Modified Layered Double Hydroxides (LDHs), Particles Comprising Such Modified LDHs, and Methods for Producing Such Modified LDHs

Abstract

The present invention relates to modified layered double hydroxides (LDHs), particles comprising such modified LDHs, resin compositions (comprising the particles and a resin), dispersions (comprising the particles and a liquid), and methods for producing such modified LDHs. The modified layered double hydroxides according to the present invention comprise a modified layered double hydroxide of formula (I) below, which comprises a modified outer layer: [[[M1 2+ ] y (M2 2+ ) z ] 1-x [M3 3+ ] x (OH2)](A n- ) x / n mH2O (I) During the ceremony, M1 and M2 are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M3 is a trivalent metal such as Al and / or Fe, especially Al; A n- is one or more intercalating n-valent anions, m, x, y, and z are values ​​within the ranges indicated below, 0≦m<2 0 <x≦0.5 0.5≦y+z≦1 The outer layer is modified with a derivative of an organic acid or its salt.

Description

[Technical Field]

[0001] The present invention relates to a modified layered double hydroxide (LDH), particles comprising the modified layered double hydroxide (LDH), a resin composition comprising the particles and a resin, a dispersion comprising the particles and a liquid, and a method for producing the modified layered double hydroxide (LDH). [Background technology]

[0002] Conventional hydrotalcite particles have been developed for a variety of applications, including as a thermal stabilizer for polyvinyl chloride resin, a neutralizing agent for the residues resulting from the use of catalysts in the polymerization of polyolefins, an acid acceptor for halogen-containing rubber, and an insulating material for agricultural films. Furthermore, a suspension comprising particles of conventional hydrotalcite may be used as a liquid antacid or thermal stabilizer. Summary of the Invention [Problem to be solved by the invention]

[0003] A problem with conventional hydrotalcite particles used in polymer compositions is that they only have a single function, such as acting as an acid scavenger.

[0004] The object of the present invention is to obviate or at least mitigate the above problems, thereby enabling efficient and effective functioning (or functionality or functionality or functionality) of modified layered double hydroxides. [Means for solving the problem]

[0005] For such purposes, a compound of formula (I): [[[M1 2+ ] y (M2 2+ ) z ] 1-x [M3 3+ ] x (OH)2](A n- ) x / n mH2O (I) [In the formula, M1 and M2 are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M3 is a trivalent metal such as Al and / or Fe, especially Al; A n- is one or more intercalating n-valent anions (or intercalating n-valent anions), m, x, y and z are values ​​within the ranges shown below. 0≦m<2 0 <x≦0.5 0.5≦y+z≦1] This is achieved by a modified layered double hydroxide (LDH) of the above-mentioned formula (1). Such a modified layered double hydroxide (LDH) comprises a modified outer layer, and such outer layer is modified with an organic acid derivative or a salt thereof.

[0006] It should be noted that, in this application, modified layered double hydroxide (LDH) means a material containing exchangeable anions and HO (as an interlayer, i.e., as an intermediate layer between stacked hydroxide basic layers). This application further relates to the use of modified layered double hydroxides (LDHs) by taking advantage of their dual functionality, i.e., acid scavenger and nucleation. Thus, in a first aspect, the present invention provides a modified layered double hydroxide (LDH). The modified LDH comprises one or more intercalating n-valent anions (also called intercalating n-valent anions) and an outer layer. The intercalating n-valent anions (also called intermediate layer or interlayer) comprise an n-valent anion (where the valency is n), and the outer layer has been modified with an organic acid derivative or a salt thereof.

[0007] It should also be noted that in certain embodiments, the functional group of the modified outer layer of the modified layered double hydroxide (LDH) may be referred to as a carboxylic acid derivative. Such derivatives may include the carboxylic acid itself, carboxylates (or carboxylate salts or carboxylate esters) (deprotonated carboxylic acids), amides, esters, thioesters, and acylphosphates. Furthermore, the organic acid derivative may be represented by a salt of the corresponding organic acid derivative.

[0008] It should also be noted that in one embodiment, the modified layered double hydroxide (LDH) may contain various metals (or different metals), which may be selected from the group M1, M2 and M3. In other words, there may be multiple or various metals (or different metals) present for each of M1, M2 and M3 in the modified layered double hydroxide (LDH).

[0009] The advantage of the modified layered double hydroxides (LDHs) according to the present invention is that such layered double hydroxides (LDHs) have dual functionality. Such dual functionality allows, for example, the reduction of resources (additives) during and / or after the synthesis of the polymer. Preferably, after polymerization, the polymer is provided with a modified layered double hydroxide (LDH) and / or an additive. As a result, such syntheses can be carried out more economically and in a more environmentally friendly manner. In particular, it has been found that the above-mentioned dual function (or functionality or functionality) (or dual functionality) can be achieved by modifying (or altering or denaturing or modifying or modifying) the outer layer (or outer layer) of LDH with an organic acid derivative or its salt.

[0010] It should be noted that throughout this application, the synthesis of a polymer includes all steps (or stages) that produce (or generate or form) the final polymeric product / composition. In other words, synthesis involves polymerization of the desired polymer and mixing (e.g., extrusion) the polymer with the modified layered double hydroxide (LDH) and / or additives.

[0011] Such a mixing step may include mixing, preferably a step of mixing in the solid state and / or a step of dispersing (or dispersing) the polymer after polymerization with the modified layered double hydroxide (LDH) and / or additive (or additive). If necessary, the step of dispersing such a mixture may be carried out in an extruder.

[0012] The modified layered double hydroxides (LDHs) according to the present invention can replace acid scavengers (or acid scavengers) and nucleating agents (or nucleating agents) in the synthesis of polymers. As a result, the complexity (or hassle) of supplying additives during polymer synthesis is reduced. Additionally, it has been found that the modified layered double hydroxides (LDHs) according to the present invention provide cleaner polymers compared to polymer compositions using conventional acid scavengers and nucleating agents.

[0013] For example, it may be possible to replace a migratory component such as metallic soap. The result is improved specific migration limits (SMLs) and / or volatile organic compound (VOC) emissions.

[0014] It has been found that: The modified layered double hydroxides (LDHs) according to the present invention may be used efficiently and effectively in the synthesis of polypropylene, polyethylene and polystyrene. It should be noted that: Polypropylene includes homopolymers, copolymers (random and heterophasic copolymers), etc. Polyethylene includes high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), etc.

[0015] A further advantage of the modified layered double hydroxides (LDHs) according to the present invention is that they are compatible with conventional additives (polymer additives) such as antioxidants, UV stabilizers, dispersing agents, etc. Furthermore, the modified layered double hydroxides (LDHs) according to the present invention are compatible with additive formulations (or mixtures or blends) and / or concentrates. Therefore, the modified layered double hydroxides (LDHs) according to the present invention may be used efficiently and effectively in the synthesis of polymers. Preferably, when used / introduced after polymerisation of the polymer, a polymer composition is provided comprising a modified layered double hydroxide (LDH) according to the present invention and one or more of the above-mentioned additives.

[0016] A further advantage of the modified layered double hydroxides (LDHs) according to the present invention is that they are compatible with various techniques for polymer synthesis. For example, extrusion processes, injection processes, additive formulations (or mixtures or blends), and concentrates (or concentrates) are included. Extrusion (or extrusion) and / or injection (or injection) may include thermoforming, extrusion blow molding, sheet extrusion, extrusion compression molding, pipe extrusion, film casting, blown film, raffia extrusion, tape extrusion, fiber extrusion, meltblown material (or meltblown material), spunbond fabric (or spunbond fabric), injection molding, injection stretch blow molding, injection blow molding, compression molding, rotational molding, 3D printing (or 3D print or 3D printing). Therefore, the modified layered double hydroxides (LDHs) according to the present invention may be used efficiently and effectively in the synthesis of polymers.

[0017] For example, a polymer composition comprising a modified layered double hydroxide (LDH) according to the present invention may be used as a film on cups, trays, pallets, and the like.

[0018] In a preferred embodiment according to the present invention, the derivative of an organic acid or its salt is mono- or di-carboxy-C 1-12 Alkyl, C 1-12 Alkyl sulfonyl hydroxide, C 1-12 Alkylphosphonic acid, bis C 1-12 Alkyl phosphonates, N-substituted isocyanurates, mono-, di- or tri-carboxy-C 3-8 Cycloalkanes, the following formula (II): [ka] (II) [In the formula, k is an integer from 1 to 3, n is an integer from 0 to 5, A represents cycloalkyl, aryl or heteroaryl; L represents a direct bond or NH; R1 is independently hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amido, C 1-6 one or more selected from alkyl, hydroxyphosphoryl, Het, or Ar; Ar represents aryl; Het represents a heterocycle; R2 represents C, P or S; R3 is hydroxy and is present when L represents a direct bond, or R3 is hydroxy or C when L represents NH. 1-6 is alkyl, R4 is hydroxy or C 1-6alkylcarbonyl and present when R2 represents P, or R4 is a double-bonded oxygen (or oxygen having a double bond or doubled bonded oxygen) and present when R2 represents S. One or more of the organic acid derivatives may be selected from the following:

[0019] In a preferred embodiment, n is an integer of 0-2.

[0020] Mono-, di- or tri-carboxy-C 3-8 The cycloalkane may be substituted with one or more C 1-6 Note that alkyl may be included. For example, such a substituent may be located at the para position of a mono-carboxycyclohexane.

[0021] In a further preferred embodiment according to the present invention, the derivative of an organic acid or a salt thereof is a mono- or di-carboxy-C 1-12 Alkyl, C 1-12 Alkyl sulfonyl hydroxide, C 1-12 Alkylphosphonic acid, bis C 1-12 Alkyl phosphonates, represented by the following formula (II): [ka] (II) [In the formula, k is an integer from 1 to 3, n is an integer from 0 to 5, A represents cycloalkyl, aryl or heteroaryl; L represents a direct bond or NH; R1 is independently hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amido, C 1-6 one or more selected from alkyl, hydroxyphosphoryl, Het, or Ar; Ar represents aryl; Het represents a heterocycle; R2 represents C, P or S; R3 is hydroxy and is present when L represents a direct bond, or R3 is hydroxy or C when L represents NH. 1-6 is alkyl, R4 is hydroxy or C 1-6 alkylcarbonyl and present when R2 represents P, or R4 is a double-bonded oxygen (or oxygen having a double bond or doubled bonded oxygen) and present when R2 represents S. The organic acid derivatives may be selected from one or more of the following: Preferably, formula (II) is the following formula (III): [ka] (III) is expressed by

[0022] In a further preferred embodiment according to the invention, when A is cycloalkyl, this cycloalkyl is norbornane, norbornene, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl or cyclohexenyl.

[0023] In a further preferred embodiment according to the present invention, n is an integer of 0-2.

[0024] It should be noted that: Derivatives of various organic acids or salts thereof may be present in the modified layered double hydroxides (LDHs) according to the present invention. Therefore, the organic acid derivative or its salt may be directly bound to the outer layer of the LDH, thereby providing a modified layered double hydroxide (LDH) according to the present invention.

[0025] It should also be noted that in Formula II and / or Formula III, when R2 represents C, R4 is absent.

[0026] The advantage of the organic acid derivatives or salts thereof is that they provide efficient and effective modified layered double hydroxides (LDHs), which preferably have at least dual functionality. In the present disclosure, as mentioned above, the dual functionality is preferably a function as an acid scavenger (or acid scavenger or acid scavenger) and a nucleating agent (or nucleating agent or nucleating agent).

[0027] A further advantage of the above organic acid derivatives or salts thereof is that they suppress and / or reduce undesirable effects from halogens in the resulting polymer composition after synthesis. Therefore, compositions comprising a modified layered double hydroxide (LDH) according to the present invention and a polymer are less susceptible to such undesirable (or adverse) effects.

[0028] In a currently more preferred embodiment according to the invention, A may be aryl or heteroaryl.

[0029] It has been found that A being aryl or heteroaryl allows for efficient and effective acid scavenging and nucleation, for example, in polymer synthesis.

[0030] In a preferred embodiment, the modified layered double hydroxide according to the present invention has the following formula (I): [[[M1 2+ ] y (M2 2+ ) z ] 1-x[M3 3+ ] x (OH)2](A n- ) x / n mH2O (I) [In the formula, M1 and M2 are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M3 is a trivalent metal such as Al and / or Fe, especially Al; A n- is one or more intercalating n-valent anions (or intercalating n-valent anions), m, x, y, and z are values ​​within the ranges shown below. 0≦m<2 0 <x≦0.5 0.5≦y+z≦1] and a modified outer layer, which is modified with a derivative of an organic acid or a salt thereof. The derivatives of organic acids or their salts are mono- or di-carboxy-C 1-12 Alkyl, C 1-12 Alkyl sulfonyl hydroxide, C 1-12 Alkylphosphonic acid, bis C 1-12 Alkyl phosphonates, represented by the following formula (II): [ka] (II) [In the formula, k is an integer from 1 to 3, n is an integer from 0 to 5, A represents cycloalkyl, aryl, heteroaryl, norbornane, or norbornene; L represents a direct bond or NH; R1 is independently hydroxyl, carboxyl, C 1-6Alkoxycarbonyl, arylcarbonylamino, amino, amido, C 1-6 one or more selected from alkyl, hydroxyphosphoryl, Het, or Ar; Ar represents aryl; Het represents a heterocycle; R2 represents C, P or S; R3 is hydroxy and is present when L represents a direct bond, or R3 is hydroxy or C when L represents NH. 1-6 is alkyl, R4 is hydroxy or C 1-6 alkylcarbonyl, which is present when R2 represents P, or R4 is a double-bonded oxygen (or oxygen having a double bond or doubled bonded oxygen), which is present when R2 represents S; A is independently selected from aryl or heteroaryl. The organic acid derivatives may be selected from one or more of the following:

[0031] In a currently more preferred embodiment according to the present invention, n is an integer from 0 to 2.

[0032] The modified layered double hydroxides have been found to provide efficient and effective nucleation and acid scavenging.

[0033] In a further preferred embodiment, the modified layered double hydroxide according to the present invention has the following formula (I): [[[M1 2+ ] y (M2 2+ ) z ] 1-x [M3 3+ ] x (OH)2](A n- ) x / nmH2O (I) [In the formula, M1 and M2 are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M3 is a trivalent metal such as Al and / or Fe, especially Al; A n- is one or more intercalating n-valent anions (or intercalating n-valent anions), m, x, y and z are values ​​within the ranges shown below. 0≦m<2 0 <x≦0.5 0.5≦y+z≦1] and a modified outer layer, which is modified with a derivative of an organic acid or a salt thereof. Formula (II) may be converted to the following formula (III): [ka] (III) wherein A is independently selected from aryl or heteroaryl. It is expressed as: Such modified layered double hydroxides have been found to provide efficient and effective nucleation (or nucleation) and acid scavenging (or acid scavenging).

[0034] Furthermore, when the modified layered double hydroxides (LDHs) according to the present invention are included in polymerizations, such as the polymerization of polypropylene, polyethylene, polylactic acid, polybutylene terephthalate, polybutylene adipate terephthalate, etc., ΔT is achieved.

[0035] The advantage of such a crystallization temperature is that efficient and effective acid scavenging and nucleation of the modified layered double hydroxides (LDHs) according to the present invention can be achieved.

[0036] In a preferred embodiment according to the present invention, the derivative of an organic acid or its salt is selected from the group consisting of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalenedicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1,3,5-tricarboxylic acid, 4-(benzoylamino)benzoic acid, malonic acid, One or more may be selected from the group consisting of disodium, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthalenecarboxylic acid, 2-tert-butylbenzoic acid, 4-aminobenzoic acid, 4-biphenylcarboxylic acid, 4-toluenesulfonic acid, bis(2-ethylhexyl) hydrogen phosphate, butylphosphonic acid, 4-phthalimidobenzoic acid, 4-tert-butylbenzoic acid, 1,3,5-triazine-2,4,6-triol, 1,4-cyclohexanedicarboxylic acid, and 4-propylcyclohexanecarboxylic acid. Preferably, the organic acid derivative or salt thereof may be one or more selected from the group consisting of benzoic acid, cis-1,2-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (2,3-norbornanedicarboxylic acid), pimelic acid, phenylphosphonic acid, benzene-1,3,5-tricarboxylic acid, 1,3,5-triazine-2,4,6-triol, 4-aminobenzoic acid, 1,4-cyclohexanedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 4-propylcyclohexanecarboxylic acid, butylphosphonic acid, and 4-toluenesulfonic acid.

[0037] In a currently further preferred embodiment according to the present invention, the derivative or salt of an organic acid is selected from the group consisting of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalenedicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1 One or more of the above may be selected from the group consisting of 4-(benzoylamino)benzoic acid, ... Preferably, the organic acid derivative or salt thereof may be one or more selected from the group consisting of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, pimelic acid, phenylphosphonic acid, 2,6-naphthalenedicarboxylic acid.

[0038] An advantage of the above acids is that modified layered double hydroxide (LDH) particles with a Tc of at least 122°C are achieved.

[0039] In a currently more preferred embodiment according to the present invention, the derivative of an organic acid or its salt may be cis-1,2-cyclohexanedicarboxylic acid.

[0040] It has been found that the modified layered double hydroxides (LDHs) according to the present invention (comprising one or more of the above organic acid derivatives or salts thereof, particularly cis-1,2-cyclohexanedicarboxylic acid) provide at least efficient and effective acid scavengers and nucleators. Thus, it provides efficient and effective dual functionality.

[0041] In a currently more preferred embodiment according to the present invention, the modified layered double hydroxide (LDH) comprises an X-ray diffraction peak in the range of 4° (2θ) to 9° (2θ).

[0042] It was found that cis-1,2-cyclohexanedicarboxylic acid allows the modified layered double hydroxide (LDH) to contain X-ray diffraction peaks in the range of 4° (2θ) to 9° (2θ).

[0043] In a currently more preferred embodiment according to the present invention, the derivative of an organic acid or its salt comprises 1,3,5-triazine-2,4,6-triol.

[0044] It should be noted that: 1,3,5-triazine-2,4,6-triol is an N-substituted isocyanurate.

[0045] It has been discovered that the above 1,3,5-triazine-2,4,6-triol provides an average Tc (or average Tc) of 121.90°C. Furthermore, such organic acid derivatives enable efficient and effective acid scavenging and nucleation.

[0046] In a currently preferred embodiment according to the present invention, the organic acid derivative or salt thereof includes a mono-, di-, or tri-carboxycyclohexane, preferably 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid.

[0047] The advantage of such an acid is that particles of modified layered double hydroxide (LDH) with a Tc of at least 120.5°C are achieved.

[0048] In a currently more preferred embodiment according to the present invention, A n- may be one or more selected from the group consisting of carbonate ions, nitrate ions, sulfate ions, or combinations thereof. Preferably, A n- may be a carbonate ion (or carbonate salt ion).

[0049] A n- The advantage of the above groups is that the acid scavenging of the modified layered double hydroxides (LDHs) according to the present invention is improved.

[0050] The following was found: n-By having the above, the modified layered double hydroxide (LDH) according to the present invention is provided with the properties of an acid scavenger (or acid scavenger).

[0051] The present invention also relates to particles comprising the modified layered double hydroxides (LDHs) according to the invention.

[0052] Particles comprising modified layered double hydroxides (LDHs) provide the same effects and advantages as those described for the modified layered double hydroxides (LDHs) according to the present invention.

[0053] It has been found that: The particles according to the invention offer advantageous effects, especially in the synthesis of polypropylene and polyethylene.

[0054] In a currently preferred embodiment according to the present invention, the particles may have an average secondary particle diameter measured by a dynamic light scattering method in the range of 1 nm to 2000 nm, preferably in the range of 3 nm to 1500 nm, and more preferably in the range of 5 nm to 1000 nm.

[0055] It should be noted that dynamic light scattering is based on a quality control method that includes particle size determination (based on volume distribution). After treating the sample with ultrasound, the particle size distribution in water was measured using a Microtrac S3500 particle size analyzer by laser diffraction. To a 0.35 g sample (or specimen), 2 mL of MeOH was added, and after 1 minute, 35 mL of 0.2 w / v % sodium hexametaphosphate (peptizer) was added. The sample was then subjected to ultrasonic vibration for 5 minutes. The sample was stirred, and 1 mL of the sample was removed using a pipette and injected into a particle size analyzer.

[0056] It has been found that particles having an average secondary particle diameter (or average secondary particle diameter) measured by dynamic light scattering (in the range of 1 nm to 2000 nm, preferably in the range of 3 nm to 1500 nm, and more preferably in the range of 5 nm to 1000 nm) provide efficient and effective acid scavenging and nucleation.

[0057] In a currently more preferred embodiment according to the present invention, the particles have an average secondary particle size (or average secondary particle diameter) measured by laser diffraction in the range of 0.01 μm to 20 μm, preferably in the range of 0.04 μm to 3 μm, and more preferably in the range of 0.1 μm to 1 μm.

[0058] The present invention also relates to a resin composition comprising particles according to the present invention and a resin, the particle concentration of which is in the range of 1 ppm to 10,000 ppm, preferably 50 ppm to 5,000 ppm, and more preferably 100 ppm to 3,000 ppm.

[0059] The resin composition according to the present invention provides effects and advantages similar to those described for the modified layered double hydroxides (LDHs) according to the present invention and for particles comprising the modified layered double hydroxides (LDHs) according to the present invention.

[0060] Please note that the resin according to the present invention comprises particles according to the present invention in an amount of 1 ppm to 10,000 ppm, preferably 50 ppm to 5,000 ppm, more preferably 100 ppm to 3,000 ppm based on the resin.

[0061] In a preferred embodiment according to the present invention, one or more resins may be selected from the group of polyolefins, polyvinyl chloride, polyvinyl alcohol, polylactic acid.

[0062] It has been found that one or more resins selected from the group consisting of polyolefin, polyvinyl chloride, polyvinyl alcohol, and polylactic acid enable efficient and effective acid removal (or acid scavenging) and nucleation (or nucleation).

[0063] The present invention also relates to a dispersion (or dispersion liquid or dispersion). The dispersion comprises particles according to the present invention and a liquid (or liquid). The particles according to the present invention have a concentration in the range of 1 ppm to 10,000 ppm, preferably in the range of 50 ppm to 5,000 ppm, and more preferably in the range of 100 ppm to 3,000 ppm.

[0064] The dispersions according to the present invention provide the same effects and advantages as those described for the modified layered double hydroxides (LDHs) according to the present invention, the particles comprising the modified layered double hydroxides (LDHs) according to the present invention, and the resin compositions according to the present invention.

[0065] In a preferred embodiment, the liquid is one or more selected from the group consisting of water, ethanol, methanol, propanol, and ethyl acetate.

[0066] The present invention also relates to a method for producing the modified layered double hydroxide (LHD) according to the present invention, which comprises reacting a compound of formula (I): [[[M1 2+ ] y (M2 2+ ) z ] 1-x [M3 3+ ] x (OH)2](A n- ) x / n mH2O (I) [In the formula, M1 and M2 are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M3 is a trivalent metal such as Al and / or Fe, especially Al; A n- is one or more intercalating n-valent anions (or intercalating n-valent anions), m, x, y and z are values ​​within the ranges shown below. 0≦m<2 0 <x≦0.5 0.5≦y+z≦1] The method includes contacting the layered double hydroxide of the formula (I) with a derivative of an organic acid or a salt thereof.

[0067] The process for producing (or preparing or forming or generating) the modified layered double hydroxide (LDH) according to the present invention provides effects and advantages similar to those described for the modified layered double hydroxide (LDH) according to the present invention, the particles comprising the modified layered double hydroxide (LDH) according to the present invention, the dispersion (or dispersion liquid or dispersion) according to the present invention and the resin composition according to the present invention.

[0068] The method for producing (or preparing or forming or producing) a modified layered double hydroxide (LDH) according to the present invention comprises a step of contacting the outer layer of the layered double hydroxide with a derivative of an organic acid or a salt thereof.

[0069] It has been found that the method according to the present invention efficiently and effectively provides modified layered double hydroxides (LDHs) comprising a modified outer layer.

[0070] Additionally, the method according to the present invention may further comprise the synthesis of a polymer (eg, a polymer composition) using a modified layered double hydroxide (LDH) according to the present invention. The method involves, for example, mixing the modified layered double hydroxide (LDH) with various polymer carriers (via additive blends, masterbatches and / or concentrates, or in the form of powders) in a polymer melt extruder.

[0071] In a preferred embodiment according to the present invention, the derivative of an organic acid or its salt is mono- or di-carboxy-C 1-12 Alkyl, C 1-12 Alkyl sulfonyl hydroxide, C 1-12 Alkylphosphonic acid, bis C 1-12 Alkyl phosphonates, represented by the following formula (II): [ka] (II) [In the formula, k is an integer from 1 to 3, n is an integer from 0 to 5, A represents cycloalkyl, aryl or heteroaryl; L represents a direct bond or NH; R1 is independently hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amido, C 1-6 one or more selected from alkyl, hydroxyphosphoryl, Het, or Ar; Ar represents aryl; Het represents a heterocycle; R2 represents C, P or S; R3 is hydroxy and is present when L represents a direct bond, or R3 is hydroxy or C when L represents NH. 1-6 is alkyl, R4 is hydroxy or C 1-6 alkylcarbonyl and present when R2 represents P, or R4 is a double-bonded oxygen (or oxygen having a double bond or doubled bonded oxygen) and present when R2 represents S. One or more of the organic acid derivatives are selected from the group consisting of:

[0072] In a preferred embodiment, n is an integer of 0-2.

[0073] In a currently more preferred embodiment according to the invention, A may be aryl or heteroaryl.

[0074] In a currently further preferred embodiment according to the present invention, the derivative or salt of an organic acid is selected from the group consisting of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalenedicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1 One or more of the above may be selected from the group consisting of 4-(benzoylamino)benzoic acid, ...

[0075] In a preferred embodiment, the organic acid derivative or salt thereof may be one or more selected from the group consisting of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, pimelic acid, phenylphosphonic acid, 2,6-naphthalenedicarboxylic acid.

[0076] The present invention also relates to the use of the modified layered double hydroxides according to the present invention, the particles according to the present invention, the resin compositions according to the present invention, and / or the dispersions according to the present invention in the polymer industry. In this disclosure, the polymer industry includes the synthesis of polymers, the manufacture of polymer compositions, and the conversion of polymer compositions into consumables.

[0077] The use of modified layered double hydroxides (LDHs) in the polymer industry provides effects and advantages similar to those described for the modified layered double hydroxides (LDHs) according to the invention, particles comprising the modified layered double hydroxides (LDHs) according to the invention, dispersions according to the invention, resin compositions according to the invention and processes for producing the modified layered double hydroxides (LDHs) according to the invention.

[0078] It has been found that the modified layered double hydroxides (LDHs) according to the present invention are particularly useful in the synthesis of polymers, such as polypropylene (including homopolymers, random copolymers, and heterophase copolymers), polyethylene (including high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE)). In the synthesis of polymers, the modified layered double hydroxides (LDHs) according to the present invention may be used as acid scavengers and nucleating agents.

[0079] In a further preferred embodiment of the present invention, the modified layered double hydroxides (LDHs) according to the present invention are used to increase the crystallization temperature in the processing of crystalline thermoplastic polymers and / or semi-crystalline polymers.

[0080] In a further preferred embodiment according to the invention, the increase in crystallization temperature (or crystallization temperature) is an increase of at least 0.5°C, preferably at least 1°C, more preferably at least 2°C, even more preferably at least 3°C, even more preferably at least 4°C, and most preferably at least 5°C (according to EN ISO 11357-3:2018).

[0081] It should be noted that ΔT represents the difference (or subtraction) between the crystallization temperature with the modified layered double hydroxide (LDH) and the crystallization temperature without the modified layered double hydroxide (LDH).

[0082] In a further preferred embodiment according to the invention, the crystalline thermoplastic polymer (or crystalline thermoplastic polymer) is polypropylene, the crystallization temperature of which is at least 120.05°C, preferably at least 121°C, more preferably at least 122°C, even more preferably at least 123°C, even more preferably at least 124°C, and most preferably at least 125°C (according to EN ISO 11357-3:2018).

[0083] Further advantages, features and details of the present invention will be explained based on preferred embodiments of the present invention, with reference to the drawings and accompanying experiments. [Brief explanation of the drawings]

[0084] [Figure 1] FIG. 1 shows the X-ray diffraction of a modified layered double hydroxide (LDH) (modified with cis-1,2-cyclohexanedicarboxylic acid) according to the present invention. [Figure 2] FIG. 2 shows the FT-IR of a modified layered double hydroxide (LDH) (modified with cis-1,2-cyclohexanedicarboxylic acid) according to the present invention. [Figure 3] Figure 3 shows a test piece (or specimen) for a tensile test (or tensile test or tensile test). [Figure 4] Figure 4 shows the decomposition curves for both the modified layered double hydroxide (LDH) (modified with cis-1,2-cyclohexanedicarboxylic acid) samples synthesized according to the first and second methods. [Figure 5] FIG. 5 shows the TGA of cis-1,2-cyclohexanedicarboxylic acid magnesium salt and cis-1,2-cyclohexanedicarboxylic acid. [Figure 6] FIG. 6 shows the XRD pattern of the synthesized specimen (or sample). [Figure 7] FIG. 7 shows the XRD pattern of particles of modified layered double hydroxide (LDH) (modified with cis-1,2-cyclohexanedicarboxylic acid). [Figure 8] FIG. 8 shows the FT-IR spectrum of the synthesized sample. [Figure 9] FIG. 9 shows an SEM image of the synthesized specimen. [Figure 10] FIG. 10 shows the XRD patterns of the specimens described in Table 5. [Figure 11] FIG. 11 shows the FT-IR spectrum of the specimen (or sample) described in Table 5. [Figure 12] FIG. 12 shows the XRD patterns of various LDH particles according to the present invention. [Figure 13] FIG. 13 shows the FT-IR spectra of various LDH particles according to the present invention. [Figure 14] FIG. 14 shows the WAXD patterns of layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid. DETAILED DESCRIPTION OF THE INVENTION

[0085] In this experiment, a modified layered double hydroxide (LDH) according to the present invention was synthesized. The synthesis began with weighing 50 g of layered double hydroxide into a two-necked flask. 200 ml of demineralized water was added to the flask and stirred at 18°C. A reflux condenser was attached to the first neck of the flask, and a dropping funnel was attached to the second neck. 5 g of cis-1,2-cyclohexanedicarboxylic acid (HHPA) (dissolved in 50 ml of EtOH) was added to the dropping funnel. The layered double hydroxide was then slowly added (approximately 1 drop / second) to the stirred dispersion. After the addition of cis-1,2-cyclohexanedicarboxylic acid (dissolved in EtOH), the dispersion was heated to reflux temperature for 2 hours. The solid was filtered and washed five times with demineralized water. After washing, the resulting solid was dried.

[0086] The solid was analyzed using FT-IR, SEM, and XRD. It was found that a modified layered double hydroxide (LDH) with both acid scavenging and nucleation functions had been synthesized.

[0087] XRD analysis revealed the following:

[0088] X-ray diffraction is used to determine the basal spacing and crystallographic structure of layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid.

[0089] X-ray diffraction spectra are recorded using a Panalytical X-pert powder spectrometer equipped with a PIXcal 1D-Medipix3 Collaboration RTMS detector using a scanning line detector. For such measurements, Cu Kα radiation (λ=1.54 Angstroms (Å)) was used. The step size of the goniometer was 0.026° (2θ) (counting time: 296.565 seconds). Spectra are recorded at 45 kV and 40 mA.

[0090] Focal length: 12.0mm Width (or width): 0.4 mm Take-off angle: 6.0° Beta-filter: Nickel (thickness: 0.020mm) Soller slit: 0.02rad Fixed incident beam mask: 15 mm (width: 11.60 mm) Anti-scatter slit: Fixed slit (1 / 2°, height = 0.76 mm) Divergence slit: Fixed slit (1 / 4°, height = 0.38 mm)

[0091] For the diffracted beam path, a radius of 240.0 mm was used. Anti-scatter slit: AS slit (8.0 mm) (PIXcel) (fixed type) (height = 8.0 mm) Large Solar Slit: 0.02rad Large Beta Filter: Nickel (Thickness: 0.020mm)

[0092] The X-ray diffraction pattern obtained for this material is shown in Figure 1. X-ray diffraction is used to determine the basal spacing and crystallographic structure of layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid. As shown in FIG. 1, the positions of the peaks 003 (7.5 angstroms (Å)) and 006 (3.8 angstroms (Å)) correspond to the carbonate (CO3) intercalated in the layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention. 2- ) is shown. The peaks observed in FIG. 1 indicate that the layered double hydroxide modified with cis-1,2-cyclohexanedicarboxylic acid is a layered double hydroxide.

[0093] XRF analysis (or X-ray fluorescence analysis) revealed the following:

[0094] X-ray fluorescence data are recorded on a Panalytical Axios spectrometer equipped with a Rh tube. A sample (or specimen) is prepared by mixing the material (7.0 g), an inert binder material, and Elvacite 2046 (2 mL of acetone solution, 40 g / 200 mL) in a mortar. After the acetone has evaporated, pellets of this material are pressed. The content of MII and MIII in a sample is determined using an X-ray fluorescence spectrometer, and M II O and M III O3 and expressed as a percentage (%) of the total weight of the sample.

[0095] The modified layered double hydroxide (LDH) according to the present invention (modified with cis-1,2-cyclohexanedicarboxylic acid) was analyzed using FT-IR. FT-IR scans were recorded on a Thermo Scientific Nicolet iS10 equipped with a Smart iTX ATR sampling accessory and a diamond crystal. Scan number (or number of scans) = 32 Resolution = 4 Data spacing (or data interval) = 0.482 cm -1 Final format = % reflectance The data obtained here is shown in Figure 2.

[0096] Figure 2 shows the ion exchange potential of unmodified layered double hydroxides (LDHs) (3200 cm -1 (upper line at 3200 cm) and layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid (3200 cm). -1 The comparison with the line below is shown. The FT-IR spectrum of the layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid shows many additional peaks compared to the unmodified layered double hydroxide (LDH). 1470cm -1 ~1660cm -1 (the range of organic bonds) and a peak located around 2800 cm -1 ~3000cm -1 The peak located around (CH / CH2 bond) is the most prominent.

[0097] Analysis of the organic components revealed the following:

[0098] Identification / quantification of the organic components of modified layered double hydroxides (LDHs) may be achieved using ion chromatography (IC) and / or liquid chromatography (LC) in combination with conductivity detection and / or mass spectrometry.

[0099] The modified layered double hydroxide (LDH) may be dissolved, preferably further diluted, in acid, and the solution is then injected into an IC column and / or LC system. Identification is then carried out using the R of the pure organic components used. t and R of the organic components of the sample (or specimen). t This can be achieved by comparing On the other hand, quantification can be achieved by preparing a calibration line for the organic component and comparing the detection intensity of the sample with that calibration line.

[0100] In further experiments, modified layered double hydroxides (LDHs) containing cis-1,2-cyclohexanedicarboxylic acid (synthesized as described above) were added to polypropylene, preferably a polypropylene homopolymer (melt flow index = 10), by extrusion. Varying concentrations of calcium stearate (CaSt) may be added to various samples (see Table 1). By using DSC analysis and mechanical properties, the performance properties were determined.

[0101] A powder blend of modified layered double hydroxide (LDH) (antioxidant) according to the present invention and polypropylene was prepared and fed into a thoroughly cleaned twin-screw extruder. The product was granulated and injection molded into tensile bars for measurement. In various samples (or specimens) (or compositions), the concentration of the modified layered double hydroxide (LDH) according to the present invention was varied, and the concentrations are shown in Table 1. Therefore, the modified layered double hydroxide (LDH) is the same in each sample. Between extrusions of the samples, the extruder was cleaned and purged with polypropylene and an antioxidant.

[0102] Table 1: Samples (or specimens) containing layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention [Table 1]

[0103] Twin screw extrusion and injection molding were carried out using the parameters disclosed in Table 2.

[0104] Table 2: Twin-screw extrusion and injection molding parameters [Table 2]

[0105] The samples were analyzed using Differential Scanning Calorimetry (DSC). The extruded samples (or specimens) were placed in aluminum (Tzero) sample cups and analyzed on a TA Instrument Q2000 DSC. The temperature program used was a 180°C to 20°C ramp. A material is heated to an increasing temperature to erase its thermal history, and then cooled at a linear rate. The analysis was carried out under an inert atmosphere by using purging nitrogen gas (N2). The parameters for performing DSC are provided in Table 3. The crystallization behavior was analyzed from the cooling curve.

[0106] Table 3. DSC parameters [Table 3]

[0107] The tensile properties are determined by injection molding samples into Type 1A sample bars (as described in ISO 527-2 standard) and testing according to Method B. An Instron 3365 tensile tester (equipped with a tension meter (or tensiometer)) was used.

[0108] Furthermore, the mold (or mold or casting) was tested for shrinkage using ISO 294-4. The shrinkage of the samples was determined as specified in ISO 294-4 standard, except that the test specimens were tensile test bars (Type 1A). The measuring instrument (or measuring device) is a micrometer, which measures dimensions with a resolution of 0.001 mm. Dimensions are measured with an accuracy of 0.01 mm. After injection molding, the shrinkage was measured at 24 hours and 72 hours. FIG. 3 shows the tensile test specimen 2, the injection direction 4, and dimensions 6, 8, 10, 12, 14, and 16. The dimension 6 is 20 mm. Dimension 8 is 10 mm. The dimension 10 is 4 mm. The dimension 12 is 80 mm. The dimension 14 is 109.3 mm. The dimension 16 is 170 mm.

[0109] To determine the nucleation behavior of polypropylene samples, samples were prepared by adding a nucleating agent (conventional) and a modified layered double hydroxide (LDH) according to the present invention. The crystallization temperature of the above samples was determined by differential scanning calorimetry. A sample (5 mg) of the injection-molded material was heated to 200°C to erase all thermal history, then cooled to 20°C and analyzed for crystallization exotherm. The results are provided in Table 1.

[0110] These results demonstrate the nucleation effect of a sample (or specimen) (comprising a sample (or specimen) of layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid) on polypropylene. The crystallization temperature was increased by 6°C, and the concentration was increased to 500 ppm, 1000 ppm, and 2000 ppm.

[0111] These results show that the sample provides an efficient and effective nucleation effect compared to conventional layered double hydroxides. Indeed, the layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention provide nucleation (or nucleation or nucleation) and acid scavenging (or acid scavenging or acid scavenging). The variables selected have very little effect. It can be concluded that the addition of CaSt does not provide any noticeable (or significant) difference compared to the sample (or specimen) without CaSt addition. Furthermore, it has been shown that increasing the concentration of layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid results in little increase in the crystallization temperature.

[0112] The mechanical properties of the sample and reference were determined and are listed in Table 1. The tensile properties (or tensile characteristics or tensile properties) are compared to polypropylene (not nucleated with CaSt). These results show that nucleation involving cis-1,2-cyclohexanedicarboxylic acid-modified layered double hydroxides (LDHs) results in a 10%-16% increase in modulus and a 50%-60% decrease in strain at break compared to that using conventional layered double hydroxides (not shown).

[0113] These results indicate that samples nucleated at 500 ppm to 2000 ppm (cis-1,2-cyclohexanedicarboxylic acid-modified layered double hydroxides (LDHs)) offer improved nucleation and / or acid scavenging compared to conventional layered double hydroxides.

[0114] Furthermore, the dimensions of the injection molded samples were measured (72 hours after production). According to the standard, shrinkage in the injection direction (S L ) and vertical shrinkage (S W ) is calculated. The results are provided in Table 1. Samples nucleated with the layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention show a shrinkage of 1% to 2% after 72 hours, which is comparable to that of conventional layered double hydroxides.

[0115] Samples containing layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid were found to have excellent isotropic shrinkage properties.

[0116] The layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention has the effect of nucleating (or nucleation or nucleating) polypropylene and the effect of scavenging (or acid scavenging) acid.

[0117] In a further embodiment, layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid were synthesized. (It should be noted that in this application, HHPA means cis-1,2-cyclohexanedicarboxylic acid. NOR means 2,3-norbornanedicarboxylic acid or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (since 2,3-norbornanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid refer to the same compound).)

[0118] The first synthesis method is started by weighing 15 g of LDH into a 250 mL round bottom flask, adding 135 mL of demineralized water (or demineralized water) and stirring at room temperature. A dropping funnel is attached to the neck of the flask and contains 1.5 g of cis-1,2-cyclohexanedicarboxylic acid and / or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (dissolved in 7 mL of ethanol). The solution of cis-1,2-cyclohexanedicarboxylic acid or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid is slowly added dropwise to the stirred dispersion of LDH. After the solution of cis-1,2-cyclohexanedicarboxylic acid and / or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid is added, the dropping funnel is replaced with a condenser (or cooler), and the dispersion of LDH (or dispersion liquid or dispersion) is heated to the reflux temperature. Once the reflux temperature was reached, the dispersion was allowed to continue refluxing for an additional 2 hours. The dispersion was cooled, filtered through a Buchner funnel (using a Whatmann 42 filter (diameter 90 mm)), washed five times with approximately 30 mL of demineralized water, and then dried overnight at 70 °C.

[0119] Alternatively, the second synthesis method begins by weighing 20 g of LDH into a 400 mL glass beaker, followed by the addition of 2 g of cis-1,2-cyclohexanedicarboxylic acid and / or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid and 200 g of demineralized (or demineralized) water. The dispersion is stirred at room temperature for 30 minutes. After stirring for 30 minutes, the beaker is covered with aluminum foil and heated to 80°C. Once the temperature reached 80°C, the reaction was maintained at this temperature for an additional 2 hours. After 2 hours, the dispersion is cooled and the solid is filtered through a Buchner funnel (using a Whatmann 42 filter (diameter 90 mm)). After filtration, the solid is dried overnight at 70°C.

[0120] The crystallization temperature (Tc) was determined on a Mettler Toledo DSC 3+ (temperature range = 50 °C - 200 °C, heating / cooling rate = 10 °C / min). The solids were analyzed according to EN ISO 11357-3:2018.

[0121] The following was found: the composition of the sample (or specimen) comprises homopolymer polypropylene (PP) (melt flow index = 3), Irganox® 1010, Irgafos® 168 and a sample of LDH in the approximate ratio 99.800 / 0.050 / 0.100 / 0.050, where the amount of LDH may be increased or decreased, being compensated for by the amount of PP. Further analysis of the crystallization temperature of the PP containing LDH particles measured by DSC is all prepared according to the settings shown in Table 4.

[0122] Table 4. Single-screw extrusion and injection molding parameters [Table 4]

[0123] Furthermore, the crystal structure of LDH was analyzed using X-ray diffraction (XRD). XRD was recorded on a Panalytical X-pert powder spectrometer (equipped with a PIXcal 1D-Medipix3 Collaboration RTMS detector using a scanning line detector). For these measurements, Cu Kα radiation (λ=1.54 Angstroms (Å)) was used. The goniometer step size was 0.1838° (2θ) (counting time = 5157.63 s, scan range = 5,000–80,001, number of points = 408). Spectra were recorded (45 kV, 40 mA). Focal length: 12.0mm Width (or width): 0.4 mm Take-off angle: 6.0° Beta-filter: Nickel (thickness = 0.020 mm) Soller slit: 0.02rad Fixed incident beam mask: 15 mm (width: 11.60 mm) Anti-scatter slit: Fixed slit (1 / 2°, height = 0.76 mm) Divergence slit: Fixed slit (1 / 4°, height = 0.38 mm)

[0124] Furthermore, after modifying (or altering or denaturing or modifying or modifying) LDH with an acid, FT-IR is used to identify (or identify) the organic compound. FT-IR spectra were obtained on a Thermo Scientific Nicolet iS10 FT-IR spectrometer equipped with an ATR unit (resolution = 4 cm). -1 (I went there). For all samples, the measurement range is 4000 cm -1 ~600cm -1 is.

[0125] To observe the distribution and morphology of the surface modification of LDH, samples were examined using a scanning electron microscope (SEM). SEM images were obtained using a Hitachi SU7000 device. Samples were measured under the following conditions: Vacc = 1.00 kV, Mag = "mentioned within the images", and WD = "mentioned within the images". The sample (or specimen) was prepared by dispersing a small amount of the sample (or specimen) in isopropyl alcohol. Approximately one or two drops of the dispersion are placed on an aluminum stub, allowed to dry, and then the stub is placed in the SEM.

[0126] Thermogravimetric analysis (TGA) of the samples was performed on a TA Instruments Q500 instrument (equipped with a Pt pan) to determine the total weight loss of the material (up to 1000°C or 750°C (after changes in the method)). Data were acquired using a dynamic rate high resolution program (Hi-Res Sensitivity = 1.0, Ramp = 50.00 °C / min, Resolution = 4.0). Helium gas was used to create an inert atmosphere for all analyses. Furthermore, it is possible to predict the total amount of cis-1,2-cyclohexanedicarboxylic acid in a sample using Equation I below. It should be noted that in Equation I, cis-1,2-cyclohexanedicarboxylic acid is shown as Q.

[0127]

number

[0128] The synthesized LDA (according to the present invention) has also been analyzed by LC-MS / MS. The method used in the synthesis of cis-1,2-cyclohexanedicarboxylic acid (CAS: 610-09-3) and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (CAS: 1724-08-9) involves the use of multiple reaction monitoring (MRM) with negative ionization mode. UPLC: Sciex ExionLC™ Detector: Sciex QTRAP 4500 Software: Analyst 1.7, MultiQuant 3.0.3 Analytical column: Waters CSH C18, 2.1 x 100 mm, 1.7 μm

[0129] MRM transitions: cis-1,2-cyclohexanedicarboxylic acid: m / z 170.9 / 126.8 and 170.9 / 152.9 Bicyclo[2.2.1]heptane-2,3-dicarboxylic acid: m / z 182.9 / 139.1 and 182.9 / 182.9 Phenylphosphonic acid and pimelic acid: m / z 159 Benzene-1,3,5-tricarboxylic acid: m / z 209 2,6-Naphthalenedicarboxylic acid: m / z 216 1,4-Cyclohexanedicarboxylic acid: m / z 171

[0130] A sample (or specimen) (approximately 0.1 g) was extracted with 1 M HCl (5 mL) (80° C., 4 hours). 5 mL of methanol was added to the extract (or extract or extract). The extract (or extract or extract) was stirred, diluted with methanol, and analyzed by LC-MS / MS. Quantitation was performed against an external calibration line (or external calibration line or external calibration line or external calibration line) (an external calibration line of standards of known concentrations of the desired component).

[0131] Extraction with 1M HCl (80° C.) was found to be sufficient to dissolve the inorganic fraction.

[0132] The results obtained for layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid are provided in Table 5. Entry 1 shows the sample of untreated LDH. Entry 2 shows a sample of layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid obtained according to the first synthesis method. Entry 3 shows a sample of layered double hydroxide (LDH) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid obtained according to the first synthesis method. Entry 4 shows a sample of layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid obtained according to the second synthesis method. Entry 5 shows a sample of layered double hydroxide (LDH) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid obtained according to the second synthesis method.

[0133] Table 5: Summary of results for LDH samples [Table 5]

[0134] It was found that the Tc of all surface-modified samples was increased compared to untreated layered double hydroxide (LDH), suggesting that both methods (the first and second methods) can be used to treat the surface of LDH. However, as can be seen from Table 5, both the samples (or specimens) modified with cis-1,2-cyclohexanedicarboxylic acid and with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (both according to the second method) show an increase in Tc compared to the sample (or specimens) obtained according to the first method. This implies that the second method can be used instead of the first method with respect to Tc.

[0135] Concentration determinations by LC / MS and TGA both show that the layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid contains more cis-1,2-cyclohexanedicarboxylic acid when prepared according to the first method instead of the second method. Such observations indicate that higher amounts of cis-1,2-cyclohexanedicarboxylic acid do not necessarily mean higher Tc. For layered double hydroxides (LDHs) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, a higher amount of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid was found in the samples from the second method compared to the samples from the first method according to LC / MS.

[0136] Figure 4 shows the decomposition curves of the layered double hydroxide (LDH) samples (samples) modified with cis-1,2-cyclohexanedicarboxylic acid (samples synthesized by the first method and samples synthesized by the second method) compared to the untreated sample (sample). The most significant difference (or disparity) among these curves can be observed within the range of 450°C to 550°C. This loss occurs only in the LDH samples modified with cis-1,2-cyclohexanedicarboxylic acid, and can therefore be attributed to the treatment with cis-1,2-cyclohexanedicarboxylic acid.

[0137] The following should be noted: At 700 °C, the upper line (or line) (or top line) represents the untreated layered double hydroxide (LDH). At 700 °C, the middle line (or line) represents the layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized using the first method. At 700 °C, the lower line (or bottom line) represents the layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized using the second method.

[0138] Figure 5 shows that the weight loss between 450 and 550 °C is caused by the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid, and not by cis-1,2-cyclohexanedicarboxylic acid (which occurs at 200 °C). This indicates that cis-1,2-cyclohexanedicarboxylic acid derived from the samples (or specimens) of layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid (samples (or specimens) obtained from both the first method and the second method) provides the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid. It should be noted that in the curve (or curves) of Mg-cis-1,2-cyclohexanedicarboxylic acid in FIG. 5, the decrease at 200° C. is caused by unreacted cis-1,2-cyclohexanedicarboxylic acid.

[0139] The following should be noted: At 400 °C in Figure 5, the lower line (or bottom line) represents cis-1,2-cyclohexanedicarboxylic acid. At 400 °C in Figure 5, the upper line (or line) (or top line) represents the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid.

[0140] Furthermore, the XRD patterns of both the LDH modified with cis-1,2-cyclohexanedicarboxylic acid and the LDH modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid showed a new crystal configuration introduced in the range of 5.9 (2θ) to 7.9 (2θ) for the LDH synthesized using the first method (see Figure 6), and a new crystal configuration introduced in the range of 6.8 (2θ) for the LDH synthesized using the second method (see Figure 6). Figure 6 also shows new crystals formed in LDH treated with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid at 8.3 (2θ) (formed not only by the second method but also by the first method). No significant changes were observed in the crystallographic structure of the LDH samples, except for a small decrease in carbonate, which can be seen in the peaks (003) and (006). In both methods, this reduction in carbonate (or carbonate salt or carbonate ester) is caused by a side effect of the reaction with the organic acid (cis-1,2-cyclohexanedicarboxylic acid or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid).

[0141] The following should be noted: Line A (or line A) in FIG. 6 shows the untreated layered double hydroxide (LDH). Line B (or line B) in FIG. 6 shows a layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized using the first method. Line C (or line C) in FIG. 6 shows a layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized using the second method. Line D (or line D) in FIG. 6 shows a layered double hydroxide (LDH) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid synthesized using the first method. Line E (or line E) in FIG. 6 shows a layered double hydroxide (LDH) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid synthesized using the second method.

[0142] Since Mg-cis-1,2-cyclohexanedicarboxylic acid has been observed in both cis-1,2-cyclohexanedicarboxylic acid-modified layered double hydroxide (LDH) samples, experiments have been devoted to treating the surface of LDH with Mg-cis-1,2-cyclohexanedicarboxylic acid instead of cis-1,2-cyclohexanedicarboxylic acid. This experiment was carried out according to the second method, in which cis-1,2-cyclohexanedicarboxylic acid was exchanged for Mg-cis-1,2-cyclohexanedicarboxylic acid. The material does not contain crystals of Mg-cis-1,2-cyclohexanedicarboxylic acid on its surface. This can be seen in the XRD pattern “B” in Figure 7. The absence of the peak at 6.8 (2θ) confirms that cis-1,2-cyclohexanedicarboxylic acid is essential for synthesizing the LDH surface containing Mg-cis-1,2-cyclohexanedicarboxylate crystals.

[0143] The following should be noted: Line A (or Line A) in FIG. 7 shows the modified layered double hydroxide (LDH) according to the second method. Line B (or line B) in Figure 7 shows a modified layered double hydroxide (LDH) according to the second method, in which cis-1,2-cyclohexanedicarboxylic acid is replaced with Mg-cis-1,2-cyclohexanedicarboxylic acid.

[0144] The FT-IR spectrum can be seen in Figure 8, and is at 1480 cm -1 ,1550cm -1 ,1600cm -1 ,1690cm -1 The presence of a peak at 2850 cm -1 ~2975cm -1 This shows the presence of peaks in the range. First, 2850cm -1 ~2975cm -1 The range of 1,2-cyclohexanedicarboxylic acid and 2,3-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid correlates with the asymmetric and symmetric CH stretching. 1690cm -1 was correlated with the amount of water between the LDH layers (or interlayers). 1600cm -1 and 1550 cm -1 are the peaks of the carboxylate groups (or carboxylate salt groups or carboxylate ester groups) of cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid. 1480cm -1 The peaks are the vibrations of the hydrogen atoms in the alkene. The presence of these peaks indicates that cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid react with LDH to form carboxylate groups (or carboxylate salt groups or carboxylate ester groups) instead of carboxylic acid groups, which are expressed at 1720 cm -1~1706cm -1 and 1440-1395cm -1 It has a peak at Furthermore, 1550cm -1 Materials made according to the first method appear to be preferred for forming carboxylates (or carboxylate salts or carboxylate esters) at 1600 cm, whereas materials made according to the second method appear to be more preferred for forming carboxylates (or carboxylate salts or carboxylate esters) at 1600 cm. -1 shows a carboxylate (or carboxylate salt or carboxylate ester).

[0145] The following should be noted: Line A (or line A) in FIG. 8 represents unreacted layered double hydroxide (LDH). Line B (or line B) in FIG. 8 shows a layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized using the first method. Line C (or line C) in FIG. 8 shows a layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized using the second method. Line D (or line D) in FIG. 8 shows a layered double hydroxide (LDH) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid synthesized using the first method. Line E (or line E) in FIG. 8 shows a layered double hydroxide (LDH) modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid synthesized using the second method.

[0146] FIG. 9 shows SEM images of the surface-treated material versus the untreated material. Photo A (or Picture A) shows an untreated sample (or specimen), with no additional crystals attached to its surface. Photograph B (or Picture B) is a layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized according to the first method, showing a small amount of crystals on the surface of the LDH. The layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid synthesized according to the second method exhibited more crystallinity, which could also be expected based on the XRD patterns. Furthermore, unlike cis-1,2-cyclohexanedicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid does not exhibit any crystals after treatment according to the first method, but after treatment according to the second method, crystals are present on the surface. Furthermore, the XRD pattern of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid shows newly formed crystals by the second method. These crystals cannot be observed in the XRD spectrum of the first method. A combination of SEM and XRD has confirmed that the surface of LDH has been modified (or altered or denatured or modified) with crystals of magnesium salts of cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (not a mixture of the salts and LDH).

[0147] Therefore, we can conclude that layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid were successfully synthesized, where the surface of the LDHs was modified with acid.

[0148] In further experiments, the nucleation behavior of the modified layered double hydroxides (LDHs) according to the present invention (surface-modified LDHs) is demonstrated. The LDH thus tested was a layered double hydroxide (LDH) modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention. Such particles were synthesized using the second experimental method described above, and the results are shown in Table 6.

[0149] Table 6: Nucleation behavior results [Table 6]

[0150] The most significant difference (or significant difference) in Tc is caused by changes in temperature. Compared to LDH-free PP, a small increase of about 2°C in Tc was observed for samples prepared at 20°C (Tc is about 120°C). When the temperature was increased to 60°C during the reaction, Tc already increased by another 1°C, and when the reaction was carried out at 80°C, it increased by about 7°C.

[0151] Furthermore, the starting powder or slurry of LDH has no significant effect on Tc, and agitation also has no significant effect on Tc. Compared to samples dried in a static oven, spray drying increased the effect on Tc.

[0152] The XRD patterns of the samples (or specimens) listed in Table 6 are shown in FIG. Notably, the peak at 6.8 (2θ) representing Mg-cis-1,2-cyclohexanedicarboxylic acid is better defined for samples exhibiting higher Tc, and is rarely or even completely absent for samples exhibiting little or no increase in Tc. This indicates that a well-defined peak (the peak at 6.8 (2θ)) results in a higher Tc.

[0153] The FT-IR spectra of the samples (or specimens) listed in Table 6 are shown in FIG. 1550cm -1 and 1600 cm -1 The peak is Mg-cis-1,2-cyclohexanedicarboxylic acid on the surface of LDH. A similar observation is made by XRD: higher Tc indicates well-defined peaks, especially at 1600 cm -1 The peak is shown. The H of the sample (or specimen) and the I of the sample (or specimen) have sharp peaks and higher Tc compared to the other samples (or specimens). For example, the F of a sample (or specimen) is a relatively small peak (1600 cm -1 ), but a relatively large peak (slightly large peak) (1550 cm -1 ) However, 1550cm -1 The peak of α was relatively large but did not result in a higher Tc. Therefore, in particular, 1600 cm -1 It can be concluded that the peaks indicate the nucleation effect in this material.

[0154] Therefore, it can be concluded that the modified layered double hydroxides (LDHs) according to the present invention have a nucleation effect.

[0155] In further experiments, particles of modified layered double hydroxides (LDHs) were synthesized and analyzed using wide-angle X-ray diffraction (WAXD).

[0156] In the synthesis of polymers (e.g., polypropylene), WAXD is used to effect particles of various LDHs according to the invention, provided that the particles contain α (alpha) and / or β (beta) nucleating agents (or nucleating agents or nucleators). It should be noted that α-nucleating agents (or α-nucleating agents or α-nucleators) form or are monoclinic (tetragonal) crystals, and β-nucleating agents (or β-nucleating agents or β-nucleators) form or are hexagonal crystals.

[0157] WAXD analysis of polypropylene containing LDH according to the invention was carried out using a Panalytical X-pert powder spectrometer equipped with a PIXcal 1D-Medipix3 Collaboration RTMS detector using a scanning line detector. For these measurements, Cu Kα radiation (λ=1.54 Angstroms (Å)) was used. The step size of the goniometer was 0.026261° (2θ). Counting time: 7.14 seconds Scan range: 5.000~69.9949 Number of points (or point number): 2475 Spectra were recorded at 45 kV and 40 mA. Focal length: 12.0mm Width (or width): 0.4 mm Take-off angle: 6.0° Beta-filter: Nickel (thickness: 0.020mm) Soller slit: 0.02rad Fixed incident beam mask: 15 mm (width: 11.60 mm) Anti-scatter slit: Fixed slit (1 / 2°, height = 0.76 mm) Divergence slit: Fixed slit (1 / 4°, height = 0.38 mm)

[0158] Table 7 shows particles of various LDHs according to the invention.

[0159] Table 7: List of molecules (tested and reacted with LDH) [Table 7]

[0160] DHT TM It should be noted that -4V is a hydrotalcite that is used as an acid scavenger in the conventional synthesis of polypropylene.

[0161] Figure 12 shows the XRD patterns of seven molecules that have a nucleation effect. All patterns show newly introduced crystals (except for pimelic acid and 1,4-cyclohexanedicarboxylic acid), which has also been observed in layered double hydroxides (LDHs) modified with cis-1,2-cyclohexanedicarboxylic acid. No repeats of peaks 003, 006, and 009 are observed. However, carbonates (or carbonate salts or carbonate esters) are excluded (which are inserted (or intercalated or intercalated) into the particles of LDH). It can therefore be concluded that the molecule was not inserted (or intercalated or intercalated).

[0162] Furthermore, pimelic acid and 1,4-cyclohexanedicarboxylic acid were found to exhibit a nucleation effect. It is expected that the LDHs are coated with an organic layer of pimelic acid or 1,4-cyclohexanedicarboxylic acid (rather than covered with Mg crystals), since F and H in the FT-IR spectrum in Figure 13 indicate the presence of organic molecules. Furthermore, the FT-IR spectrum shows the presence of carboxylate groups (or carboxylate salt groups or carboxylic acid ester groups) (1550 cm -1 or 1600cm -1 ), except for A and D (A and D are untreated and PPA-treated materials (PPA is a phosphonic acid derivative, and refers to phenylphosphonic acid, where the phosphate peak is at approximately 1150 cm -1 (See Figure 13)))).

[0163] Table 8 shows the results of the PSD, BET, concentration of molecules present on the surface of the layered double hydroxide (LDH), and acid scavenging functionality of the material. Regarding PSD, no significant changes occur after modification (or alteration or denaturation or modification or modification) with organic acids. The BET increased for all materials after modification with organic acids, indicating that the surface was modified due to this reaction. As can be seen from Table 8, the residual amount of organic acid or organic acid derivative on the surface of the layered double hydroxide (LDH) according to the invention is in many cases 10% lower than when first added to the reaction. This indicates that no organic acid is used during the reaction, or that no organic acid or derivative of the organic acid is bonded (or attached) to the surface. For phenylphosphonic acid and benzene-1,3,5-tricarboxylic acid, the surface treatment reaction was found to be substantially complete.

[0164] Furthermore, the nucleation effect and acid scavenging functionality of the layered double hydroxide (LDH) particles according to the present invention were maintained. Acid scavenging titration showed that modification with organic acids resulted in a decrease in functionality (from 2.4 mol chloride / mol LDH to 1.86 mol chloride / mol LDH). It has been found that the layered double hydroxide (LDH) particles according to the present invention can remove (or scavenge) at least 1.86 mol chloride / 1 mol LDH, and therefore have acid removal (or acid scavenging) functionality (or functionality or functionality). In addition, commercially available DHT TM Compared to -4V (which is widely used as an acid scavenger), the modified layered double hydroxide (LDH) particles according to the present invention lose up to 15% of their acid scavenging functionality. This comes at the expense of the nucleation effect.

[0165] Table 8: Summary of specifications of modified layered double hydroxides (LDHs) [Table 8]

[0166] *PIM concentrations decrease over time (PIM concentrations tested in overnight analysis). Therefore, the actual concentration of PIM is expected to be higher than the measured value.

[0167] The WAXD patterns of LDH modified with cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid are shown in FIG. This analysis shows that polypropylene without LDH contains a small amount of β-nucleation (or beta nucleation) and most of it is α-nucleation (or alpha nucleation). Addition of cis-1,2-cyclohexanedicarboxylic acid-modified LDH to polypropylene decreased β-nucleation (or beta-nucleation) and increased α-nucleation (or alpha-nucleation). Therefore, cis-1,2-cyclohexanedicarboxylic acid-modified LDH can be considered an α-nucleating agent (or alpha-nucleator). Additives to bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDHs decreased β-nucleation (or beta-nucleation) and increased α-nucleation (or alpha-nucleation), similar to those observed with cis-1,2-cyclohexanedicarboxylic acid. Therefore, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified layered double hydroxides (LDHs) could also be considered as α-nucleating agents (or alpha-nucleating agents or nucleators).

[0168] It was found that the Tc of polypropylene containing the modified layered double hydroxide (LDH) according to the present invention achieved an increase of at least 1.5°C compared to the Tc of polypropylene containing untreated layered double hydroxide (LDH). Furthermore, the modified layered double hydroxides (LDHs) according to the present invention have been found to have acid scavenging and nucleation effects. In further experiments, LDH particles of different specifications were used. Particles of modified layered double hydroxide (LDH) were synthesized according to the method described above. In the above method, zinc was used to synthesize LDH particles (with various magnesium / aluminum ratios, BET and PSD or aspect ratios).

[0169] The specific surface area of ​​the sample was determined using a Quantachrome Monosorb Surface Area Analyser. The sample (or specimen) is prepared by degassing the sample (or specimen) (under a flow of He / N2 (30 / 70) at 90°C for 15 minutes). After degassing, the sample holder is immersed in liquid nitrogen for a few minutes. Subsequently, the sample holder is heated to room temperature by the on-board heater. The amount of released He / N2 is measured with a thermal conductivity detector. Then, the signal intensity is converted into the specific surface area (unit: m) of the sample. 2 / g).

[0170] Additionally, a Microtrac S3500 is used to determine particle size distribution (PSD). The sample was dispersed in ultrapure water and methanol, homogenized by sonication (38% amplitude) in a Cole Palmer for 5 minutes, and then added to the sample chamber in approximately 1 mL.

[0171] Layered double hydroxide (LDH) particles of various specifications were reacted with cis-1,2-cyclohexanedicarboxylic acid. The DSC of the various samples is provided in Table 9.

[0172] Table 9: Results summary [Table 9]

[0173] We can conclude as follows: The modified LDH particles exhibited nucleation and acid scavenging properties. Among them, the modified LDH particles exhibited improved nucleation in samples with high BET and low PSD.

[0174] Furthermore, it can be concluded that: The modified layered double hydroxide (LDH) particles according to the present invention provide efficient and effective nucleation and acid scavenging functionality.

[0175] The present invention is not meant to be limited to the preferred embodiments and / or experiments thereof described above. To the extent that many variations are possible, the scope sought is defined (or set forth) by the following claims.

Claims

1. Formula (I): [[[M １ ２＋ ] ｙ (M ２ ２＋ ) ｚ ] １－ｘ [M ３ ３＋ ] ｘ (OH) ２ ](A ｎ－ ) ｘ／ｎ ・mH ２ O (I) [In the formula, M １ and M ２ are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd, M ３ is a trivalent metal such as Al and / or Fe, especially Al, A ｎ－ is one or more intercalating n-valent anions, m, x, y, and z are values ​​within the ranges shown below. 0≦m<2 0<x≦0.5 0.5≦y+z≦1] The modified layered double hydroxide (LDH) of the above formula (1) comprises a modified outer layer, wherein the outer layer is modified with a derivative of an organic acid or a salt thereof.

2. The organic acid derivative or salt thereof may be a mono- or di-carboxy-C １－１２ Alkyl, C １－１２ Alkyl sulfonyl hydroxide, C １－１２ Alkylphosphonic acid, bis C １－１２ Alkyl phosphonates, N-substituted isocyanurates, mono-, di- or tri-carboxy-C ３－８ Cycloalkanes, formula (II): 【Chemistry 1】 (II) [In the formula, k is an integer from 1 to 3, n is an integer from 0 to 5, A represents cycloalkyl, aryl or heteroaryl; L represents a direct bond or NH; R １ are independently hydroxy, carboxyl, C １－６ Alkoxycarbonyl, arylcarbonylamino, amino, amido, C １－６ one or more selected from alkyl, hydroxyphosphoryl, Het or Ar; Ar represents aryl; Het represents a heterocycle; R ２ represents C, P or S, R ３ is hydroxy and is present when L represents a direct bond, or R ３ When L represents NH, it is hydroxy or C １－６ is alkyl, R ４ is hydroxy or C １－６ alkylcarbonyl, R ２ represents P, or R ４ is a double-bonded oxygen, and R ２ represents S] 2. The modified layered double hydroxide (LDH) of claim 1, wherein one or more of the organic acid derivatives are selected from the group consisting of:

3. Formula (II) may be converted to formula (III): 【Chemistry 2】 (III) The modified layered double hydroxide (LDH) according to claim 2, wherein:

4. 4. The modified layered double hydroxide (LDH) of claim 2 or 3, wherein A is independently selected from aryl or heteroaryl.

5. The organic acid derivatives or salts thereof include bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalenedicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 4-(benzoylamino)benzoic acid. The modified layered double hydroxide (LDH) according to any one of claims 1 to 4, wherein one or more of the carboxylic acids are selected from the group consisting of carboxylic acids, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthalenecarboxylic acid, 2-tert-butylbenzoic acid, 4-aminobenzoic acid, 4-biphenylcarboxylic acid, 4-toluenesulfonic acid, bis(2-ethylhexyl) hydrogen phosphate, butylphosphonic acid, 4-phthalimidobenzoic acid, and 4-tert-butylbenzoic acid.

6. The modified layered double hydroxide (LDH) according to any one of claims 1 to 5, wherein the organic acid derivative or salt thereof is one or more selected from the group consisting of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, pimelic acid, phenylphosphonic acid, and 2,6-naphthalenedicarboxylic acid.

7. The modified layered double hydroxide (LDH) according to any one of claims 1 to 6, wherein the organic acid derivative or salt thereof is cis-1,2-cyclohexanedicarboxylic acid.

8. The modified layered double hydroxide (LDH) according to claim 7, wherein the modified layered double hydroxide (LDH) comprises an X-ray diffraction peak in the range of 4° (2θ) to 9° (2θ).

9. The modified layered double hydroxide (LDH) according to claim 1 or 2, wherein the organic acid derivative or its salt comprises 1,3,5-triazine-2,4,6-triol.

10. The modified layered double hydroxide (LDH) according to claim 1 or 2, wherein the organic acid derivative or salt thereof is mono-, di- or tri-carboxycyclohexane, preferably the mono-, di- or tri-carboxycyclohexane comprises 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid.

11. A ｎ－ The modified layered double hydroxide (LDH) according to any one of claims 1 to 10, wherein is one or more selected from the group consisting of carbonate ions, nitrate ions, sulfate ions and combinations thereof.

12. A ｎ－ The modified layered double hydroxide (LDH) according to any one of claims 1 to 11, wherein is a carbonate ion.

13. Particles comprising the modified layered double hydroxide (LDH) according to any one of claims 1 to 12.

14. The particles according to claim 13, having an average secondary particle diameter measured by a laser diffraction method in the range of 0.01 μm to 20 μm, preferably in the range of 0.04 μm to 3 μm, more preferably in the range of 0.1 μm to 1 μm.

15. A resin composition comprising the particles according to claim 13 or 14 in a range of 1 ppm to 10,000 ppm, preferably 50 ppm to 5,000 ppm, more preferably 100 ppm to 3,000 ppm, and a resin.

16. The resin composition according to claim 15, wherein the resin is one or more selected from the group consisting of polyolefin, polyvinyl chloride, polyvinyl alcohol, and polylactic acid.

17. A dispersion comprising particles according to claim 13 or 14 in the range of 1 ppm to 10,000 ppm, preferably 50 ppm to 5,000 ppm, more preferably 100 ppm to 3,000 ppm, and a liquid.

18. Formula (I): [[[M １ ２＋ ] ｙ (M ２ ２＋ ) ｚ ] １－ｘ [M ３ ３＋ ] ｘ (OH) ２ ](A ｎ－ ) ｘ／ｎ ・mH ２ O (I) [In the formula, M １ and M ２ are each independently a divalent metal selected from the group Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba, in particular from the group Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd, M ３ is a trivalent metal such as Al and / or Fe, especially Al, A ｎ－ is one or more intercalating n-valent anions, m, x, y, and z are values ​​within the ranges shown below. 0≦m<2 0<x≦0.5 0.5≦y+z≦1] 13. A method for producing the modified layered double hydroxide (LDH) of any one of claims 1 to 12, comprising contacting the layered double hydroxide of the formula (I) with a derivative of an organic acid or a salt thereof.

19. The organic acid derivative or salt thereof may be a mono- or di-carboxy-C １－１２ Alkyl, C １－１２ Alkyl sulfonyl hydroxide, C １－１２ Alkylphosphonic acid, bis C １－１２ Alkyl phosphonates, formula (II): 【Transformation 3】 (II) [In the formula, k is an integer from 1 to 3, n is an integer from 0 to 5, A represents cycloalkyl, aryl or heteroaryl; L represents a direct bond or NH; R １ are independently hydroxy, carboxyl, C １－６ Alkoxycarbonyl, arylcarbonylamino, amino, amido, C １－６ one or more selected from alkyl, hydroxyphosphoryl, Het or Ar; Ar represents aryl; Het represents a heterocycle; R ２ represents C, P or S, R ３ is hydroxy and is present when L represents a direct bond, or R ３ When L represents NH, it is hydroxy or C １－６ is alkyl, R ４ is hydroxy or C １－６ alkylcarbonyl, R ２ represents P, or R ４ is a double-bonded oxygen, and R ２ exists when represents S] 19. The method of claim 18, wherein one or more of the organic acid derivatives are selected from the group consisting of:

20. 20. The method of claim 19, wherein A is independently selected from aryl or heteroaryl.

21. The organic acid derivatives include bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalenedicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 4-(benzoylamino) The method according to any one of claims 19 to 20, wherein one or more of the carboxylic acids are selected from the group consisting of benzoic acid, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthalenecarboxylic acid, 2-tert-butylbenzoic acid, 4-aminobenzoic acid, 4-biphenylcarboxylic acid, 4-toluenesulfonic acid, bis(2-ethylhexyl) hydrogen phosphate, butylphosphonic acid, 4-phthalimidobenzoic acid, and 4-tert-butylbenzoic acid.

22. 19. Use of the modified layered double hydroxide (LDH) according to any one of claims 1 to 12, the particles according to claims 13 or 14, the resin composition according to claims 15 or 16, and / or the dispersion according to claim 17 in the polymer industry, said polymer industry comprising the synthesis of polymers, the manufacture of polymer compositions, the conversion of polymer compositions into consumables.

23. Use of the modified layered double hydroxide (LDH) according to any one of claims 1 to 12, the particles according to claim 13 or 14, the resin composition according to claim 15 or 16, and / or the dispersion according to claim 17 as an acid scavenger and / or nucleating agent.

24. 24. Use according to claim 23 in the processing of crystalline thermoplastic and / or semi-crystalline polymers.

25. 25. The use according to claim 24, wherein the crystalline thermoplastic polymer and / or the semi-crystalline polymer is one or more selected from the group consisting of polypropylene, polyethylene, polylactic acid, polybutylene terephthalate, polyethylene furanoate, polyoxymethylene, polyamide, polyhydroxyalkanoate.

26. 26. Use according to claim 24 or 25 for increasing the crystallization temperature in the processing of said crystalline thermoplastic polymer and / or said semi-crystalline polymer.

27. 27. Use according to claim 26, wherein the increased crystallization temperature is an increase of at least 0.5°C, preferably at least 1°C, more preferably at least 2°C, even more preferably at least 3°C, even more preferably at least 4°C, and most preferably at least 5°C according to EN ISO 11357-3:2018.

28. 28. Use according to claims 24 to 27, wherein the crystalline thermoplastic polymer is polypropylene and has a crystallization temperature according to EN ISO 11357-3:2018 of at least 120.05°C, preferably at least 121°C, more preferably at least 122°C, even more preferably at least 123°C, even more preferably at least 124°C, and most preferably at least 125°C.

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