TWI381991B - Clay comprising charge-balancing organic ions and nanocomposite materials comprising the same - 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

Clay containing charge-balanced organic ions and nano composites containing the same

The present invention relates to layered double hydroxides comprising two or more charge-balanced organic anions and uses thereof. The invention further relates to nanocomposites comprising the layered double hydroxide and uses thereof.

Layered double hydroxides (LDH) having two or more charge-balanced organic anions are known in the art. For example, US 2003/0114699 discloses a layered double hydroxide comprising a mixture of three organic anions as an anion of charge balancing. In particular, a hydrotalcite-like clay is described which comprises a mixture of stearic acid, acrylic acid and acetic acid, and an LDH comprising a mixture of stearic acid, acetic acid and hexanoic acid.

WO 2004/019137 describes the use of modified layered double hydroxides in, for example, toner resins. The modified LDHs are described as being organic anions comprising a charge balance of at least two anionic groups. An example of such an organic anion is a dicarboxylic acid ester of sebacic acid. WO 2004/019137 further discloses an LDH having a mixture of sebacic acid and stearic acid as a charge-balanced anion. It should be noted that the modified LDH in its particulate form acts as a charge control agent. The presence of dicarboxylates causes the thin layers of clay to be held together, making peeling or delamination extremely difficult or even impossible.

It is an object of the present invention to provide a nanocomposite which is more suitable for use in a modified layered double hydroxide in a nanocomposite and which provides the modified layered double hydroxide.

This object is achieved by a layered double hydroxide having a distance between individual layers of layered double hydroxides greater than 1.5 nm and comprising 2 or more having 8 or a charge-balanced organic anion of more than 8 carbon atoms, wherein at least two of the organic anions have different numbers of carbon atoms, and wherein less than 10% of the total number of charge-balanced anions has two or more anionic groups The organic anion of the charge balance of the group. The layered double hydroxides of the present invention are generally more easily exfoliated and/or layered in the polymer matrix than conventional LDHs containing organic anions, and are therefore particularly suitable for use in nanocomposites. Thus, the modified LDH is easier to handle in the polymer matrix, which in turn can result in a greater amount of modified LDH exfoliation and/or delamination. The LDH can further make the method of making the nanocomposite more energy efficient and less expensive. Another advantage of the modified LDH is that the mixing of the charge-balanced organic anions is generally more compatible and can be made more compatible with the polymeric matrix by selecting the correct combination of organic anions.

In the context of this application, the term "charge-balanced organic anion" refers to an organic ion that lacks the electrostatic charge of the crystalline clay flakes of LDH. Because clay typically has a layered structure, the charge-balanced organic ions can be located on the interlayer, edge or outer surface of the stacked clay layer. The organic ions located between the layers of the stacked clay layers are referred to as intercalating ions.

The stacked clay or organic clay can also be layered or spalled, for example, in a polymer matrix. In the context of the present specification, the term "layering" is defined as the reduction in the average stacking degree of clay particles de-layered by at least part of the clay structure, thereby producing significantly more individual per volume. The material of the clay flakes. The term "exfoliation" is defined as complete delamination, that is, periodically disappearing in the direction of a vertical clay sheet, which results in random distribution of individual layers in the medium, leaving no stacking order.

The expansion or expansion of clay (also known as the intercalation of clay) can be observed by X-ray diffraction (XRD) because the position of the base reflection (ie d( 001 ) reflection) indicates the distance between the layers, which is inserted Increase after the layer.

The decrease in the average stacking degree can be observed as the XRD reflection broadens until it disappears, or the asymmetry of the base reflection ( 001 ) increases.

The characterization of complete stratification (ie, flaking) presents analytical challenges, but can usually be inferred from the complete disappearance of the non- ( hk0 ) reflection of the original clay.

The order of the layers and thus the degree of delamination can be further visualized by transmission electron microscopy (TEM).

The LDH containing a charge-balanced organic anion has a layered structure corresponding to the following formula: Wherein 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⁺ , Mg ²⁺ , and M ³⁺ is such as Al ³⁺ , Cr ³⁺ , Trivalent metal ions of Fe ³⁺ , Co ³⁺ , Mn ³⁺ , Ni ³⁺ , Ce ³⁺ and Ga ³⁺ , m and n have values such that m/n = 1 to 10, and b has a value in the range of 0 to 10. . X is a mixture of two or more organic anions having a charge balance of 8 or more carbon atoms and optionally any other organic anion or inorganic anion, including hydroxide, carbonic acid Root, bicarbonate, nitrate, chloride, bromide, sulfonate, sulfate, hydrogen sulfate, vanadate, tungstate, borate and phosphate. For the purposes of this specification, salts, carbonates and bicarbonate anions are defined as belonging to inorganic species.

The LDH of the present invention includes hydrotalcite and hydrotalcite-like anionic LDH. Examples of such LDHs are hydroxyaluminite, bauxite, carbon mafic ore, hydrousite (sj Grenite), chromite, hydromagnesite, bauxite, hydrous iron-nickel and hydrous-manganese.

In one embodiment of the invention, the layered double hydroxide has a layered structure corresponding to the following general formula: Wherein m and n have a value such that m/n = 1 to 10, preferably 1 to 6, more preferably 2 to 4, and most preferably close to 3; b has a value in the range of 0 to 10, usually A value between 2 and 6, and often a value of about 4. X is a charge-balanced ion as defined above. m/n should preferably have a value of 2 to 4, more specifically a value close to 3.

LDH can be presented, for example, by Cavani et al. ( Catalysis Today , 11 (1991), pp. 173-301) or by Bookin et al. ( Clays and Clay Minerals , (1993), vol. 41 (5), pp. 558-564). Any of the crystal forms known in the art, such as 3H ₁ , 3H ₂ , 3R ₁ or 3R ₂ stacks.

The distance between individual clay layers in LDH is typically greater than the distance between layers of LDH containing only carbonate as the charge-balanced anion. Preferably, the distance between the layers of the LDH according to the invention is at least 1.5 nm, more preferably at least 1.8 nm and most preferably at least 2 nm. As previously outlined, the distance between individual layers can be determined using X-ray diffraction.

The LDH of the present invention contains two or more organic anions having a charge balance of 8 or more carbon atoms. At least two of the organic anions have a different number of carbon atoms. Such organic anions having at least 8 carbon atoms include monocarboxylates, dicarboxylates or polycarboxylates, monosulfonates, disulfonates or polysulfonates, monophosphonates, diphosphonates or polyphosphonates, mononitrate Roots, dinitrate and polynitrate, and monosulfate, disulfate or polysulfate. Preferably, the organic anion comprises at least 10 carbon atoms, preferably 10 to 40 carbon atoms, and most preferably 12 to 30 carbon atoms. It is contemplated that two or more organic anions are used, at least one of which has at least 8 carbon atoms, and the resulting LDH has an interlayer distance of at least 1.5 nm; therefore, one of the other organic anions may have less than 8 carbon atoms.

The organic anion further encompassing charge balancing comprises one or more such as acrylate groups, methacrylate groups, hydroxyl groups, chloride groups, amine groups, epoxy groups, thiol groups, vinyl groups, di- and polysulfide groups, A functional group of a urethane group, an ammonium group, a hydrazine, a hydrazine, a monobasic phosphonic acid group, an isocyanate group, a fluorenyl group, a hydroxyphenyl group, a hydride group, an ethoxy group, and an anhydride group. If the organically modified LDH is used in a polymeric matrix, the functional groups can interact or react with the polymer.

It should be noted that less than 10% of all charge-balanced organic anions are organic anions having two or more anionic groups. In the context of the present application, the term "anionic group" refers to a group having an anionic charge. Examples of such anionic groups are carboxylates, sulfonates, phosphonates, nitrates and sulfates. Such organic anions having 2 or more anionic groups are less preferred because they are generally capable of interconnecting two continuous layers which cause the layers to be non-exfoliated or delaminated and therefore less suitable for use Nano composites. For this reason, the amount of such organic anions as the charge-balanced anion should be kept at 10% (mole/mole), preferably less than 5%, and more preferably less than the total amount of charge-balanced organic anions. Less than 2%. In one embodiment of the invention, there are no organic anions having two or more anionic groups. Examples of organic anions suitable for use in the LDH of the present invention are monocarboxylates such as fatty acid-derived anions, naphthenic acid-derived anions, and rosin-based ions.

The LDH of the present invention may comprise two or more organic anions derived from saturated or unsaturated fatty acids having 8 to 22 carbon atoms. The modified LDH may comprise a naphthenic acid derived organic anion (i.e., a mixture of various carboxylic acids comprising a cyclopentane ring). It may also comprise a combination of rosinic acids having an anion derived from a saturated or unsaturated fatty acid.

Examples of the fatty acid-derived anion having 8 to 22 carbon atoms include those derived from octanoic acid, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, citric acid, palmitoleic acid, oleic acid, and sub- An organic anion of linoleic acid, linoleic acid, and mixtures thereof.

Rosinic acid or rosin is derived from natural sources and is readily available and relatively inexpensive compared to synthetic organic anions. Typical examples of natural sources of rosin are gum rosin, wood rosin and high oil rosin. Rosin is typically a mixture of a wide variety of different isomers of monocarboxylic acid tricyclic abietic acid, typically having 20 carbon atoms. The three ring structures of these various rosin acids differ mainly in the position of the double bonds. Usually, the rosin contains L-sea pimaric acid, neo-abietic acid, long-leafed acid, rosin acid, dehydroabietic acid, second dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, tyrosine acid and isoprene resin. a mixture of acids. Rosin derived from natural sources also includes rosin specially modified by acrylic acid, acrylic anhydride and acrylate by polymerization, isomerization, disproportionation, hydrogenation and Diels-Alder reaction, ie Rosin mixture. The product obtained by these methods is referred to as modified rosin. Natural rosin can also be chemically altered by any method known in the art, such as the carboxyl group on the rosin reacting with a metal oxide, metal hydroxide or salt to form a rosin soap or salt (so-called resinate). These chemically altered rosins are referred to as rosin derivatives.

The rosins may be modified or chemically altered by the introduction of an organic group, an anionic group or a cationic group. The organic group may be a substituted or unsubstituted aliphatic hydrocarbon or an aromatic hydrocarbon having 1 to 40 carbon atoms. The anionic group can be any anionic group known to those skilled in the art, such as carboxylate or sulfonate.

Additional details of such rosin-based materials are available from DFZinkel and J. Russell (in Naval Stores, production-chemistry-utilization , 1989, New York, Part II, Chapter 9) and JBClass ("Resins, Natural," Chapter 1: "Rosin and Modified Rosins," Kirk-Othmer Encyclopedia of Chemical Technology , online publication date: December 4, 2000).

In another embodiment of the invention, the LDH comprises 3 or more organic anions having a charge balance of 8 or more carbon atoms. Preferably, the LDH of the present invention comprises 4 or more organic anions having a charge balance of 8 or more carbon atoms. The more organic anions present as charge-balanced organic anions, the easier it is for the modified LDH to flake off or delaminate in the polymer matrix. In addition, such modified LDHs are generally more compatible with a wider range of polymeric matrices.

In addition to an organic anion having 8 or more carbon atoms, other organic anions having less than 8 carbon atoms and/or an inorganic anion as defined above may be present as a charge-balanced anion present in the modified LDH of the present invention. in.

Usually, at least 10% of the total amount of intercalated ions in the LDH type according to the present invention is a mixture of 2 or more organic anions having 8 or more carbon atoms, preferably intercalated ions At least 30%, more preferably at least 60%, and most preferably at least 90% is a mixture of 2 or more organic anions having 8 or more carbon atoms. In one embodiment of the invention, at least 10% of the total amount of charge-balanced organic anion is a fatty acid-derived anion or a rosin-based anion or a mixture of two anions; preferably, at least 30 of the total amount of charge-balanced ions More preferably, at least 60%, and most preferably at least 90% is a mixture of fatty acid-derived anions or rosin-based anions or two anions.

The LDH according to the present invention can be prepared in a manner similar to the known methods for preparing prior art organic clays. Examples of such methods for LDH can be found in WO 00/09599.

Suitable methods for preparing an organic clay according to the present invention include: a. ion exchange with organic ions; b. synthesis of clay in the presence of organic ions; c. calcination of the clay and subsequent rehydration in the presence of organic ions; d. The carbonate ions of the clay are exchanged and subsequently ion exchanged with organic ions.

Refer to Carlino ( Solid State Ionics , 1996, 98, pp. 73-84) for other methods. In this article, methods such as thermal or melt reaction methods and glycerol-implemented exchange methods are described. According to the heat or melt reaction method, the LDH and the organic anion mixture are intimately mixed at a high temperature, preferably at a temperature higher than the melting temperature of the organic anion having the highest melting temperature. According to the exchange method achieved by the glycerol, there is an glycerol-expanded intermediate of LDH, after which an organic anion mixture is introduced and then intercalation occurs. It should be noted that this method can also be carried out using a swelling agent other than glycerin, such as ethanol, 2-ethoxypropanol, 2-propanol, butanol, triethylene glycol, and the like. Alternatively, the LDH of the present invention can be prepared by melt blending a charge-balanced anion and clay.

The LDH of the present invention can be used as a coating composition, a (printing) ink formulation, an adhesive tackifier, a resin-based composition, a rubber composition, a cleaning formulation, a drilling fluid and a cement, a gypsum formulation, a non-woven fabric, and a fiber. , a foam, a film, an orthoplastic casting, a (pre)ceramic material, and a component in a mixed organic-inorganic composite material such as a polymer nano-composite. The LDH of the present invention can be further used in polymerization reactions such as solution polymerization, emulsion polymerization, and suspension polymerization. The organic clay can further serve as a crystallization aid in a semi-crystalline polymer such as polypropylene. The LDH of the present invention can be further used in applications where the independent functions of LDH and organic anions can be combined, such as in the papermaking process or the detergent industry. In addition, the LDH of the present invention can be used in controlled release applications of drugs, insecticides and/or fertilizers, and can be used as an adsorbent for organic compounds such as contaminants, colorants and the like.

The invention further relates to a nanocomposite comprising a polymeric matrix and a modified LDH according to the invention. Using the modified LDH of the present invention, a higher degree of spalling and/or delamination can be achieved in a wider variety of polymer matrices, and the amount of micron-sized modified LDH will generally be small or even absent. This enables the use of lower amounts of modified LDH in the nanocomposite. It is therefore possible to provide a nanocomposite having relatively low density and good mechanical properties. The fully exfoliated and/or layered LDH in the nanocomposite can render the material transparent to visible light and thus make it suitable for use in optical applications.

The term "nanocomposite" means a composite material in which at least one of the components comprises an inorganic phase having at least one dimension in the range of from 0.1 to 100 nanometers.

Particularly suitable for use in the nanocomposite of the present invention is an LDH comprising a mixture of charge-balanced organic anions wherein at least one of the charge-balanced organic anions is chemically altered to be more compatible or more reactive with the polymer matrix. . This improves the interaction between the LDH and the polymer matrix, improving mechanical and/or viscoelastic properties. More compatible organic anions may comprise substituted or unsubstituted aliphatic or aromatic hydrocarbons having from 1 to 40 carbon atoms. Additionally or alternatively, at least one of the organic anions may comprise an acrylate group, a methacrylate group, a hydroxyl group, a chloride group, an amine group, an epoxy group, a thiol group, a vinyl group, a di- and polysulfide group. Substrate, urethane, ammonium, sulfonate, sulfinate, hydrazine, hydrazine, monophosphonic acid, isocyanate, fluorenyl, hydroxyphenyl, hydride, ethoxy, and anhydride a reactive group of constituent groups.

Polymers which may be suitable for use in the nanocomposites of the present invention may be any polymer matrix known in the art. In the present specification, the term "polymer" means an organic substance of at least two building blocks (ie, monomers), and thus includes oligomers, copolymers, and polymeric resins. Suitable polymers for use in the polymer matrix are polyadducts and polycondensates. These polymers may additionally be homopolymers or copolymers. Preferably, the polymeric matrix has a degree of polymerization of at least 20, more preferably at least 50. In this connection, with regard to the definition of degree of polymerization, reference is made to PJ Flory, Principles of Polymer Chemistry , New York, 1953.

Examples of suitable polymers are polyolefins such as polyethylene or polypropylene, vinyl polymers such as polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride or polyvinylidene fluoride, such as Polyethylene terephthalate, polylactic acid or poly(ε-caprolactone) saturated polyester, unsaturated polyester resin, acrylate resin, methacrylate resin, polyimine, epoxy resin , phenolic resin, urea-formaldehyde resin, melamine formaldehyde resin, polyurethane, polycarbonate, polyaryl ether, polyfluorene, polysulfide, polyamine, polyether phthalimide, polyether ester, polyether ketone, polyether ester Ketones, polyoxyalkylenes, polyurethanes, polyepoxides, and blends of two or more polymers. Preference is given to using polyolefins, vinyl polymers, polyesters, polycarbonates, polyamines, polyurethanes or polyepoxides.

The organic clay according to the present invention is particularly suitable for use in thermoplastic polymers such as polyethylene, polypropylene, polystyrene, and acetal (co)polymers such as polyoxymethylene (POM), and is suitable for use in, for example, natural rubber (NR), Styrene-butadiene rubber (SBR), polyisoprene (IR), polybutadiene (BR), polyisobutylene (IIR), halogenated polyisobutylene, nitrile rubber (NBR), hydrogenated nitrile rubber ( HNBR), styrene-isoprene-styrene (SIS) and similar styrenic block copolymers, poly(epichlorohydrin) rubber (CO, ECO, GPO), ruthenium rubber (Q), chloroprene Ethylene rubber (CR), ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), polysulfide rubber (T), fluororubber (FKM), ethylene vinyl acetate rubber (EVA) Polyacrylic rubber (ACM), polynorbornene (PNR), polyurethane (AU/EU) and polyester/ether thermoplastic elastomers.

Particularly preferred are polymers or copolymers obtainable by polymerization of 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, polyvinyl chloride, polyvinylidene chloride and ethylene propylene rubber, propylene-butene copolymer, ethylene-chloride. 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, vinyl chloride-propylene copolymer and mixtures thereof. Even better polymers are polyethylene, polypropylene, polystyrene and polyvinyl chloride.

Specific examples of 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 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 polypropylene known in the art will be suitable for use in the present invention. Examples of polypropylene are given by RBLieberman in Kirk-Othmer Encyclopedia of Chemical Technology , online publication dated December 4, 2000, "Polypropylene", Chapter 1: "Properties". The particular type of polypropylene of the present invention is formed by the so-called thermoplastic polyolefin (TPO), which includes a blend of polypropylene and EPR 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, fiberglass, natural and synthetic fibers, and others). Inorganic materials), flame retardants, nucleating agents, impact modifiers, plasticizers, rheology modifiers, crosslinkers, coupling agents and degassing agents.

The optional addenda and their corresponding amounts can be selected as desired.

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

The amount of LDH of 10% by weight or less, preferably 1-10% by weight, more preferably 1-5% by weight, for the preparation of the polymer nano-composite (ie, containing the layered-to-flaking-organic modified LDH basis) The polymer-containing composition of the invention) is especially advantageous.

An amount of LDH of from 10 to 70% by weight, more preferably from 10 to 50% by weight, is particularly advantageous for the preparation of the so-called parent mixture, that is to say a highly concentrated additive premix for, for example, a polymer compound. Although the clay in the parent mixture is generally not completely delaminated and/or exfoliated, when the parent mixture is blended with another polymer to obtain a true rubber-based nanocomposite, (if needed) can be subsequently Achieve further stratification and/or spalling.

The nanocomposite of the present invention can be prepared according to any method known to those skilled in the art. One skilled in the art can intimately mix the polymer matrix with the organic clay according to the present invention by using, for example, a melt-blending technique. This method is preferred because the method is simple, cost effective, and easy to apply to existing plants. It is also contemplated to prepare the clay of the present invention in the presence, after or after polymerization of the monomers and/or oligomers to form a polymer matrix, in the presence of a polymer matrix or in the presence of monomers and/or oligomers. Further details on the preparation and handling of polypropylene can be found in "Polypropylene" by RBLieberman in Kirk-Othmer Encyclopedia of Chemical Technology , online dated December 4, 2000, Chapter 2: "Manufacture", and Chapter 3: "Processing "in.

The nanocomposite of the present invention can be used in any application in which the composite materials are conventionally used. Nano composites are suitable for carpets, automotive parts, container closures, lunch boxes, closures, medical devices, household items, food containers, dishwashers, outdoor equipment, blown bottles, disposable non-woven fabrics, cables and Wire and packaging. Further details regarding polypropylene can be found in RBLieberman's Kirk-Othmer Encyclopedia of Chemical Technology , online publication dated December 4, 2000, "Polypropylene", Chapter 5: "Uses", and Basell titled "Polypropylene: Textile," Rigid Packaging, Consumer, Film, Automotive, Electrical/Electronics and Home Appliances, Booklet 022 PPe 10/01.

Rubber-containing nanocomposites are suitable for use in tire manufacturing, such as in green tires, truck tires, construction tires and aircraft tires, in winter tires, including gloves, condoms, balloons, catheters, Used in footwear for latex, foam, carpet backing and rubberized coir and hair latex products for use in civil engineering products such as bridge supports and rubber-metal laminate supports. In belts and hoses for non-tire automotive applications including engine mounts, rubber supports, seals, insulation rings, gaskets and compartments, for use in conductors and cables, and for pipe seals, medical closures, Rollers, small solid tires, mounts for household appliances and commercial appliances, rubber balls and tubes, milking equipment and other agricultural basic applications.

If the rubber is a polyoxyxene rubber and the modified layered double hydroxide is in accordance with the present invention, the nano composite materials can be applied to coating products including pressure sensitive adhesives, plastic hard shells and release coatings, and For fiber processing applications, sealants, adhesives, encapsulants and solar cell devices including fabric and hair care applications.

The invention is further illustrated by the following examples.

Instance

Commercially available fatty acids are used in accepted form. Kortacid PH05 (a blend of palmitic acid and stearic acid) is supplied by Oleochemicals GmbH, a company of Akzo Nobel Chemicals.

In addition, stable rosin is also used. The stabilized rosin is produced indoors by melting Chinese gum rosin and heating it to 235 °C. Melting 3.5% by weight Vultac Add rosin during -2 (from Arkema Inc.). The molten rosin was stirred at 235 ° C for 15 hours, after which the resin was cooled and set aside.

Example 1

The 68.2 g of magnesium oxide (Zolitho 40, from Martin Marietta Magnesia Specialties LLC) and 43.6 grams of aluminum hydroxide (Alumill F505) were mixed in 840 grams of demineralized water and ground to an average particle diameter of 2.5 μm (d _50). The slurry was fed into an oil-heated autoclave equipped with a high-speed stirrer and heated to 80 °C. Then 132 grams of Kortacid will be passed in 15 minutes. A 50/50 suspension by weight of PH05 and stabilized rosin prepared as above was added to the autoclave. The acid suspension was heated to 80 °C prior to addition. After the acid addition, the autoclave was closed and heated to 170 ° C and maintained in this condition for 1 hour. The autoclave was then cooled to about 40 ° C and the resulting slurry was removed. The slurry was then centrifuged at 2,000 rpm for about 10 minutes. The liquid was decanted and the solid was dried overnight in an oven under vacuum at 80 °C.

The resulting hydrotalcite-like clay containing fatty acids and rosin-based ions was analyzed by X-ray diffraction to determine the intermediate channel spacing or d-spacing. The XRD pattern of the hydrotalcite clay prepared as above shows a micro-hydrotalcite-related non-(hk0) reflection indicating the intercalation of an anionic clay. Intercalation display 28 Characteristic d(001) value - which is 7.6 than pure hydrotalcite clay Or 8.0 The d spacing is much larger.

Comparative example 2

300 grams of magnesium oxide (Zolitho 40, from Martin Marietta Magnesia Specialties LLC) and 230 grams of aluminum hydroxide (Alumill F505) mixed in 648 grams of demineralized water and ground to an average particle size (d ₅₀ ) of 2.5 μm. The slurry was fed into an oil-heated autoclave equipped with a high-speed stirrer and heated to 120 °C. 670 grams of stearic acid (from Acros) was then added to the autoclave over a period of 30 minutes. The fatty acid was heated to 120 °C prior to addition. After the acid addition, the autoclave was heated to 170 ° C and maintained in this condition for 1 hour. The autoclave was then cooled to about 40 ° C and the resulting slurry was removed. The slurry was filtered using a glass filter and the resulting solid was dried overnight in an oven under vacuum at 80 °C.

The resulting hydrotalcite-like clay containing fatty acids was analyzed by X-ray diffraction to determine the intermediate channel spacing or d spacing. The XRD pattern of the hydrotalcite clay prepared as above shows a micro-hydrotalcite-related non-(hk0) reflection indicating the intercalation of an anionic clay. Intercalation display 29 The characteristic d (001) value.

Example 3

Commercially available fatty acids are used in accepted form. Kortacid PH05 (a blend of palmitic acid and stearic acid) is supplied by Oleochemicals GmbH, a company of Akzo Nobel Chemicals.

50 grams of magnesium oxide (Zolitho 40, from Martin Marietta Magnesia Specialties LLC) and 39 grams of aluminum hydroxide (Alumill F505) mixed in 648 grams of demineralized water and ground to an average particle size (d ₅₀ ) of 2.5 μm. The slurry was fed into an oil-heated autoclave equipped with a high-speed stirrer and heated to 120 °C. Then 102 grams of Kortacid will be passed in 30 minutes. PH05 was added to the autoclave. The fatty acid blend was heated to 120 °C prior to addition. After the acid addition, the autoclave was heated to 170 ° C and maintained in this condition for 1 hour. The autoclave was then cooled to about 40 ° C and the resulting slurry was removed. The slurry was then centrifuged at 2,000 rpm for about 10 minutes. The liquid was decanted and the solid was dried overnight in an oven under vacuum at 80 °C.

The resulting hydrotalcite-like clay comprising the fatty acid blend was analyzed by X-ray diffraction to determine the intermediate channel spacing or d spacing. The XRD pattern of the hydrotalcite clay prepared as above shows a micro-hydrotalcite-related non-(hk0) reflection indicating the intercalation of an anionic clay. Intercalation display 28 The characteristic d (001) value.

Comparative Example 4 and Example 5

The modified layered double hydroxide of Example 2 was separately ground using a Hosokawa Alpine 50 ZPS circoplex multi-treatment mill. The resulting powder had a d50 value of 1.9 μm and a d90 value of 5.7 μm as determined according to DIN 13320.

Preparation of 50% by weight of powdered modified LDH of Comparative Example 2 and 50% by weight of Intol The parent mixture of 1502 (SBR rubber from Polimeri). The Intol 1502 was fed into an open double roller mill (Agila), after which the powdered modified LDH was added over a period of 30 minutes. The twin roll mill operates at a temperature between 50 ° C and 70 ° C with a friction factor of 1.2.

The resulting precursor mixture was diluted with the same rubber precursor onto an open two-roll mill operating under the same conditions as described above to a final concentration of 10 phr of modified LDH in the rubber. In the second step, a sample of the diluted compound was placed in an internal mixer at 60 ° C and 50 rpm (equipped with a 60 CC mixing chamber Rheomix containing a roller rotor) 600 of Rheocord 90) Peel off for 10 minutes.

In a twin roll mill, approximately 50 grams of the resulting sample was then with 0.52 phr of dicumyl peroxide (Perkadox from Akzo Nobel) BC-ff) mixed. The twin roll mill operates at a temperature between 50 ° C and 70 ° C with a friction factor of 1.2. The resulting mixture was finally compression molded into a 2 mm thick sheet at 170 ° C and 400 kN for 15 minutes to obtain a SBR rubber nano composite (Comparative Example 4 nano composite).

The nanocomposite was analyzed using a transmission electron microscope. The resulting TEM image is shown in Figure 1.

The modified LDH of Example 3 was ground using the same procedure as above. The obtained powder had a d50 value of 4.0 μm and a d90 value of 10.5 μm.

A powdery modified LDH containing 50% by weight of Example 3 and 50% by weight of Intol were prepared in the same manner as above. The second parent mixture of 1502.

A TEM image of this nanocomposite (Nano composite of Example 5) is shown in Figure 2.

The TEM images of Figures 1 and 2 show the distribution of clay in the SBR rubber matrix. It can be clearly seen that Figure 1 shows large clay particles in the rubber matrix which are not present in Figure 2. Moreover, the distribution of the thin layer of clay in Figure 2 is superior to the distribution observed in Figure 1. In summary, the nanocomposite comprising the LDH of the present invention shows that the clay is more susceptible to delamination/flaking and exhibits a clay distribution in the LDH modified SBT rubber matrix of Example 2.

Figure 1 shows a TEM image of a SBR rubber nanocomposite of Comparative Example 4.

2 is a TEM image of the SBR rubber nanocomposite of Example 5.

Claims (11)

a layered double hydroxide having a distance between individual layers of the layered double hydroxide of greater than 1.5 nm and comprising 2 or more charge balances having 8 or more carbon atoms An organic anion wherein at least two of the organic anions have a different number of carbon atoms, and wherein less than 10% of the total number of charge-balanced anions is an organic anion having a charge balance of two or more anionic groups. The layered double hydroxide of claim 1, which comprises 3 or more organic anions having a charge balance of 8 or more carbon atoms, wherein the layered double hydroxide preferably comprises 4 or More than 4 charge-balanced organic anions. The layered double hydroxide of any one of claims 1 and 2, wherein the organic anions having 8 or more carbon atoms constitute at least 50% of the total number of ions of charge balance. A nanocomposite comprising the layered double hydroxide of any one of claims 1 to 3 in a polymer matrix. The nanocomposite of claim 4, wherein the polymeric matrix comprises a (co)polymer obtainable by polymerizing at least one ethylenically unsaturated monomer. The nanocomposite of claim 4, wherein the polymer is rubber. The nanocomposite according to any one of claims 4 to 6, wherein at least one of the organic anions having 8 or more carbon atoms is selected from the group consisting of an acrylate group, a methacrylate group, a hydroxyl group, Chloride, amine, epoxy, thiol, vinyl, di- and polysulfide, urethane, ammonium, ruthenium, osmium, monophosphonate, isocyanate, sulfhydryl, hydroxybenzene A reactive group of a group consisting of a hydride group, a hydride group, and an anhydride group. The nanocomposite according to any one of claims 4 to 6, which comprises from 1 to 10% by weight, based on the total weight of the nanocomposite, of the layered double hydroxide. A parent mixture comprising from 10 to 70% by weight, based on the total weight of the composite, of the layered double hydroxide of any one of claims 1 to 3, and from 30 to 90% by weight of the polymer. Use of the layered double hydroxide according to any one of claims 1 to 3 for a coating composition, an ink formulation, an adhesive tackifier, a resin-based composition, a rubber composition, a cleaning formulation , drilling fluids, cement, gypsum formulations, non-woven fabrics, foams, films, orthoplastic castings, ceramic materials, polymeric reactants, paper, detergents, for pharmaceuticals, pesticides and/or fertilizers Controlled release applications, or adsorbents in organic compounds. Use of a nanocomposite according to any one of claims 4 to 8 for carpets, automotive parts, container closures, lunch boxes, closures, medical devices, household items, food containers, dishwashers , outdoor equipment, blown bottles, disposable non-woven fabrics, cables and wires, or packaging.