polymer matrices, for example, mixing can lead to depolymerization.

Therefore, the subject of the present invention is to propose a new method for producing layered double hydroxides in which the alkalinity and / or amount of water in the final product can be reduced. In addition, the subject of the invention are new layered double hydroxides.

This goal is achieved using the method of producing layered double hydroxides containing charge-compensating anions, which includes the steps of:

(a) preparing a suspension or solution of a precursor comprising a source of divalent metal ions, a source of trivalent metal ions, water and a water miscible solvent in which at least 5 g / l of the charge-compensating ion precursor can be dissolved;

(b) processing the suspension or solution of the precursor to obtain layered double hydroxides,

in which the precursor of charge-compensating ions is added to the suspension or solution before, during or after stage (b) and in which, if the charge-compensating anion is an organic anion, at least 50 wt.% of the precursors of charge-compensating anions based on the total mass of the charge-compensating anion precursors is a salt, provided that the charge-balancing anion is not a carbonate.

The use of a solvent in the method of the present invention allows to obtain layered double hydroxides containing a relatively low amount of water. Layered double hydroxides usually exhibit enhanced thermal stability.

The method of the present invention is particularly suitable for producing layered double hydroxides containing organic anions as charge-compensating anions. Such layered double hydroxides modified with organic compounds have a reduced alkalinity, i.e. when redispersed, for example, in water, they will have a lower pH than traditional layered double hydroxides obtained in the usual way. Using the method of the present invention, a higher degree of intercalation of organic anions can be achieved. In general, layered double hydroxides, and in particular layered double hydroxides modified with organic compounds, will have increased compatibility with the polymer with which they will be mixed.

In the method of the present invention, the solvent may be any water-miscible solvent in which at least 5 g / L of the charge-compensating anion precursor can be dissolved. The miscibility of the solvent with water can be estimated using ASTM D 1722-98. The solubility of the anion precursor may depend on the pH and / or temperature of the mixture. In the method of the present invention, conditions are selected such as, for example, the reaction temperature, which allows the dissolution of at least 5 g / l of the charge-compensating anion precursor. Examples of such solvents include alcohols such as methanol, ethanol, n- propyl alcohol, isopropyl alcohol, n- butanol, isobutanol and tert- butanol; alkanopoliols such as ethylene glycol, propylene glycol and glycerin; ethers such as dimethyl ether, diethyl ether or dibutyl ether; alkane polyol diesters such as dimethylene glycol, diethylene glycol, dimethylpropylene glycol and diethylpropylene glycol, and alkoxylated alcohols of the formula

where R ₁ represents a C ₁ -C ₆ -alkyl or phenyl, R ₂ is hydrogen or methyl and n is an integer of 1-5; amines such as triethylamine; nonionic polymeric solvents such as polyethylene glycols, polypropylene glycols, lauryl polyethylene glycol; ionic liquids; pyridines; dimethyl sulfoxides and pyrrolidones, such as n-methylpyrrolidone.

In one embodiment, the solvent is a substance that can form an azeotrope with water. The use of an azeotropic mixture in the method of the present invention facilitates easier removal of the solvent and more efficient removal of water. Preferably, the solvent is an alcohol containing one hydroxyl group. Examples of such alcohols include monohydric alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutanol and tert-butanol and the alkoxylated alcohols mentioned above.

In one embodiment of the present invention, the solvent is an alkoxylated alcohol. Examples of such alkoxylated alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, ethylene glycol mono-butyl ethylene glycol ether, mono-tert-butyl ether of ethylene glycol glycol mono-tert-butyl ether monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -propilovy ether, diethylene glycol monoisopropyl ether diethylene glycol monobutyl Marketing ether, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol mono t-butyl ether, propylene glycol monohexyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono dipropylene glycol n- propyl ether, dipropylene glycol monoisopropyl ether and dipropylene glycol monobutyl ether. Of these alcohols, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether are less preferred since they are teratogenic and can cause health problems.

The most preferred alkoxylated alcohols are propylene glycol monomethyl ether and propylene glycol monoethyl ether. Solvents are available, for example, from Shell (Oxitol / Proxitol), Dow (Dowanol) and Union Carbide (Carbitol / Cellosolve).

Two or more solvents may also be used in the method of the invention. In addition, you can use another organic solvent that is not miscible with water and / or in which at least 5 g / l of the charge-compensating anion precursor can be dissolved. Suitable examples of such organic solvents include alkanes such as pentane, hexane and heptane; ketones such as methylamyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; unsaturated acrylic esters such as butyl acrylate, methyl methacrylate, hexamethylene diacrylate and trimethylol propane triacrylate, and aromatic hydrocarbons such as benzene, toluene and xylene.

The amounts of water and solvent used in the method of this invention can vary over a wide range. In one embodiment of the invention, the amount of solvent is less than 50 wt.% Based on the total weight of water and solvent, preferably less than 40 wt.% And most preferably less than 30 wt.%.

Sources of divalent metal ions and trivalent metal ions used in the methods of the present invention can be any known to those skilled in the art. These sources include nitrates, chlorides, perchlorates, as well as aluminates. Insoluble or partially insoluble sources of divalent and trivalent metal ions typically include oxides or hydroxides, carbonates of divalent and trivalent metals. Preferably, the sources are insoluble or partially soluble. Most preferably, the sources of divalent and trivalent metal ions are oxides or hydroxides.

In the context of the present application, “soluble salts” refer to sources of divalent and trivalent metal ions that completely dissolve and form a clear solution at room temperature. In the context of this application, the term "insoluble or partially insoluble" refers to sources that do not completely dissolve and form a suspension at room temperature.

Examples of divalent metal ions include 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 include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ³⁺ , Ce ^3+, and Ga ³⁺ . In layered double hydroxides obtained by the method of this invention, you can use three or more metal ions. Among these ions, a combination of Mg ²⁺ and Al ^{3+ is} preferred.

Examples of suitable sources of magnesium that are insoluble or partially insoluble include magnesium oxide, magnesium hydroxide, basic carbonate, magnesium bicarbonate, dolomite and sepiolite. A combination of two or more sources of magnesium is also possible.

A source of aluminum that is insoluble or partially insoluble is usually hydroxide or alumina. Examples of such aluminum sources are aluminum trihydroxide, for example gibbsite and bayerite, aluminum oxyhydroxide, such as boehmite, diaspore or goethite, or transitional aluminum oxides, which are known in the art.

Due to the use of the indicated insoluble or partially soluble sources of divalent and trivalent metal ions in the method of the present invention, the proposed method is more environmentally friendly, because significantly less salts are left in the process effluent, if any. In addition, sources of ions of divalent and trivalent metals and, in particular, sources of magnesium and aluminum are usually cheaper than the corresponding salts, usually used in the preparation of layered double hydroxides. In addition, the method of the present invention is usually simpler, because includes fewer stages and / or does not require wastewater treatment. In addition, these methods can be implemented much faster, which in turn increases the production rate of a layered double hydroxide modified with organic compounds, compared with traditional methods.

In a preferred embodiment of the present invention, insoluble or partially soluble sources of divalent and trivalent metal ions and, in particular, magnesium and aluminum sources are ground prior to step (b). In the methods of this invention, the sources of divalent and trivalent metal ions have a d50 value of less than 20 microns and a d90 value of less than 50 microns. Preferably, d50 is less than 15 microns and d90 is less than 40 microns, more preferably d50 is less than 10 microns, and even more preferably d50 is less than 8 microns and d90 is less than 20 microns, and most preferably d50 is less than 6 microns, and d90 is less than 10 microns. The particle size distribution can be determined by methods known to those skilled in the art, for example by laser diffraction according to DIN 13320. The grinding step accelerates the formation of layered double hydroxides. It can also reduce the amount of impurities, such as gibbsite or brucite, when the source of ions of divalent and trivalent metals are sources of magnesium and aluminum.

In the context of this application, the terms “processing” and “processed”, for example, the processing in step (b), refers to the processing of a suspension at elevated temperatures. Such treatment may be heat treatment or solvothermal treatment. In the context of this application, the terms "heat treatment" and "thermal" refers to the processing of a suspension or solution at atmospheric pressure. The temperature is usually 40-120 ° C., Preferably 50-100 ° C. And most preferably 60-90 ° C.

In addition, the terms “solvothermal treatment” and “solvothermally” refer to the treatment of a suspension or precursor solution at a pressure higher than atmospheric pressure and a temperature usually higher than the boiling point of a suspension or solution of a precursor at atmospheric pressure. The pressure is usually 1-200 bar, preferably 2-150 bar, and most preferably 3-100 bar. Typically, the temperature is 100 ° C or higher, preferably 100-300 ° C, more preferably 110-250 ° C, and most preferably 120-200 ° C.

The method of the present invention can be carried out in the absence of CO ₂ or any carbonate in the precursor suspension to ensure that the carbonate will not be incorporated into the layered double hydroxide as a charge-compensating anion.

The method of the invention also relates to the production of a layered double hydroxide containing an organic anion as a charge-compensating anion. Such layered double hydroxides are called “organically modified layered double hydroxides” or “organoclay”.

In one embodiment of the invention, the organic anion is added to the suspension or solution of the precursor before or during step (b). Thus, an organically modified layered double hydroxide is obtained in a single step, which makes the process simpler and faster and therefore more economically attractive.

The charge compensating anion precursor may be an alkali or alkaline earth metal salt, or a divalent and / or trivalent metal salt, or an acid, or a mixture thereof. In the method of the present invention, less than 50 wt.% Charge-compensating anions, based on the total weight of the charge-compensating anion precursors, are added to the suspension in the form of a salt. In order to reduce the amount of salt in the wastewater, it is preferable to use a mixture of an acid of an organic anion with a salt of a divalent and / or trivalent metal and an organic anion or acid of an organic anion. As shown above, less than 50 wt.% Charge-compensating anions based on the total weight of the charge-compensating anion precursors are used in the form of a salt, preferably less than 30 wt.% Of the charge-compensating anions are salt and more preferably less than 10 wt.% Charge -compensating anions are a salt. It is important to note the fact that in order to further reduce the amount of salts in the wastewater and / or in the final product, the salts of charge-compensating anions are absent in the method of the invention.

In one embodiment of the invention, the charge-compensating anion is organic. The organic anion precursor may be an alkali or alkaline earth metal salt, or a divalent and / or trivalent metal salt, or an acid, or a mixture thereof. Organic anions can be used in the amounts indicated above.

Suitable examples of organic anions include acetic acid, succinic acid, terephthalic acid, benzoic acid, caprylic acid, capric acid, lauryl acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, decenoic acid, palmitoleic acid, palmitoleic acid, palmitoleic acid linolenic acid and rosin.

It is recommended that part of the organic anions be added before or during step (b) and the rest is added after the formation of a layered double hydroxide.

Alternatively, the organic anion is added after the formation of the layered double hydroxide, when the layered double hydroxide already contains a charge-compensating anion, which is selected from the group consisting of hydroxyl, nitrate, chloride, bromide, phosphate, phosphonate, sulfonate, sulfate, bisulfate, or mixtures thereof. This invention relates to the method described above, which also includes the steps of:

(c) obtaining a suspension from a suspending medium and a layered double hydroxide containing a charge-compensating anion, which is selected from the group consisting of hydroxyl, nitrate, phosphate, phosphonate, sulfonate, sulfate, bisulfate and halide;

(d) treating the suspension to obtain an organically modified layered double hydroxide, wherein the organic anion precursor is added during step (c) or (d).

It is preferable to select the charge-compensating anion of the layered double hydroxide (LDH) used in step (c) from the group consisting of hydroxyl, nitrate, chloride, bromide or mixtures thereof. The indicated charge-compensating anion is easily exchanged with an organic anion. This exchange can be accelerated using the solvent of this invention, which is not possible in similar methods carried out in water.

Alternatively, the invention relates to a method for producing a layered double hydroxide containing an organic anion as a charge-compensating anion, which comprises the steps of:

(a) preparing a suspension of a layered double hydroxide containing a charge-compensating anion, which is selected from the group consisting of hydroxyl, nitrate, phosphate, phosphonate, sulfonate, sulfate, bisulfate and halide, a solvent and optionally water;

(b) processing the suspension or solution of the precursor to obtain a layered double hydroxide,

wherein the organic anion precursor is added to the suspension during step (a) or (b) and the solvent is mixed with water and may contain at least 5 g / l of the organic anion precursor dissolved therein.

The layered double hydroxide used may be a layered double hydroxide obtained by the method of the present invention, or, alternatively, a layered double hydroxide can be obtained by conventional methods.

If the method of the invention includes a step of exchanging charge-compensating anions with organic anions after a layered double hydroxide is formed, the step of forming LDH and the step of exchange can be carried out thermally or solvothermally, or the step of formation can be carried out thermally, and the step of exchange is hydrothermal or vice versa.

In the context of this application, the term “charge-compensating anion” refers to anions that compensate for the deficiency of electrostatic charge on LDH crystalline flakes. Since LDH usually has a layered structure, charge-compensating anions can be located between layers, on the edges, or on the outer surface of adjacent LDH layers. Such anions localized in the interlayer space of the joined LDH layers are called intercalated ions.

Such combined LDHs containing an organic anion or organoclay can also delaminate or exfoliate, for example, in a polymer matrix. In the context of the present description, the term "delamination" is defined as a decrease in the average degree of adhesion of LDH particles due to at least partial disruption of the layered structure of LDH, which leads to a material containing significantly more individual LDH flakes in volume. The term “peeling” is defined as complete peeling, i.e. the disappearance of periodicity in the direction perpendicular to the LDH flakes, which leads to chaotic dispersion of individual layers in the medium and the absence of any ordering.

Swelling or expansion of LDH, also called intercalation in LDH, can be observed using x-ray diffraction (XRD), because position of basal planes, i.e. reflexes d (001) , indicates the distance between the layers, which increases after intercalation.

A decrease in the average degree of adhesion can be observed as broadening up to the disappearance of X-ray diffraction lines or as an increase in the asymmetry of basal reflexes (001) .

Characterization of complete bundle, i.e. exfoliation, needs analysis, but in general it can be judged by the complete disappearance of non-basal ( hko ) reflexes from the initial LDH.

The ordering of the layers and, therefore, the degree of delamination can be determined by transmission electron microscopy (TEM).

The LDHs of this invention may be any LDHs known to those skilled in the art, but the morphology, physical and chemical properties may be different. Typically, these LDHs are mineral LDHs capable of expanding or swelling. Such LDHs have a layered structure consisting of charged crystalline flakes (also called individual LDH layers), alternating with charge-compensating anions. The terms "expand" or "swell" in the context of this application refers to an increase in the distance between charged crystalline flakes. Expanding LDHs can swell in suitable solvents, such as water, and can further expand and modify by exchanging charge-compensating ions with other (organic) charge-balancing ions; such modification is also known as intercalation.

The invention further relates to layered double hydroxides, which can be obtained by the method of this invention. Layered double hydroxides according to this invention and, in particular, organically modified layered double hydroxides contain little water, have a lower alkalinity and increased thermal stability compared to layered double hydroxides obtained in water. The LDHs of the present invention generally have enhanced compatibility with polymers and can be used in a wide variety of polymers, in particular in polymers whose properties deteriorate when mixed with LDH. In such cases, the resulting polymer will have a reduced degree of depolymerization, a reduced degree of discoloration and / or a reduced degree of degradation of antioxidants.

Due to the reduced alkalinity of the obtained organically modified layered hydroxides when used in a mixture of compounds used for the vulcanization of sulfur rubber, they will have a weaker effect on the vulcanization time compared to unmodified layered double hydroxides.

In one embodiment of the invention, LDH can be obtained with a morphology that will be different from the morphology of traditional LDH. The average length to diameter ratio (L / D ratio) for individual plates in LDH or organically modified LDH may be greater than 200; it is preferred that the L / D ratio is at least 300, more preferably that the L / D ratio is at least 500, and even more preferably, the L / D ratio is at least 1000. The L / D ratio can be determined by electron microscopy, for example scanning electron microscopy (SEM) and / or TEM. The length is the largest size of the plates in a direction perpendicular to the direction of adhesion, and the diameter refers to the thickness of the clay particles in the direction of adhesion. If the clay has exfoliated and / or exfoliated, the diameter may become equal to the thickness of one layer.

Layered double hydroxides according to this invention have a layered structure, and their composition corresponds to the General formula:

[M _m ²⁺ M _n ³⁺ (OH) _{2m + 2n} ] X _{n / z} ^z- .bH ₂ O (I)

where M ²⁺ is a divalent metal ion such as Zn ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Cu ²⁺ , Sn ²⁺ , Ba ²⁺ , Ca ²⁺ and Mg ²⁺ , M ³⁺ is a trivalent metal ion, such as Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ³⁺ , Ce ³⁺ and Ga ³⁺ , m and n have the meanings that the ratio m / n = 1-10 and b has a value in the range of 0-10. X is a charge-compensating anion known to those skilled in the art. The charge-compensating anion may be organic or inorganic. It is intended to use one or more organic anions and / or one or more inorganic anions.

Examples of known inorganic anions include hydroxide, carbonate, bicarbonate, nitrate, chloride, bromide, sulfonate, sulfate, bisulfate, vanadates, tungstates, borates, phosphates, modifying anions 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. It is preferable to select an inorganic anion from the group consisting of hydroxide, carbonate, bicarbonate, nitrate, chloride, bromide, sulfonate, sulfate, bisulfate, or mixtures thereof.

The organic anion used in the method of the present invention may be any known anion. An organic anion suitable for use in this method can be obtained from a salt or acid with an organic anion. The use of an organic anion derived from a salt such as alkali metal stearate may be advantageous due to its higher solubility in a solvent compared to an organic anion derived from an acid. Alternatively, an organic anion derived from an acid may have the advantage that the salt ions do not enter the wastewater, so that the wastewater does not require additional treatment to remove the salt ions, which makes the process cheaper and simpler.

Such organic anions include mono-, di- or polycarboxylic acids, sulfonic acids, phosphonic acids and sulfuric acids. Preferably, the organic anion contains at least 2 carbon atoms, more preferably at least 8 carbon atoms, even more preferably at least 10 carbon atoms and most preferably at least 12 carbon atoms, while the organic anion contains no more than 1000 carbon atoms, preferably not more than 500 carbon atoms, more preferably not more than 100 carbon atoms and most preferably not more than 50 carbon atoms.

Preferably, the organically modified layered double hydroxides obtained by the method of the present invention have a distance between individual layers of more than 1.5 nm. This gives such organically modified layered double hydroxides an advantage when used in polymer matrices. In polymer matrices (for example, in nanocomposite materials or compositions for applying), the greater the interlayer distance, the easier it is to process layered double hydroxides in the polymer matrix according to this invention, which, in addition, makes it easy to delaminate and / or peel layered double hydroxides, and this allows you to get a mixture of modified layered double hydroxides and a polymer matrix with improved physical properties. Preferably, the layer spacing in the LDH of the invention is 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. The distance between the individual layers can be determined by x-ray diffraction and transmission electron microscopy (TEM), as described above.

In addition, it is contemplated that the charge-compensating organic anion contains one or more functional groups such as hydroxyl, amine, carboxylic acid, and vinyl. When using such organically modified LDHs in polymer matrices, these functional groups can interact or react with the polymer.

Suitable examples of organic anions according to this invention include anions of monocarboxylic acids, such as fatty acids and rosin.

In one embodiment, the organic anion is a fatty acid with 8-22 carbon atoms or a salt thereof. Such a fatty acid or its salt may be saturated or unsaturated. Suitable examples of such fatty acids or their salts are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, decenoic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid and mixtures thereof.

In another embodiment of the present invention, the organic anion is rosin or a salt thereof. Rosin is obtained from natural sources, it is available and relatively inexpensive compared to synthetic organic anions. Typical examples of natural sources of rosin are gum rosin, wood rosin and tall oil rosin. Typically, rosin is a suspension of a wide variety of different isomers of monocarboxylic tricyclic rosin acids, typically containing about 20 carbon atoms. The tricyclic structures of various rosin acids differ mainly in the position of the double bonds. Typically, rosin is a suspension of substances including levopimaric acid, neo-abietic acid, palustric acid, abietic acid, dehydroabietic acid, seco-dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, and pimop. Rosin from natural sources also includes rosins, i.e. rosin suspensions modified by polymerization, isomerization, disproportionation, hydrogenation, and Diels-Alder reactions with acrylic acid, anhydrides, and acrylic esters. Products obtained by such methods are called modified rosins. Natural rosin can also be chemically modified by any method known in the art, for example by reacting the carboxy groups of rosin with metal oxides, metal hydroxides or their salts to form rosin soap or salts (so-called resinates). Such chemically modified rosins are called rosin derivatives.

Such rosins can 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 with 1-40 carbon atoms. The anionic group can be any anionic group known in the art, such as a carbosilate or sulfonate group.

Further details on such rosin-based materials can be found in DFZinkel and J. Russel (in Naval Stores, production-chemistry-utilization , 1989, New York, Section II, Chapter 9) and JDClass (“Resins, Natural”, Chapter 1 : Rosins and Modified Rosins ”, Kirk-Othmer Encyclopedia of Chemical Technology , available on-line from December 4, 2000).

In one embodiment, the intercalated ions are a mixture of fatty acid and rosin.

Typically, at least 10% of the total amount of intercalated ions in the LDH according to this invention are organic anions, preferably at least 30%, more preferably at least 60% and most preferably at least 90% of the total number of intercalated ions. In a preferred embodiment, at least 10% of the total amount of intercalated ions are fatty acid anions or rosins or a suspension of both anions, preferably at least 30%, more preferably at least 60% and most preferably at least 90% of the total intercalated ions are an anion of a fatty acid or rosin, or a mixture of both anions.

In the preparation of organically modified LDHs, the molar ratio between the charge-compensating anions and the aluminum contained in the LDH can be any. The ratio may be in the 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 proposed to use a ratio of 1.

The LDHs of the present invention include hydrotalcites and hydrotalcite-like substances such as meixnerite, manasseite, pyroaurite, syogrenite, stite, barberonite, tacovite, reevezite and disautelsite. Preferred LDH is hydrotalcite, which is LDH with a layered structure corresponding to the general formula:

[Mg _m ²⁺ Al _n ³⁺ (OH) _{2m + 2n} ] X _{n / z} ^z- .bH ₂ O (Ii)

where m and n are such that the ratio m / n = 1-10, preferably 1-6, and b has a value in the range 0-10, usually 2-6, and often about 4. X is a charge-compensating ion, such as described above.

Preferably, the m / n ratio is 2-4, more specifically, is close to 3.

LDH may be in any crystalline form known in the art, as described by Cavani et al. ( Catalysis Today , 11 (1991), p. 173-301) or Bookin et al. ( LDHs and LDH Minerals , (1993), Vol. 41 (5), p. 558-564). If LDH is hydrotalcite, then hydrotalcite can be a polytype with adhesion, for example 3H ₁ , 3H ₂ , 3R ₁ or 3R ₂ .

The LDH of the present invention can be used as a component in coating compositions, printing inks, tackifiers, synthetic resins, rubber compositions, cleaning products, drilling fluids and cements, filler materials, non-woven materials, fibers, foams, membranes materials for orthoplastics; precursors of ceramic materials; and hybrid organo-inorganic composite materials, such as polymer-based nanocomposites. In addition, the LDH of the invention can be used in polymerization reactions such as solution polymerization, emulsion polymerization, and slurry polymerization. Organoclay can also serve as a crystallization seed in semi-crystalline polymers such as polypropylene. The LDHs of the present invention can also be used where the individual functions of LDHs and organic anions can be combined, for example, in papermaking or in the detergent industry. In addition, the LDH according to this invention can be used for the controlled release of, for example, drugs, pesticides and / or fertilizers and as an adsorbent for organic compounds such as contaminants, dyes, and the like.

In addition, the invention relates to nanocomposite materials comprising a polymer and LDH according to this invention, in which LDH contains an organic anion with at least 8 carbon atoms. Typically, organically modified LDHs will substantially peel and / or exfoliate, and the number of micron-sized modified LDH particles will be low or even zero. The presence of completely exfoliated and / or exfoliated LDH in nanocomposite materials leads to the fact that the materials become transparent in visible light and thus they become suitable for use in optics.

The term "nanocomposite material" refers to a composite material in which at least one component is an inorganic phase with at least one measurement in the range of 0.1-100 nm.

Particularly suitable for use in the nanocomposite materials are the LDHs prepared according to the present invention, containing a mixture of charge-compensating organic anions, of which at least one anion is chemically modified so as to be more compatible with the polymer matrix or more reactive. This facilitates the intercalation between LDH and the polymer matrix, which provides improved mechanical and / or viscoelastic properties. More compatible organic anions can be substituted or unsubstituted aliphatic or aromatic hydrocarbons with 1-40 carbon atoms. Alternatively or additionally, at least one of the organic anions can be a reactive group selected from acrylate, methacrylate, hydroxyl, chloride, amine, epoxy, thiol, vinyl, di- and polysulfide, carbamate, ammonium, sulfonic, sulfine groups, sulfonium, phosphonium, phosphinium, isocyanate, mercapto, hydroxyphenyl, hydride, acetoxyl and anhydride.

The polymer used in the nanocomposite material of the present invention may be any known polymer matrix. In this description of the invention, the term "polymer" refers to an organic substance consisting of at least two blocks (ie, monomers) including oligomers, copolymers and polymer resins. Suitable polymers for the polymer matrix are both polyadducts and polycodensates. In addition, the polymers can be homopolymers or copolymers. Preferably, the polymer matrix has a degree of polymerization of at least 20, more preferably at least 50. In this regard, for the determination of the degree of polymerization, see PJ Flory, Principles of Polymer Chemistry , New York, 1953.

Examples of suitable polymers include polyolefins such as polyethylene or polypropylene, vinyl polymers such as polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride or polyvinylidene fluoride, saturated polyesters such as polyethylene terephthalate, polylactic acid, poly (ε-caprolactyl resins), , methacrylate resins, polyimides, epoxies, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, polyurethanes, polycarbonates, poly silt ethers, polysulfones, polysulfides, polyamides, polyetherimides, polyether esters, polyether ketones, polyketones with simple and complex ether groups, polysiloxanes, polyurethanes, polyepoxides, and blends of two or more polymers. Polyolefins, vinyl polymers, polyesters, polycarbonates, polyamides, polyurethanes or polyepoxides are preferably used.

The organoclay of this invention is particularly suitable for use in thermoplastic polymers such as polyethylene, polypropylene, polystyrene, and acetal copolymers such as polyoxymethylene (POM), and in rubbers such as natural rubber (NR), styrene-butadiene rubber (SBR) , polyisoprene (IR), polybutadiene (BR), polyisobutylene (IIR), halogenated polyisobutylene, nitrile butadiene rubber (NBR), hydrogenated nitrile butadiene rubber (HNBR), styrene-isoprene-styrene rubber (SIS) and similar styrene-polymeric block-styrene (epichloride rhine) rubbers (CO, ECO, GPO), silicone rubbers (Q), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), polysulfide rubber (T), fluororubber (FKM), ethylene vinyl acetate rubber (EVA), polyacrylic rubbers (AFM), polynorbornene (PNR), polyurethanes (AU / EU) and polyester / ether thermoplastic elastomers.

Particularly preferred are polymers and copolymers obtained by polymerization of at least one ethylenically unsaturated monomer. Examples of such polymers are polyolefins and modified polyolefins known to those skilled in the art. Polyolefins or modified polyolefins may be homopolymers or copolymers. Suitable examples of such modified polyolefins include polyethylene, polypropylene, polybutylene, polystyrene, polyvinyl chloride, polyvinylidene chloride and ethylene-propylene rubber, propylene-butadiene copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, acrylonitrile, acrylonitrile, acrylonitrile acrylate-styrene copolymer (AAS), methyl methacrylate-butadiene-styrene copolymer (MBS), chlorinated polyethylene, chlorinated polypropylene, ethylene acrylate copolymer, vinyl chloride-propylene th copolymer and mixtures thereof. Even more preferred polymers are polyethylene, polypropylene, polystyrene and polyvinyl chloride.

Specific examples of polyethylene are high density polyethylene, low density polyethylene, straight chain low density polyethylene, ultra low density polyethylene and ultra high molecular weight polyethylene. Examples of ethylene-based copolymers are ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA) and ethylene-acrylic acid copolymer (EAA).

The most preferred polymer is polypropylene. Any known polypropylene is suitable for use in the present invention. Examples of polypropylene are given in the monograph Polypropylene, Chapter 1: “Properties”, by RBLieberman in Kirk-Othmer Encyclopedia of Chemical Technology , available on-line from December 4, 2000. A special class of polypropylenes according to this invention are the so-called thermoplastic polyolefins ( TPOs), which include mixtures or reactor grades of polypropylene and ethylene propylene rubber.

The nanocomposite material of the invention may also contain additives commonly used in the art. Examples of such additives include pigments, dyes, UV stabilizers, heat stabilizers, antioxidants, fillers (such as talc, chalk, limestone, hydroxyapatite, silica, carbon black, fiberglass, natural and synthetic polymer fibers, and other (non) organic fillers) , flame retardants, nucleating agents, additives that increase shock resistance, plasticizers, rheology modifiers, crosslinking agents, coupling reagents and degassing agents.

Such optional additives and their respective amounts can be selected as necessary.

The amount of LDH in the nanocomposite material is preferably 0.01-75 mass%, more preferably 0.05-50 mass%, even more preferably 0.1-30 mass%, based on the total weight of the mixture.

The fact that LDH is 10% by mass or less, preferably 1-10% by mass, more preferably 1-5% by mass, is a particular advantage for producing polymer-based nanocomposite materials, i.e. polymer-containing compositions according to this invention, containing organically modified LDH delaminated until peeling.

LDH is used in an amount of 10-70 wt.%, More preferably 10-50 wt.% To obtain the so-called concentrates, i.e. highly concentrated additional premixes, for example, for compounding polymers. Although clay in such concentrates usually does not completely exfoliate or exfoliate, further exfoliation and / or exfoliation can be achieved, if necessary, at a later stage by mixing the concentrate with a polymer to produce true polymer-based nanocomposites.

The nanocomposite material of the present invention can be prepared by any method known to those skilled in the art. One of skill in the art can thoroughly mix the polymer matrix and the organoclay according to the invention, using, for example, a melt mixing technique. This method is preferred since It is simple, cheap and easy to use in existing plants. It is also proposed to prepare the clay according to this invention in the presence of a polymer matrix or in the presence of monomers and / or oligomers before, during or after polymerization of the monomers and / or oligomers to form a polymer matrix. Other details of the preparation and processing of polypropylene can be found in the monograph “Polypropylene”, Chapter 2: “Production” and chapter 3: “Processing”, by RBLieberman in Kirk-Othmer Encyclopedia of Chemical Technology , available on-line from December 4, 2000.

The nanocomposite material of the present invention can be used in any field in which these composite materials are traditionally used. Nanocomposite materials can be used in carpets, car parts, container lids, prepared food boxes, lids, medical sensors, household items, food containers, dishwashers, outdoor fittings, blow bottles, disposable non-woven fibers, cables and wires and packaging . Other details about polypropylene can be found in the monograph Polypropylene, Chapter 5: “Uses,” by RBLieberman in Kirk-Othmer Encyclopedia of Chemical Technology , available on-line from December 4, 2000, and brochure 022 PPE 10/01 of Basel entitled “Polypropylene: textiles, hard packaging, consumer, film, automobile, electrical / electronic and home electrical appliances”.

Nanocomposite materials containing rubber can be used in the manufacture of tires, such as crude tires, tires for trucks, tractors, SUVs and aircraft, winter tires, in the manufacture of latex products, including gloves, condoms, balloons, catheters, latex fibers, foams carpet rugs and rubberized coconut fiber and hair, shoes, civilian technological products such as bridge supports; supports laminated with metal and rubber, belts and hoses, in cars, in addition to tires, including the engine stand, rubber supports, gaskets, gaskets, sinks and covers, wires and cables, gaskets, medical covers, rollers, small solid tires, racks for household and industrial applications, rubber balls and sleeves, milking machines and other agricultural applications.

If the rubber is silicone and the modified layered hydroxide is in accordance with the present invention, these nanocomposite materials can be used in coated products, including pressure-sensitive adhesives, plastic hard coatings and release adhesives for paper, fiber finishes, including fabric finishes , and hair care products, sealants, and sealants and photocell cells.

Below the present invention is illustrated by examples.

EXAMPLES

The following chemicals were used:

Kortacid® PH05: a mixture of palmitic and stearic acids from Oleochemicals GmbH, Akzo Nobel Chemicals.

Kortacid® PKGH: C ₁₂ -C ₂₂ fatty acid mixture from Oleochemicals GmbH, Akzo Nobel Chemicals.

Dehydrated Rosin: ex Hexion Specially Products.

Hydrogenated Rosin: Foral® AX-E, ex Eastman Chemical.

Prifac® 7990: Modified Fatty Acid (ex Uniqema).

The following solvents were used:

isopropyl alcohol (ex Acros).

Ethyl proxitol®: ethoxypropan-2-ol (ex Shell).

Dowanol® DPNP: propoxy-2-methylethoxypropan-2-ol (ex Dow Chemicals).

Dowanol DPM: dipropylene glycol methyl ester (ex Dow Chemicals).

Dowanol PMA: Propylene glycol methyl ester acetate (ex Dow Chemicals).

Dowanol PPh: propylene glycol phenyl ether (ex Dow Chemicals).

Butylcarbitol: diethylene glycol monobutyl ether (ex Acros).

Example 1

250 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 250 g of isopropyl alcohol (ex Acros) were loaded into a 1 L high-speed glass reactor stirrer and heated to 80 ° C. Then, 90 g of Kortacid® PH05 in 250 ml of isopropanol were added to the reactor over 45 minutes. Before addition, the fatty acid mixture was heated to 80 ° C. After adding acid, the reactor was kept at 80 ° C for another 3 hours. Then the reactor was cooled to about 50 ° C and the resulting suspension was unloaded. After that, the suspension was centrifuged at 4000 rpm for about 20 minutes. The liquid was decanted and the solid residue was dried in a vacuum oven overnight at 80 ° C. The resulting clay of the hydrotalcite type containing a mixture of fatty acids was analyzed by Retngen diffraction to determine the interplanar distance or d-distance. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal reflections ( hk0 ) related to hydrotalcite, indicating an intercalation of anionic clay. The intercalate exhibits a characteristic value of d ( 001 ), corresponding to a value of 2 theta = 1.72.

The beginning of thermal decomposition of an organically modified layered double hydroxide according to thermogravimetric analysis (TGA) corresponds to 270 ° C.

Example 2

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of ethyl proxitol (ex Shell) were loaded into a 500 ml glass reactor with high-speed mixer and heated to 80 ° C. Then 7.5 g of Kortacid® PH05 in 10 g of ethylproxitol were added to the reactor over 15 minutes. Before addition, the fatty acid mixture was heated to 80 ° C. After acid addition, the reactor was heated to distill the water / ethylproxitol azeotrope to a temperature of 130 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was unloaded. The suspension was then centrifuged at 2500 rpm for about 10 minutes. The liquid was decanted and the solid residue was dried in a vacuum oven for 3 hours at 80 ° C. The resulting clay of the hydrotalcite type containing a mixture of fatty acids was analyzed by Retngen diffraction to determine the interplanar distance or d-distance. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 46.5 Å.

Example 3

34.5 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of Dowanol DPNP were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 80 ° C. Then 7.5 g of Kortacid® PH05 in 10 g of Dowanol DPNP was added to the reactor over 15 minutes. Before addition, the fatty acid mixture was heated to 80 ° C. After acid addition, the reactor was heated to distill off the water / Dowanol DPNP mixture at a temperature of 130 ° C. The dry product was cooled to room temperature and the solid residue was dried in a vacuum oven for 3 hours at 80 ° C. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 47.0 Å.

Example 4

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of Dowanol DPM were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 80 ° C. Then 6.0 g of Kortacid® PKGH was heated to 80 ° C and added to the reactor. After acid addition, the reactor was heated to distill off the water / Dowanol DPM mixture at a temperature of 130 ° C. The dry product was cooled to room temperature and the solids were dried in a vacuum oven for 3 hours at 80 ° C. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 32 Å.

Example 5

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of Dowanol PMA were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 80 ° C. Then 6.0 g of Kortacid® PKGH was added to the reactor. Before adding the mixture of fatty acids was heated to 80 ° C. After acid addition, the reactor was heated to distill off the water / Dowanol PMA mixture at a temperature of 130 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at a speed of 2500 rpm for about 10 minutes. The liquid was decanted and the solids were dried in a vacuum oven for 3 hours at 80 ° C. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 48 Å.

Example 6

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of Dowanol PPh were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 80 ° C. Then 6.0 g of Kortacid® PKGH was added to the reactor. Before adding the mixture of fatty acids was heated to 80 ° C. After acid addition, the reactor was heated to distill off the water / Dowanol PPh mixture at a temperature of 130 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at 4000 rpm for about 10 minutes. The clear liquid was drained and the solids (upper layer of the suspension) and the gel (lower layer of the suspension) were washed with acetone and dried in a vacuum oven for 3 hours at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 29 Å.

Example 7

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of butyl carbitol were loaded into a 500 ml glass reactor with a high-speed stirrer and heated up to 80 ° C. Then 6.0 g of Kortacid® PKGH was added to the reactor. Before adding the mixture of fatty acids was heated to 80 ° C. After acid addition, the reactor was heated to distill off the water / butylcarbitol mixture at a temperature of 120 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at 4000 rpm for about 10 minutes. The transparent liquid and solids (upper layer of the suspension) were unloaded and the gel (lower layer of the suspension) was washed with acetone and dried in a vacuum oven for 3 hours at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 30 Å.

Example 8

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of Dowanol PPh were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 80 ° C. Then 9.75 g of dehydrogenated rosin was added to the reactor. Before adding rosin was heated to 80 ° C. After acid addition, the reactor was heated to distill off the water / Dowanol PPh mixture at a temperature of 130 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at 4000 rpm for about 10 minutes. The clear liquid was drained and the gel (lower layer of the suspension) was washed with acetone and dried in a vacuum oven for 3 hours at 80 ° C. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 25 Å.

Example 9

62.5 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 150 g of ethyl proxitol (ex Shell) were loaded into a 500 ml glass reactor with high speed stirrer and heated to 85 ° C. Then, 4.06 g of Kortacid® PKGH and 12.18 g of hydrogenated rosin were added to the reactor. Before adding the mixture of fatty acid / rosin was heated to 85 ° C. In addition, 50 g of ethylproxitol was added. After adding the mixture, the reactor was heated to distill the water / ethylproxitol azeotrope to a temperature of 120 ° C. Then the reactor was cooled to about 50 ° C, 100 g of ethylproxitol was added and the resulting suspension was unloaded. The suspension was centrifuged at a speed of 2500 rpm for about 10 minutes. The liquid was decanted and the solids washed with acetone and dried in a vacuum oven for 3 hours at 80 ° C. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 29 Å.

Example 10

62.5 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 150 g of ethyl proxitol (ex Shell) were loaded into a 500 ml glass reactor with high speed stirrer and heated to 85 ° C. Then 12.15 g of Kortacid® PKGH and 100 g of ethylproxitol were added to the reactor. Before adding the mixture of fatty acids was heated to 85 ° C. After adding a mixture of fatty acids and ethylproxitol, the reactor was heated to distill the water / ethylproxitol azeotrope to a temperature of 120 ° C. Then the reactor was cooled to about 50 ° C, 100 g of ethylproxitol was added and the resulting suspension was unloaded. The suspension was centrifuged at a speed of 2500 rpm for about 10 minutes. The liquid was decanted and the solids washed with acetone and dried in a vacuum oven for 3 hours at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 28 Å.

Example 11

62.5 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 150 g of 2- (2-ethylhexyloxy) ethanol were loaded into 500 ml glass reactor with a high speed stirrer and heated to 85 ° C. Then, 12.15 g of Kortacid® PKGH was added to the reactor. Before adding the mixture of fatty acids was heated to 85 ° C. After adding a mixture of fatty acids, the reactor was heated to distill off the water / 2- (2-ethylhexyloxy) ethanol azeotrope to reach a temperature of 125 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at 4000 rpm for about 10 minutes. The liquid was decanted and the solids washed with acetone and dried in a vacuum oven for 5 hours at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 30 Å.

Example 12

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of ethyl proxitol (ex Shell) were loaded into a 500 ml glass reactor with high speed stirrer and heated to 85 ° C. Then, 5.78 g of Kortacid® PKGH and 0.28 g of aminododecanoic acid were added to the reactor. Before adding the mixture of fatty acids was heated to 85 ° C. After adding a mixture of fatty acids, the reactor was heated to distill the water / ethylproxitol azeotrope to a temperature of 120 ° C. 100 g of ethylproxitol was added to the suspension. Then the reactor was cooled to about 50 ° C, 100 g of ethylproxitol was added and the resulting suspension was unloaded. The suspension was centrifuged at 4000 rpm for about 10 minutes. The liquid was decanted and the solids washed with acetone and dried in a vacuum oven overnight at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 25 Å.

Example 13

31.25 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 200 g of ethylproxitol were loaded into a 500 ml glass reactor with a high-speed stirrer and heated up to 85 ° C. Then, 3.75 g of Kortacid® PKGH and 4.87 g of dehydrogenated rosin were added to the reactor. Before adding the mixture of fatty acids / rosin was heated to 85 ° C. After adding the mixture, 150 g of ethylproxitol was added and the reactor was heated to distill the water / ethylproxitol azeotrope to a temperature of 120 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at 4000 rpm for about 10 minutes. The liquid was decanted and the solids were dried in a vacuum oven for 5 hours at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 29 Å.

Example 14

50 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 150 g of ethylproxitol were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 85 ° C. Then 6.3 g of Kortacid® PKGH and 6.3 g of dehydrogenated rosin in 50 g of ethylproxitol were added to the reactor over 15 minutes. Before adding the mixture of fatty acids / rosin was heated to 85 ° C. After adding the mixture, the reactor was heated to distill the water / ethylproxitol azeotrope to a temperature of 120 ° C. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was centrifuged at a speed of 2500 rpm for about 10 minutes. The liquid was decanted and the solids washed with acetone and dried in a vacuum oven overnight at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 29 Å.

Example 15

100 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 21 g of ethyl proxitol (ex Shell) were loaded into a 500 ml glass reactor with a high-speed stirrer and heated to 85 ° C. Then, 25.16 g of Kortacid® PKGH dissolved in 21.85 g of ethylproxitol was added to the reactor over 30 minutes. Before adding the mixture of fatty acids was heated to 85 ° C. The resulting mixture was stirred for 3 hours. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was then centrifuged at 4000 rpm for about 10 minutes. The liquid was decanted and the solids were washed with water and dried in a vacuum oven overnight at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 37.7 Å.

Example 16

100 g of a 20 wt.% Aqueous suspension of a layered hydrotalcite type double hydroxide according to Formula II with a Mg / Al ratio of 2 and hydroxyl as a charge-compensating anion and 12.5 g of ethyl proxitol (ex Shell) were loaded into a 500 ml glass reactor with high speed stirrer and heated to 85 ° C. Then, 25.16 g of Kortacid® PKGH dissolved in 12.5 g of ethylproxitol was added to the reactor over 30 minutes. Before adding the mixture of fatty acids was heated to 85 ° C. The resulting mixture was stirred for 3 hours. Then the reactor was cooled to about 50 ° C and the resulting suspension was discharged. The suspension was then centrifuged at 4000 rpm for about 10 minutes. The liquid was decanted and the solids were washed with water and dried in a vacuum oven overnight at 80 ° C.

A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The intercalate exhibits a characteristic value of d (001) equal to 38.4 Å.

Example 17

1.995 g of magnesium oxide (Zolitho® 40, ex Martin Marietta Magnesia Specialties LLC) and 1.728 g of aluminum trihydroxide (Alumill F505) were mixed in 7500 g of demineralized water and ground to an average particle size (d ₅₀ ) of 1.5 μm. Part of the suspension was diluted with demineralized water to a solids content of 8.8 wt.%. 1.36 kg of the diluted suspension was loaded into an oil-heated autoclave with a high-speed stirrer and heated to 80 ° C. Before adding the suspension, 1.25 kg of 2-ethoxypropanol was added to the autoclave and heated to 80 ° C. The autoclave was then heated to 120 ° C and 354 g of a 50/50 mixture by weight of Kortacid® PH05 and Prifac 7990 was added over 15 minutes. Before adding the mixture of fatty acids was heated to 120 ° C. After adding acid, the autoclave was heated to 170 ° C and held for 1 hour. Then the autoclave was cooled to about 40 ° C and the resulting suspension was unloaded. The suspension was filtered and washed intensively with acetone. The resulting material was dried in a vacuum oven overnight at 80 ° C.

The resulting clay of hydrotalcite type containing a mixture of fatty acids was analyzed by x-ray diffraction to determine the interplanar distance or d-distance. A diffractogram of a hydrotalcite-type clay obtained as described above shows weak non-basal (hk0) reflections related to hydrotalcite, which indicates intercalation of anionic clay. The diffraction pattern gives d (001) values of 52 and 30 Å. In addition, SEM analysis of the washed powder reveals a very high ratio (L / D> 10000) for the resulting rectangular plates.

Example 18

665 g of magnesium oxide (Zolitho® 40, ex Martin Marietta Magnesia Specialties LLC) and 576 g of aluminum trihydroxide (Alumill F505) were mixed in 2500 g of demineralized water and ground to an average particle size (d ₅₀ ) of 1.5 μm. Part of the suspension was diluted with demineralized water to a solids content of 9.6 wt.%. 229 g of the diluted suspension was loaded into an oil-heated autoclave and high-speed stirrer and heated to 90 ° C. Before adding the suspension, 209 g of 2-ethoxypropanol was added to the autoclave and heated to 80 ° C. Then the autoclave was heated to 120 ° C and kept at this temperature for 15 minutes. Then the autoclave was heated to 170 ° C and held for 1 hour. After the reaction, the autoclave was cooled below 60 ° C and the resulting suspension was unloaded. The suspension was filtered and washed thoroughly with acetone. The resulting material was dried in a vacuum oven overnight at 80 ° C.

The resulting hydrotalcite clay was analyzed by x-ray diffraction to determine the interplanar distance or d-distance. The diffraction pattern of hydrotalcite clay obtained as described above shows (hk0) and (001) reflections typical of the hydrotalcite structure and weak signals related to brucite.

Claims (14)

1. A method of obtaining a layered double hydroxide containing a charge-compensating anion, which includes the stages:
(a) preparing a suspension or solution of a precursor comprising a source of divalent metal ions, a source of trivalent metal ions, water and a water miscible solvent in which at least 5 g / l of the charge-compensating anion precursor can be dissolved;
(b) processing the suspension or solution of the precursor to obtain layered double hydroxides,
in which the precursor of charge-compensating anions is added to the suspension or solution before, during or after step (b), and in which, if the charge-compensating anion is an organic anion, less than 50 wt.% the mass of the precursors of the charge-balancing anions are a salt, provided that the charge-balancing anion is not a carbonate. 2. The method according to claim 1, in which the solvent is an alcohol with one hydroxyl group, which is selected from the group consisting of ethanol, n-propyl alcohol, isopropyl alcohol, butanol and alkoxylated alcohol according to the formula

in which R ₁ represents C ₁ -C ₈ alkyl or phenyl, R ₂ is hydrogen or methyl and n is an integer of 1-5. 3. The method according to claim 1 or 2, in which the charge-compensating anion is an organic anion. 4. The method according to claim 2, in which the organic anion contains 8 or more carbon atoms, preferably 10-50 carbon atoms. 5. The method according to claim 3, in which the organic anion is added to the suspension or solution of the precursor to step (b). 6. The method according to claim 3, in which the organic anion is added after the formation of a layered double hydroxide, and the layered double hydroxide contains a charge-compensating anion, which is selected from the group consisting of hydroxyl, nitrate, phosphate, phosphonate, sulfonate, sulfate, bisulfate and halide. 7. The method according to any one of claims 1, 2, 4, 5 or 6, in which the divalent metal ion is Mg ²⁺ , and the trivalent metal ion is Al ³⁺ . 8. The method according to claim 1, further comprising the steps of:
(c) preparing a suspension from a suspending medium and a layered double hydroxide containing a charge-balancing anion, which is selected from the group consisting of hydroxyl, nitrate, phosphate, phosphonate, sulfonate, sulfate, bisulfate and halide;
(d) processing the suspension to obtain a layered double hydroxide containing an organic anion as a charge-compensating anion,
wherein the organic anion precursor is added during step (c) or (d). 9. The method of claim 8, wherein the suspending medium comprises water and / or a solvent which is mixed with water and in which at least 5 g / L of the organic anion precursor can be dissolved. 10. A method of obtaining a layered double hydroxide containing an organic anion as a charge-compensating anion, which includes the steps of:
(a) preparing a suspension of a layered double hydroxide containing a charge-balancing anion selected from the group consisting of hydroxyl, nitrate, phosphate, phosphonate, sulfonate, sulfate, bisulfate and halide, as well as a solvent and optionally water;
(b) processing the suspension or solution of the precursor to obtain a layered double hydroxide,
moreover, the organic anion precursor is added to the suspension during stage (a) or (b), and the solvent is mixed with water and may contain at least 5 g / l of the organic anion precursor dissolved therein. 11. A layered double hydroxide containing a charge-compensating anion obtained by the method according to one of the preceding paragraphs. 12. The layered double hydroxide according to claim 11, in which the charge-compensating anion is an organic anion, and the distance between the individual layers of the layered double hydroxide exceeds 1.5 nm. 13. Nanocomposite material comprising a polymer and a layered double hydroxide according to claim 11 or 12. 14. A concentrate containing a polymer and a layered double hydroxide according to claim 11 or 12, in which the amount of the layered double hydroxide is 10-70 wt.%.