Modified layered double hydroxide (LDH), particles comprising said LDH and process for producing said ldh

Abstract

The present invention relates to a modified layered double hydroxide (LDH), particles comprising said modified LDH, a resin composition comprising a resin and said particles, a dispersion comprising a liquid and said particles, and a method for producing said modified LDH. The modified layered double hydroxide according to the present invention comprises a modified layered double hydroxide according to formula (I) [[[M12 +] y (M22 +) z] 1-x [M33 +] x (OH) 2] (An-) x / n.mH2O (I) wherein: M1 and M2 are each independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; a divalent metal, in particular each independently selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; m3 is a trivalent metal such as Al and / or Fe; in particular Al; and An-is one or more intercalated n-valent anions, wherein m, x, y and z are values within the range represented by: 0 < = mlt; 2, 0lt; x < = 0.5, 0.5 < = y + z < = 1, the modified layered double hydroxide according to the invention further comprising a modified outer layer wherein the outer layer is modified with an organic acid derivative or a salt thereof.

Description

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

[0002] Conventional hydrotalcite particles have been developed for various uses, including heat stabilizers for polyvinyl chloride resins, neutralizers for residues derived from the use of polyolefin polymerization catalysts, acid acceptors for halogen-containing rubbers, thermal insulation agents for agricultural films, and the like. In addition, suspensions containing conventional hydrotalcite particles can be used as liquid antacids or heat stabilizers.

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

[0004] The present invention aims to eliminate or at least reduce the above problems and to enable the modified layered double hydroxide to function efficiently and effectively.

[0005] This object is achieved by modified layered double hydroxides (LDH) according to formula (I),

[0006] [[[M 1 2+ ] y (M 2 2+ ) z ] 1-x [M 3 3+ ] x (OH) 2 ](A n- ) x / n ·mH 2 O

[0007] (I)

[0008] in:

[0009] M 1 and M 2 Each is independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; in particular, each is independently a divalent metal selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd;

[0010] M 3 is a trivalent metal such as Al and / or Fe; in particular Al; and

[0011] A n- is one or more intercalated n-valent anions,

[0012] where m, x, y, and z are values ​​in the range represented by:

[0013] 0≤m<2

[0014] 0 <x≤0.5

[0015] 0.5≤y+z≤1,

[0016] The modified layered double hydroxide (LDH) further comprises a modified outer layer, wherein the outer layer is modified with an organic acid derivative or a salt thereof.

[0017] It should be noted that in this application, modified layered double hydroxide (LDH) refers to a layered double hydroxide having exchangeable anions and H 2 O as a substance of the intermediate layer, the intermediate layer being the intermediate layer between the stacked hydroxide alkaline layers. The present application also relates to using the modified LDH by utilizing the dual functions of the acid scavenger and nucleation of the modified LDH. Therefore, in a first aspect, the present invention provides a modified LDH, wherein the modified LDH comprises: one or more intercalated n-valent anions, also referred to as an intermediate layer comprising n-valent anions having a valence of n; and an outer layer modified with an organic acid derivative or a salt thereof.

[0018] It should also be noted that in certain embodiments, the functional groups of the modified outer layer of the modified LDH can be referred to as carboxylic acid derivatives. The derivatives can include carboxylic acids themselves, carboxylates (deprotonated carboxylic acids), amides, esters, thioesters, and acyl phosphates. In addition, organic acid derivatives can be represented by salts of the corresponding organic acid derivatives.

[0019] It should also be noted that in embodiments, the modified LDH may comprise a member selected from the group consisting of 1 、M 2 and M 3 In other words, for M 1 、M 2 and M 3 Each of the metals may be present in the modified LDH.

[0020] The advantage of the modified LDH according to the present invention is that the LDH has a dual function. The dual function enables the reduction of resources (additives) during and / or after the synthesis of, for example, a polymer. Preferably, the modified LDH and / or the additive are provided to the polymer after polymerization. As a result, the synthesis can be carried out in a more environmentally friendly and cost-effective manner. In particular, it was found that modifying the outer layer of the LDH with an organic acid derivative or a salt thereof can achieve the dual function.

[0021] It should be noted that throughout this application, the synthesis of a polymer includes all stages leading to the final product / composition of the polymer. In other words, the synthesis includes the polymerization of the desired polymer and the mixing of the polymer with the modified LDH and / or additives, such as extrusion.

[0022] The mixing may include mixing the polymerized polymer with the modified LDH and / or additives (preferably in solid state) and / or dispersing the polymer and the modified LDH and / or additives. Optionally, the dispersing of the mixture may be performed in an extruder.

[0023] The modified LDH according to the present invention can replace acid scavengers and nucleating agents in the synthesis of polymers. Therefore, the complexity of additive feeding during polymer synthesis is reduced. In addition, it is found that compared with polymer compositions with conventional acid scavengers and nucleating agents, the modified LDH according to the present invention provides a cleaner polymer.

[0024] For example, replacement of migrating components such as metal soaps can be achieved. Thus, the specific migration limit (SML) and / or emissions of volatile organic compounds (VOC) are improved.

[0025] It is found that the modified LDH according to the present invention can be efficiently and effectively used in the synthesis of polypropylene, polyethylene and polystyrene. It should be noted that polypropylene includes homopolymers, (random and heterogeneous) copolymers and the like, and polyethylene includes high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) and the like.

[0026] Another advantage of the modified LDH according to the present invention is that the modified LDH is compatible with conventional (polymer) additives such as antioxidants, UV stabilizers, dispersants and the like. In addition, the modified LDH according to the present invention is also compatible with additive blends and / or concentrates. Therefore, the modified LDH according to the present invention can be efficiently and effectively used in the synthesis of polymers. Preferably, after the polymer polymerization, a polymer composition comprising the modified LDH according to the present invention and one or more of the above-mentioned additives is provided.

[0027] Another advantage of the modified LDH according to the present invention is that the modified LDH is compatible with the various technologies in polymer synthesis. For example, extrusion, injection process, additive blending, concentration. Extrusion and / or injection can include thermoforming, extrusion blow molding, sheet extrusion, extrusion compression molding, tube extrusion, film casting, blown film, raffia extrusion (raffia extrusion), belt extrusion, fiber extrusion, meltblown materials, spunbond fabrics, injection molding, injection stretch blow molding, injection blow molding, compression molding, rotational molding, 3D printing. Therefore, the modified LDH according to the present invention can be efficiently and effectively used in the synthesis of polymers.

[0028] For example, polymer compositions comprising modified LDHs according to the present invention can be used as films in cups, trays, pallets, and the like.

[0029] In a preferred embodiment according to the present invention, the organic acid derivative or its salt may be one or more selected from the following: monocarboxyl C 1-12 Alkyl or dicarboxyl C 1-12 Alkyl, C 1-12 Alkylsulfonyl hydroxide, C 1-12 Alkylphosphonic acid, di-C 1-12 Alkylphosphonates, N-substituted isocyanurates, monocarboxylic C 3-8 Cycloalkanes, dicarboxyl C 3-8 Cycloalkanes or tricarboxyl C 3-8 Cycloalkanes, organic acid derivatives according to formula (II),

[0030]

[0031] in:

[0032] k is an integer from 1 to 3;

[0033] n is an integer from 0 to 5;

[0034] A represents a cycloalkyl group, an aryl group or a heteroaryl group;

[0035] L represents a direct bond or NH;

[0036] R 1 are independently selected from hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amide, C 1-6 One or more of alkyl, hydroxyphosphoryl, Het or Ar;

[0037] Ar represents an aryl group;

[0038] Het represents a heterocycle;

[0039] R 2Indicates C or P or S;

[0040] Where R 3 is a hydroxyl group and is present when L represents a direct bond, or wherein R 3 is hydroxyl or, when L represents NH, is C 1-6 Alkyl; and

[0041] Where R 4 Is hydroxyl or C 1-6 alkylcarbonyl, and when R 2 It exists when P is expressed, or when R 4 is a double bond oxygen and when R 2 Indicates that S exists.

[0042] In a preferred embodiment, n is an integer from 0 to 2.

[0043] It should be noted that the monocarboxyl C 3-8 Cycloalkanes, dicarboxyl C 3-8 Cycloalkanes or tricarboxyl C 3-8 The cycloalkanes may contain substituents, preferably one or more C 1-6 For example, the substituent may be located in the para position of the monocarboxycyclohexane.

[0044] In another preferred embodiment according to the present invention, the organic acid derivative or its salt may be one or more selected from the following: monocarboxyl C 1-12 Alkyl or dicarboxyl C 1-12 Alkyl, C 1-12 Alkylsulfonyl hydroxide, C 1-12 Alkylphosphonic acid, di-C 1-12 Alkylphosphonates, organic acid derivatives according to formula (II),

[0045]

[0046] in:

[0047] k is an integer from 1 to 3;

[0048] n is an integer from 0 to 5;

[0049] A represents a cycloalkyl group, an aryl group or a heteroaryl group;

[0050] L represents a direct bond or NH;

[0051] R 1 are independently selected from hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amide, C 1-6 One or more of alkyl, hydroxyphosphoryl, Het or Ar;

[0052] Ar represents an aryl group;

[0053] Het represents a heterocycle;

[0054] R 2 Indicates C or P or S;

[0055] Where R 3 is a hydroxyl group and is present when L represents a direct bond, or wherein R 3 is hydroxyl or, when L represents NH, is C 1-6 Alkyl; and

[0056] Where R 4 Is hydroxyl or C 1-6 alkylcarbonyl, and when R 2 It exists when P is expressed, or when R 4 is a double bond oxygen and when R 2 Preferably, formula II is represented by formula III,

[0057]

[0058] In a further preferred embodiment according to the present invention, when A is cycloalkyl, the cycloalkyl is norbornane, norbornene, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl or cyclohexenyl.

[0059] In a further preferred embodiment according to the present invention, n is an integer from 0 to 2.

[0060] It should be noted that different organic acid derivatives or salts thereof may be present in the modified LDH according to the present invention. Thus, the organic acid derivative or salt thereof may be directly bonded to the outer layer of the LDH to provide the modified LDH according to the present invention.

[0061] It should also be noted that when R 2 When C is indicated, R 4 Not present in Formula II and / or Formula III.

[0062] The advantage of the above organic acid derivatives or salts thereof is that these organic acid derivatives or salts thereof provide highly efficient and effective modified LDH, which is preferably capable of performing at least dual functions. As mentioned above, the dual functions are preferably functions as an acid scavenger and a nucleating agent.

[0063] Another advantage of the above organic acid derivatives or their salts is to prevent and / or reduce the undesirable effects of halogens in the polymer composition obtained after synthesis. Therefore, the composition comprising a polymer and the modified LDH according to the present invention is less affected by said undesirable effects.

[0064] In further presently preferred embodiments according to the present invention, A may be aryl or heteroaryl.

[0065] It was found that A being an aryl or heteroaryl group enables efficient and effective acid scavenging and nucleation in, for example, the synthesis of polymers.

[0066] In a preferred embodiment, the modified layered double hydroxide according to the invention comprises the formula (I),

[0067] [[[M 1 2+ ] y (M 2 2+ ) z ] 1-x [M 3 3+ ] x (OH) 2 ](A n- ) x / n ·mH 2 O

[0068] (I)

[0069] in:

[0070] M 1 and M 2 Each is independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; in particular, each is independently a divalent metal selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd;

[0071] M 3 is a trivalent metal such as Al and / or Fe; in particular Al; and

[0072] A n- is one or more intercalated n-valent anions,

[0073] where m, x, y, and z are values ​​in the range represented by:

[0074] 0≤m<2

[0075] 0 <x≤0.5

[0076] 0.5≤y+z≤1,

[0077] The modified layered double hydroxide according to the present invention further comprises a modified outer layer, wherein the outer layer is modified with an organic acid derivative or a salt thereof.

[0078] The organic acid derivative or its salt may be one or more selected from the following: monocarboxyl C 1-12Alkyl or dicarboxyl C 1-12 Alkyl, C 1-12 Alkylsulfonyl hydroxide, C 1-12 Alkylphosphonic acid, di-C 1-12 Alkylphosphonates, organic acid derivatives according to formula (II),

[0079]

[0080] in:

[0081] k is an integer from 1 to 3;

[0082] n is an integer from 0 to 5;

[0083] A represents a cycloalkyl group, an aryl group, a heteroaryl group, a norbornene group or a norbornene group;

[0084] L represents a direct bond or NH;

[0085] R 1 are independently selected from hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amide, C 1-6 One or more of alkyl, hydroxyphosphoryl, Het or Ar;

[0086] Ar represents an aryl group;

[0087] Het represents a heterocycle;

[0088] R 2 Indicates C or P or S;

[0089] Where R 3 is a hydroxyl group and is present when L represents a direct bond, or wherein R 3 is hydroxyl or, when L represents NH, is C 1-6 Alkyl; and

[0090] Where R 4 Is hydroxyl or C 1-6 alkylcarbonyl, and when R 2 It exists when P is expressed, or when R 4 is a double bond oxygen and when R 2 It exists when S is represented, and

[0091] wherein A is independently selected from aryl or heteroaryl.

[0092] In further currently preferred embodiments according to the present invention, n is an integer from 0 to 2.

[0093] The modified layered double hydroxides were found to provide efficient and effective nucleation and acid scavenging.

[0094] In a further preferred embodiment, the modified layered double hydroxide according to the invention comprises the formula (I),

[0095] [[[M 1 2+ ] y (M 2 2+ ) z ] 1-x [M 3 3+ ] x (OH) 2 ](A n- ) x / n ·mH 2 O

[0096] (I)

[0097] in:

[0098] M 1 and M 2 Each is independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; in particular, each is independently a divalent metal selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd;

[0099] M 3 is a trivalent metal such as Al and / or Fe; in particular Al; and

[0100] A n- is one or more intercalated n-valent anions,

[0101] where m, x, y, and z are values ​​in the range represented by:

[0102] 0≤m<2

[0103] 0 <x≤0.5

[0104] 0.5≤y+z≤1,

[0105] The modified layered double hydroxide according to the present invention further comprises a modified outer layer, wherein the outer layer is modified with an organic acid derivative or a salt thereof.

[0106] Wherein Formula II is represented by Formula III,

[0107] and

[0108] wherein A is independently selected from aryl or heteroaryl.

[0109] The modified layered double hydroxides were found to provide efficient and effective nucleation and acid scavenging.

[0110] Furthermore, when the modified LDH according to the present invention is included in a polymerization, such as that of polypropylene, polyethylene, polylactic acid, polybutylene terephthalate, polybutylene adipate terephthalate, and the like, ΔT is achieved.

[0111] The advantage of said crystallization temperature is that efficient and effective acid scavenging and nucleation of the modified LDH according to the present invention is achieved.

[0112] In a preferred embodiment according to the present invention, the organic acid derivative or its salt 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, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalene dicarboxylic 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, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthoic 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, 4-propylcyclohexanecarboxylic acid. Preferably, the organic acid derivative or its salt can be one or more selected from the group consisting of benzoic acid, cis-1,2-cyclohexanedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (2,3-norbornane dicarboxylic acid), heptane dicarboxylic acid, phenylphosphonic acid, benzene-1,3,5-tricarboxylic acid, 1,3,5-triazine-2,4,6-triol, 4-aminobenzoic acid, 1,4-cyclohexane dicarboxylic acid, 2-carboxyethyl (phenyl) phosphinic acid, 4-propylcyclohexanecarboxylic acid, butylphosphonic acid, 4-toluenesulfonic acid.

[0113] In another currently preferred embodiment according to the present invention, the organic acid derivative or its salt can be one or more 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-naphthalene dicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine- 4-formic acid, 4-pyridinecarboxylic acid, benzene-1,3,5-tricarboxylic acid, 4-(benzoylamino)benzoic acid, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl (phenyl) phosphinic acid, 2-naphthoic 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. Preferably, the organic acid derivative or its salt can be selected from the group of bicyclo [2.2.1] heptane-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, pimelic acid, phenylphosphonic acid, 2,6-naphthalenedicarboxylic acid.

[0114] An advantage of the acid is that modified LDH particles are obtained having a Tc of at least 122°C.

[0115] In another currently preferred embodiment according to the present invention, the organic acid derivative or salt thereof may be cis-1,2-cyclohexanedicarboxylic acid.

[0116] It is found that the modified LDH according to the present invention comprising one or more of the above organic acid derivatives or salts thereof, in particular comprising cis-1,2-cyclohexanedicarboxylic acid, provides at least one highly efficient and effective acid scavenger and nucleating agent, thus providing a highly efficient and effective dual function.

[0117] In further presently preferred embodiments according to the present invention, the modified LDH comprises an X-ray diffraction peak in the range of 4° 2θ to 9° 2θ.

[0118] It has been found that cis-1,2-cyclohexanedicarboxylic acid is able to achieve a modified LDH comprising an X-ray diffraction peak in the range of 4° 2θ to 9° 2θ.

[0119] In another presently preferred embodiment according to the present invention, the organic acid derivative or salt thereof comprises 1,3,5-triazine-2,4,6-triol.

[0120] It should be noted that 1,3,5-triazine-2,4,6-triol is an N-substituted isocyanurate.

[0121] The 1,3,5-triazine-2,4,6-triol was found to provide an average Tc of 121.90° C. Furthermore, the organic acid derivative enables efficient and effective acid scavenging and nucleation.

[0122] In another currently preferred embodiment according to the present invention, the organic acid derivative or its salt comprises monocarboxycyclohexane, dicarboxycyclohexane or tricarboxycyclohexane, preferably wherein the monocarboxycyclohexane, dicarboxycyclohexane or tricarboxycyclohexane is 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid.

[0123] An advantage of the acid is that modified LDH particles are obtained having a Tc of at least 120.5°C.

[0124] In another currently preferred embodiment according to the present invention, A n- It can be one or more selected from the group consisting of carbonate ions, nitrate ions, sulfate ions or combinations thereof. Preferably, A n- It may be a carbonate ion.

[0125] A n- An advantage of the above groups is that the acid scavenging of the modified LDH according to the invention is improved.

[0126] It has been found that A with intercalation n- The modified LDH according to the present invention is provided with acid scavenger properties.

[0127] The invention also relates to particles comprising the modified LDH according to the invention.

[0128] The particles including the modified LDH provide the same effects and advantages as those described with respect to the modified LDH according to the present invention.

[0129] It has been found that the particles according to the invention provide beneficial effects in particular in the synthesis of polypropylene and polyethylene.

[0130] In currently preferred embodiments according to the present invention, the particles may have an average secondary particle diameter in the range of 1 nm to 2000 nm, preferably in the range of 3 nm to 1500 nm, more preferably in the range of 5 nm to 1000 nm, as measured by a dynamic light scattering method.

[0131] It should be noted that dynamic light scattering is based on quality control methods, including particle size determination (based on volume distribution). After the sample is ultrasonicated, the particle size distribution in water is measured by laser diffraction method on Microtrac S3500 particle size analyzer. 2mLMeOH is added to 0.35g of sample, and 35mL of 0.2w / v% sodium hexametaphosphate (deflocculant) is added after 1 minute. The sample is then subjected to ultrasonic vibration for 5 minutes. Stir the sample, and take out 1mL from the sample with a pipette and inject it into the particle size analyzer.

[0132] It has been found that particles having an average secondary particle size in the range of 1 nm to 2000 nm, preferably in the range of 3 nm to 1500 nm, more preferably in the range of 5 nm to 1000 nm as measured by dynamic light scattering methods provide efficient and effective acid scavenging and nucleation.

[0133] In a further currently preferred embodiment according to the present invention, the particles have an average secondary particle size in the range of 0.01 to 20 μm, preferably in the range of 0.04 to 3 μm, more preferably in the range of 0.1 to 1 μm, measured by laser diffraction methods.

[0134] The present invention also relates to a resin composition comprising a resin and the particles according to the present invention in the range of 1 ppm to 10000 ppm, preferably 50 ppm to 5000 ppm, more preferably 100 ppm to 3000 ppm.

[0135] The resin composition according to the present invention provides the same effects and advantages as those described with respect to the modified LDH according to the present invention and the particles comprising the modified LDH according to the present invention.

[0136] It should be noted that the resin according to the invention comprises from 1 ppm to 10000 ppm, preferably from 50 ppm to 5000 ppm, more preferably from 100 ppm to 3000 ppm of particles according to the invention compared to the resin.

[0137] In a preferred embodiment according to the present invention, the resin may be one or more selected from the group consisting of polyolefin, polyvinyl chloride, polyvinyl alcohol, and polylactic acid.

[0138] It has been found that the resin is one or more selected from the group consisting of polyolefins, polyvinyl chloride, polyvinyl alcohol, polylactic acid to achieve efficient and effective acid scavenging and nucleation.

[0139] The invention also relates to a dispersion comprising a liquid and particles according to the invention in the range from 1 ppm to 10000 ppm, preferably from 50 ppm to 5000 ppm, more preferably from 100 ppm to 3000 ppm.

[0140] The dispersion according to the present invention provides the same effects and advantages as those described for the modified LDH according to the present invention, the particles comprising the modified LDH according to the present invention and the resin composition according to the present invention.

[0141] In a preferred embodiment, the liquid is one or more selected from the group consisting of water, ethanol, methanol, propanol, ethyl acetate.

[0142] The present invention also relates to a method for producing a modified LDH according to the present invention, which method comprises contacting a layered double hydroxide according to formula (I) with an organic acid derivative or a salt thereof,

[0143] [[[M 1 2+ ] y (M 2 2+ ) z ] 1-x [M 3 3+ ] x (OH) 2 ](A n- ) x / n ·mH 2 O

[0144] (I)

[0145] in:

[0146] M 1 and M 2 Each is independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; in particular, each is independently a divalent metal selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd;

[0147] M 3 is a trivalent metal such as Al and / or Fe; in particular Al; and

[0148] A n- is one or more intercalated n-valent anions,

[0149] where m, x, y, and z are values ​​in the range represented by:

[0150] 0≤m<2

[0151] 0 <x≤0.5

[0152] 0.5≤y+z≤1.

[0153] The method for producing the modified LDH according to the present invention provides the same effects and advantages as those described for the modified LDH according to the present invention, the particles comprising the modified LDH according to the present invention, the dispersion according to the present invention and the resin composition according to the present invention.

[0154] The method for producing the modified LDH according to the present invention includes the step of contacting the outer layer of the layered double hydroxide with an organic acid derivative or a salt thereof.

[0155] It has been found that the method according to the present invention efficiently and effectively provides a modified LDH comprising a modified outer layer.

[0156] In addition, the method according to the present invention can also include using the modified LDH according to the present invention to synthesize polymers, such as polymer compositions. The method includes, for example, mixing the modified LDH in a polymer melt extruder via an additive blend, masterbatch and / or concentrate with various polymer carriers, or mixing in powder form.

[0157] In a preferred embodiment according to the present invention, the organic acid derivative or its salt is one or more selected from the following: monocarboxyl C 1-12 Alkyl or dicarboxyl C 1-12 Alkyl, C 1-12 Alkylsulfonyl hydroxide, C 1-12 Alkylphosphonic acid, di-C 1-12 Alkylphosphonates, organic acid derivatives according to formula (II),

[0158]

[0159] in:

[0160] k is an integer from 1 to 3;

[0161] n is an integer from 0 to 5;

[0162] A represents a cycloalkyl group, an aryl group or a heteroaryl group;

[0163] L represents a direct bond or NH;

[0164] R 1 are independently selected from hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amide, C 1-6 One or more of alkyl, hydroxyphosphoryl, Het or Ar;

[0165] Ar represents an aryl group;

[0166] Het represents a heterocycle;

[0167] R 2 Indicates C or P or S;

[0168] Where R 3 is a hydroxyl group and is present when L represents a direct bond, or wherein R 3 is hydroxyl or, when L represents NH, is C 1-6 Alkyl; and

[0169] Where R 4 Is hydroxyl or C 1-6 alkylcarbonyl, and when R 2 It exists when P is expressed, or when R 4 is a double bond oxygen and when R 2 Indicates that S exists.

[0170] In a preferred embodiment, n is an integer from 0 to 2.

[0171] In further presently preferred embodiments according to the present invention, A may be aryl or heteroaryl.

[0172] In another currently preferred embodiment according to the present invention, the organic acid derivative or its salt can be one or more 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-naphthalene dicarboxylic 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, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthoic 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.

[0173] In a preferred embodiment, the organic acid derivative or its salt 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, and 2,6-naphthalene dicarboxylic acid.

[0174] The present invention also relates to the use of the modified layered double hydroxide according to the invention, the particles according to the invention, the resin composition according to the invention and / or the dispersion according to the invention in the polymer industry, wherein the polymer industry comprises the synthesis of polymers, the production of polymer compositions, the conversion of polymer compositions into consumables.

[0175] The use of the modified LDH in the polymer industry provides the same effects and advantages as described for the modified LDH according to the invention, the particles comprising the modified LDH according to the invention, the dispersion according to the invention, the resin composition according to the invention and the method for producing the modified LDH according to the invention.

[0176] It has been found that the modified LDH according to the present invention is particularly beneficial for synthesizing polymers, such as homopolymers, random copolymers and heterophasic copolymers containing polypropylene, polyethylene including high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and the like. In the synthesis, the modified LDH according to the present invention can be used as an acid scavenger and nucleating agent.

[0177] In a further preferred embodiment according to the invention, the modified LDH according to the invention is used to increase the crystallization temperature in the processing of crystalline thermoplastic polymers and / or semicrystalline polymers.

[0178] In a further preferred embodiment according to the present invention, the increased crystallization temperature is increased by 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, most preferably at least 5°C according to EN ISO 11357-3:2018.

[0179] It should be noted that ΔT represents the crystallization temperature in the case where no modified LDH is contained minus the crystallization temperature in the case where the modified LDH is contained.

[0180] In a further preferred embodiment according to the present invention, 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, most preferably at least 125°C.

[0181] Further advantages, features and details of the invention are elucidated on the basis of preferred embodiments thereof, with reference to the drawings and the accompanying experiments.

[0182] - Figure 1 : shows the X-ray diffraction of LDH modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention;

[0183] - Figure 2 : shows the FT-IR of LDH modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention;

[0184] - Figure 3 : shows the tensile test specimen;

[0185] - Figure 4 : shows the decomposition curves of two cis-1,2-cyclohexanedicarboxylic acid-modified LDH samples synthesized according to the first method and the second method;

[0186] - Figure 5 : TGA of cis-1,2-cyclohexanedicarboxylic acid magnesium salt and cis-1,2-cyclohexanedicarboxylic acid is shown;

[0187] - Figure 6 : shows the XRD pattern of the synthesized sample;

[0188] - Figure 7 : shows the XRD pattern of LDH particles modified with cis-1,2-cyclohexanedicarboxylic acid;

[0189] - Figure 8 : shows the FT-IR spectrum of the synthesized sample;

[0190] - Figure 9: shows a SEM image of the synthesized sample;

[0191] - Fig.10 : shows the XRD patterns of the samples mentioned in Table 5;

[0192] - Fig.11 : shows the FT-IR spectra of the samples mentioned in Table 5;

[0193] - Fig.12 : shows the XRD patterns of different LDH particles according to the present invention;

[0194] - Fig.13 : shows FT-IR spectra of different LDH particles according to the present invention; and

[0195] - Fig.14 : Shows the WAXD spectra of LDH modified with cis-1,2-cyclohexanedicarboxylic acid and LDH modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid.

[0196] In the experiment, the modified LDH according to the present invention has been synthesized. The synthesis starts with weighing 50g of layered double hydroxide into a two-necked flask, and 200ml of demineralized water is added to the flask and stirred at 18°C. A reflux condenser is installed on the first neck of the flask, and a dropping funnel is installed on the second neck of the flask. 5g of cis-1,2-cyclohexanedicarboxylic acid (HHPA) dissolved in 50ml EtOH is added to the dropping funnel and then slowly (about 1 drop per second) added to the stirred layered double hydroxide dispersion. After adding cis-1,2-cyclohexanedicarboxylic acid dissolved in EtOH, the dispersion is heated to reflux temperature for 2 hours. The solid is filtered and washed 5 times with demineralized water. After washing, the solid obtained is dried.

[0197] The solids were analyzed using FT-IR, SEM and XRD.It has been found that a modified LDH having both acid scavenging and nucleating functions has been synthesized.

[0198] XRD analysis shows:

[0199] X-ray diffraction was used to determine the basal spacing and crystal structure of cis-1,2-cyclohexanedicarboxylic acid-modified LDH.

[0200] X-ray diffraction spectra were recorded on a Panalytical X-pert powder spectrometer with a PIXcal1D-Medipix3 collaborative RTMS detector using a scan line detector. For these measurements, Cu Kα radiation was used. The goniometer step size was 0.026° 2θ and the counting time was 296.565 s. The spectra were recorded at 45 kV and 40 mA.

[0201] The focal length is 12.0 mm, the width is 0.4 mm, and the take-off angle is 6.0°. The thickness of the beta filter nickel is 0.020 mm. The Soller slit is 0.02 radians. The fixed incident beam mask is 15 mm and has a width of 11.60 mm. The anti-scatter slit is a fixed slit 1 / 2° and a height of 0.76 mm. The divergence slit is a fixed slit 1 / 4° and a height of 0.38 mm.

[0202] For the diffracted beam path, a radius of 240.0 mm was used. The anti-scatter slit was an AS slit 8.0 mm (PIXcel) fixed type with a height of 8.0 mm. The large Soller slit was 0.02 radians. The large beta filter nickel was 0.020 mm thick.

[0203] The X-ray diffraction pattern of the obtained material is Figure 1 X-ray diffraction was used to determine the basal spacing and crystal structure of cis-1,2-cyclohexanedicarboxylic acid-modified LDH. Figure 1 Marked in, peak 003 and 006 The position of indicates the intercalated carbonate (CO 3 2- ). Figure 1 The peaks observed in indicate that the cis-1,2-cyclohexanedicarboxylic acid-modified layered double hydroxide is a layered double hydroxide.

[0204] XRF analysis showed:

[0205] X-ray fluorescence data were recorded on a Panalytical Axios spectrometer equipped with a Rh tube. The samples were prepared by mixing the material (7.0 g) and an inert binder material, Elvacite 2046 (2 mL acetone solution, 40 g / 200 mL) in a mortar. After evaporation of the acetone, pellets of the material were pressed. The X-ray fluorescence spectrometer was used to determine the MII content and the MIII content of the samples, which are shown as percentages of the total sample weight, respectively. II O and M III O 3 .

[0206] Cis-1,2-cyclohexanedicarboxylic acid modified LDH according to the present invention 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. Number of scans = 32, resolution = 4, data spacing = 0.482 cm -1 And the final format = reflectivity %. The data obtained is Figure 2 Shown in.

[0207] Figure 2 The unmodified LDH (3200 cm -1 The upper line at 3200 cm) and cis-1,2-cyclohexanedicarboxylic acid-modified LDH (3200 cm -1 The FT-IR spectrum of the LDH modified with cis-1,2-cyclohexanedicarboxylic acid shows many additional peaks compared to the unmodified LDH. The most notable one is the peak at about 1470 cm -1 Up to 1660cm -1 (range of organic bonds) and 2800cm -1 Up to 3000cm -1 (CH / CH 2 key).

[0208] Analysis of the organic components showed:

[0209] Identification / quantification of the organic components of the modified LDH can be achieved using ion chromatography and / or liquid chromatography (LC) in combination with conductivity detection and / or mass spectrometry.

[0210] The modified LDH can be dissolved in acid, preferably further diluted, before injecting the solution into an IC column and / or LC system. Identification can then be performed by comparing the R t With the use of pure organic components R t Quantitation can be achieved by preparing a calibration line for the organic components and comparing the detector intensity of the sample to the calibration line.

[0211] In additional experiments, modified LDHs containing cis-1,2-cyclohexanedicarboxylic acid synthesized as described above were added to polypropylene, preferably a polypropylene homopolymer having a melt flow index of 10, by extrusion. Concentrations were varied, and calcium stearate (CaSt) may have been added to various samples (see Table 1). Properties were determined using DSC analysis and mechanical properties.

[0212] Prepare a powder blend of polypropylene, the modified LDH according to the present invention, and an antioxidant, and feed it into a completely clean twin-screw extruder. The product is granulated and injection molded into a tensile rod for measurement. The concentration of the modified LDH according to the present invention in different samples (or compositions) varies and is indicated in Table 1. Therefore, the modified LDH in each sample is the same. Between sample extrusions, the extruder is cleaned by purging with polypropylene and antioxidant.

[0213] Table 1: Samples comprising LDH modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention.

[0214]

[0215] Twin screw extrusion and injection molding were performed using the parameters disclosed in Table 2.

[0216] Table 2: Twin-screw extrusion and injection molding parameters.

[0217]

[0218] The samples were analyzed using differential scanning calorimetry (DSC). The extruded samples were placed in aluminum (Tzero) sample cups and analyzed by a TAInstrument Q2000 DSC. The temperature program used was from 180°C down to 20°C. The material was heated to an elevated temperature to eliminate the previous thermal history and then cooled at a linear rate. The temperature was measured by using a nitrogen purge (N 2) were analyzed in an inert atmosphere. The parameters used to perform DSC are provided in Table 3. The crystallization behavior was analyzed from the cooling curves.

[0219] Table 3: DSC parameters.

[0220] Starting temperature (℃) 50 <![CDATA[Heating rate (°C min -1 )]]> 10 Upper limit temperature (℃) 200 <![CDATA[Cooling rate (°C min -1 )]]> 10 Lower temperature(℃) 20

[0221] The tensile properties were determined by injection molding the samples into Type 1A sample bars as described in ISO 527-2 standard and testing according to Method B. An Instron 3365 tensile tester with a tensiometer was used.

[0222] In addition, the mold shrinkage was tested using ISO 294-4. The shrinkage of the sample was determined as described in standard ISO 294-4, except that the test specimen was a tensile test bar (Type 1A). The measuring device was a micrometer that measured dimensions with a resolution of 0.001 mm. The dimensions were measured with 0.01 mm accuracy. The shrinkage was measured 24 hours and 72 hours after injection molding. Figure 3 A tensile test specimen 2 is shown having an injection direction 4 and dimensions 6, 8, 10, 12, 14, and 16. Dimension 6 is 20 mm, dimension 8 is 10 mm, dimension 10 is 4 mm, dimension 12 is 80 mm, dimension 14 is 109.3 mm, and dimension 16 is 170 mm.

[0223] In order to determine the nucleation behavior of polypropylene, polypropylene samples with added (conventional) nucleating agents and added modified LDH according to the present invention were prepared. The crystallization temperature of the samples was determined by differential scanning calorimetry. A 5 mg sample of the injection molded material was heated to 200 ° C to eliminate all thermal history and then cooled to 20 ° C to analyze the crystallization exotherm. The results are provided in Table 1.

[0224] These results show the nucleation effect of samples containing cis-1,2-cyclohexanedicarboxylic acid modified LDH samples on polypropylene. As the concentration increases to 500 ppm, 1000 ppm, 2000 ppm, the crystallization temperature increases by 6°C.

[0225] These results show that the samples provide efficient and effective nucleation compared to conventional layered double hydroxides. In fact, the cis-1,2-cyclohexanedicarboxylic acid modified LDH according to the present invention provides nucleation and acid scavenging. The selected variables have little effect. It can be concluded that the addition of CaSt does not provide a significant difference compared to the sample without CaSt. In addition, increasing the concentration of cis-1,2-cyclohexanedicarboxylic acid modified LDH shows almost no increase in crystallization temperature.

[0226] The mechanical properties of the samples and references were determined and are listed in Table 1. The tensile properties were compared to non-nucleated polypropylene (with CaSt). These results show that the nucleated LDH containing cis-1,2-cyclohexanedicarboxylic acid modified LDH has a 10% to 16% increase in modulus and a 50% to 60% decrease in break strain compared to using conventional layered double hydroxides (not shown).

[0227] These results indicate that samples nucleated with LDH modified with 500 ppm to 2000 ppm cis-1,2-cyclohexanedicarboxylic acid provide improved nucleation and / or acid scavenging compared to conventional layered double hydroxides.

[0228] In addition, the dimensions of the injection molded samples were measured 72 hours after production. The shrinkage in the injection direction (SL) and perpendicular (SW) was calculated according to the standard. The results are provided in Table 1. The samples nucleated with LDH modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention showed a shrinkage of 1% to 2% after 72 hours. This is comparable to conventional layered double hydroxides.

[0229] It was found that samples comprising cis-1,2-cyclohexanedicarboxylic acid modified LDH had excellent isotropic shrinkage properties.

[0230] The LDH modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention has a nucleating effect and an acid scavenging effect on polypropylene.

[0231] In further experiments, cis-1,2-cyclohexanedicarboxylic acid-modified LDH and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH were synthesized (it should be noted that in this application, HHPA refers to cis-1,2-cyclohexanedicarboxylic acid, and NOR refers to 2,3-norbornanedicarboxylic acid or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, because 2,3-norbornanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid refer to the same compound).

[0232] The first synthesis method starts with weighing 15g LDH into a 250mL round-bottom flask, and adding 135mL demineralized water and stirring at room temperature. A dropping funnel is attached to the neck of the flask, which holds 1.5g cis-1,2-cyclohexanedicarboxylic acid and / or bicyclo [2.2.1] heptane-2,3-dicarboxylic acid dissolved in 7mL ethanol. Cis-1,2-cyclohexanedicarboxylic acid or bicyclo [2.2.1] heptane-2,3-dicarboxylic acid solution is slowly added dropwise to the stirred LDH dispersion. After adding cis-1,2-cyclohexanedicarboxylic acid and / or bicyclo [2.2.1] heptane-2,3-dicarboxylic acid solution, a cooling device is used to replace the dropping funnel, and the LDH dispersion is heated to reflux temperature. Once the reflux temperature is reached, the dispersion continues to reflux for another two hours. The dispersion was allowed to cool and the solid was filtered on a Buchner funnel with a Whatmann 42 filter of 90 mm diameter and washed 5 times with about 30 mL of demineralized water. After washing, the solid was dried at 70° C. overnight.

[0233] Alternatively, the second synthesis method starts with weighing 20g LDH into a 400mL glass beaker, and then adding 2g cis-1,2-cyclohexanedicarboxylic acid and / or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid and 200g 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 reaches 80°C, the reaction is maintained at this temperature for another two hours. After two hours, the dispersion is cooled and the solid is filtered on a Buchner funnel with a Whatmann 42 filter of 90mm diameter. After filtering, the solid is dried overnight at 70°C.

[0234] The crystallization temperature (Tc) was determined by Mettler Toledo DSC 3+ in the temperature range of 50°C to 200°C and a heating rate / cooling rate of 10°C min -1 The analysis has been performed according to EN ISO 11357-3:2018.

[0235] It was found that the sample composition comprises homopolymer polypropylene (PP) having a melt flow index of 3 in the approximate ratio of 99.800 / 0.050 / 0.100 / 0.050, 1010, 168 and LDH samples, where the amount of LDH could be increased or decreased and compensated by the amount of PP. All further crystallization temperature analyses of LDH particles containing PP measured by DSC were performed according to the settings mentioned in Table 4.

[0236] Table 4: Single screw extrusion and injection molding parameters.

[0237]

[0238] In addition, crystal analysis of LDH was performed using X-ray diffraction (XRD). The XRD was recorded on a Panalytical X-pert powder spectrometer with a PIXcal1D-Medipix3 collaborative RTMS detector using a scanning line detector. For these measurements, Cu Kα radiation was used. The goniometer step size was 0.1838° 2θ, the counting time was 5157.63 s, the scan range was 5.000-80.001, and the number of points was 408. The spectra were recorded at 45 kV and 40 mA. The focal length was 12.0 mm, the width was 0.4 mm, and the emission angle was 6.0°. The thickness of the nickel beta filter was 0.020 mm. The Soller slit was 0.02 radians. The fixed incident beam mask was 15 mm and had a width of 11.60 mm. The antiscatter slit was a fixed slit 1 / 2° with a height of 0.76 mm. The divergence slit was a fixed slit 1 / 4° with a height of 0.38 mm.

[0239] In addition, FT-IR was used for the identification of organic compounds after LDH was modified with acid. -1 The FT-IR spectra obtained with high resolution were carried out by a Thermo scientific Nicolet iS10 FT-IR spectrometer with an ATR unit. The measurement range for all samples was 4000 cm -1 Up to 600cm -1 .

[0240] To observe the distribution and morphology of the surface modification on the LDH, the samples were examined by scanning electron microscopy (SEM). The SEM images were obtained with a SU7000 device from Hitachi. The samples were measured at Condition = Vacc = 1.00 kV, Mag = "mentioned in the image", WD = "mentioned in the image". The samples were prepared by dispersing a small amount of the sample in isopropanol. About one to two drops of the dispersion were placed on an aluminum column and dried, and the column was then placed in the SEM.

[0241] Thermogravimetric analysis (TGA) of the samples was performed on a TA instruments Q500 equipped with a Pt disk to determine the total weight loss of the material up to 1000 °C or 750 °C after the method change. The data were acquired using a dynamic rate high resolution program (high resolution sensitivity 1.0, ramp 50.00 °C min -1 , resolution 4.0). In all analyses, helium was used to create an inert atmosphere. In addition, the total amount of cis-1,2-cyclohexanedicarboxylic acid on the sample can be predicted using equation I. It should be noted that cis-1,2-cyclohexanedicarboxylic acid is referred to as Q in equation I.

[0242]

[0243] The synthesized LDH according to the present invention was also analyzed by LC-MS / MS. For the analysis of cis-1,2-cyclohexanedicarboxylic acid (CAS: 610-09-3) and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (CAS: 1724-08-9), the method used included the use of multiple reaction monitoring (MRM) with negative ionization mode. UPLC: Sciex ExionLCTM, detector: SciexQTRAP 4500, software: Analyst 1.7, MultiQuant 3.0.3, analytical column: Waters CSH C18, 2.1×100 mm, 1.7 μm.

[0244] 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-naphthalene dicarboxylic acid: m / z 216 and 1,4-cyclohexane dicarboxylic acid: m / z 171.

[0245] The sample (~0.1 g) was extracted with 5 mL 1M HCl at 80°C for 4 hours. 5 mL methanol was added to the extract. The extract was vortexed, diluted with methanol and analyzed by LC-MS / MS. Quantification was performed relative to an external calibration line of known concentrations of the desired component standards. The analysis was performed in duplicate.

[0246] Extraction in 1 M HCl at 80°C proved sufficient to dissolve the inorganic fraction.

[0247] The results obtained for cis-1,2-cyclohexanedicarboxylic acid-modified LDH and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH are provided in Table 5. Entry 1 refers to an untreated LDH sample, Entry 2 refers to a sample of cis-1,2-cyclohexanedicarboxylic acid-modified LDH obtained according to the first synthesis method, Entry 3 refers to a sample of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH obtained according to the first synthesis method, Entry 4 refers to a sample of cis-1,2-cyclohexanedicarboxylic acid-modified LDH obtained according to the second synthesis method, and Entry 5 refers to a sample of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH obtained according to the second synthesis method.

[0248] Table 5: Summary of LDH sample results.

[0249] Item 1 Entry 2 Entry 3 Entry 4 Entry 5 DSC_Tc(℃) 120.9 125.6 123.0 126.1 126.9 Concentration LC / MS (%) N / A 5.75 3.65 4.80 4.30 Concentration TGA (%) N / A 9.23 N / A 6.82 N / A

[0250] Compared to the untreated LDH, it has been found that the Tc of all surface modified samples increases, which means that both methods (first method and second method) can be used to treat the surface of LDH. However, as can be seen in Table 5, compared to the samples obtained according to the first method, the samples modified with cis-1,2-cyclohexanedicarboxylic acid and the samples modified with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid according to the second method both show an increased Tc. This means that in terms of Tc, the second method can be used instead of the first method.

[0251] Concentration determinations according to both LC / MS and TGA indicated that the cis-1,2-cyclohexanedicarboxylic acid-modified LDH contained more cis-1,2-cyclohexanedicarboxylic acid when produced according to the first method rather than the second method. This observation suggests that a higher amount of cis-1,2-cyclohexanedicarboxylic acid does not necessarily mean a higher Tc. For the bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH, according to LC / MS, a higher amount of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid was found in the second method sample compared to the first method sample.

[0252] Figure 4 Decomposition curves of the LDH samples modified with cis-1,2-cyclohexanedicarboxylic acid synthesized by the first method and the LDH samples modified with cis-1,2-cyclohexanedicarboxylic acid synthesized by the second method compared with the untreated sample are shown. The most significant difference between the curves can be observed between the range of 450°C and 550°C. This loss only occurs in the LDH sample modified with cis-1,2-cyclohexanedicarboxylic acid, and can therefore be said to be caused by the treatment with cis-1,2-cyclohexanedicarboxylic acid.

[0253] It should be noted that the top line at 700°C refers to untreated LDH, the middle line at 700°C refers to cis-1,2-cyclohexanedicarboxylic acid-modified LDH synthesized using the first method, and the bottom line at 700°C refers to cis-1,2-cyclohexanedicarboxylic acid-modified LDH synthesized using the second method.

[0254] Figure 5 It is shown that the weight loss at 450°C to 550°C is caused by the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid, but not by cis-1,2-cyclohexanedicarboxylic acid at 200°C. This indicates that the cis-1,2-cyclohexanedicarboxylic acid form on the cis-1,2-cyclohexanedicarboxylic acid-modified LDH samples obtained from both (the first and second) methods provides the magnesium salt of cis-1,2-cyclohexanedicarboxylic acid. It should be noted that Figure 5The decrease in the Mg-cis-1,2-cyclohexanedicarboxylic acid curve at 200 °C is caused by the unreacted cis-1,2-cyclohexanedicarboxylic acid.

[0255] It should be noted that Figure 5 The bottom line at 400°C refers to cis-1,2-cyclohexanedicarboxylic acid, and the top line at 400°C refers to cis-1,2-cyclohexanedicarboxylic acid magnesium salt.

[0256] In addition, the XRD patterns of both the cis-1,2-cyclohexanedicarboxylic acid-modified LDH and the bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH showed that a new crystal configuration was introduced in the range of 5.9 2θ to 7.9 2θ for the cis-1,2-cyclohexanedicarboxylic acid synthesized using the first method, and a new crystal configuration was introduced at 6.8 2θ for the second method (see Figure 6 ). Figure 6 New crystals formed at 8.3 2θ for LDH treated with bicyclo[2.2.1]heptane-2,3-dicarboxylic acid are also shown, but this phenomenon only occurs when the second method is used, and the formation of such new crystals is not observed when the first method is used. No significant changes are observed in the crystal structure of the LDH samples except for a small reduction in carbonate groups visible at peaks (003) and (006). This reduction in carbonate groups is caused by the side effects of the reaction with the organic acid cis-1,2-cyclohexanedicarboxylic acid or bicyclo[2.2.1]heptane-2,3-dicarboxylic acid in both methods.

[0257] It should be noted that Figure 6 , line A refers to untreated LDH, line B refers to cis-1,2-cyclohexanedicarboxylic acid-modified LDH synthesized using the first method, line C refers to cis-1,2-cyclohexanedicarboxylic acid-modified LDH synthesized using the second method, line D refers to bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH synthesized using the first method, and line E refers to bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH synthesized using the second method.

[0258] Since Mg-cis-1,2-cyclohexanedicarboxylic acid was observed in all LDH samples modified with cis-1,2-cyclohexanedicarboxylic acid, the experiment was dedicated to treating the surface of LDH with Mg-cis-1,2-cyclohexanedicarboxylic acid instead of cis-1,2-cyclohexanedicarboxylic acid. The experiment was conducted according to the second method, in which cis-1,2-cyclohexanedicarboxylic acid was replaced by Mg-cis-1,2-cyclohexanedicarboxylic acid. Materials without Mg-cis-1,2-cyclohexanedicarboxylic acid crystals on the surface have been found, such as Figure 7The absence of a peak at 6.8 2θ confirms that the reaction with cis-1,2-cyclohexanedicarboxylic acid must be performed to synthesize the LDH surface with Mg-cis-1,2-cyclohexanedicarboxylate crystals.

[0259] It should be noted that Figure 7 , line A refers to the modified LDH according to the second method, and line B refers to the modified LDH according to the second method, in which cis-1,2-cyclohexanedicarboxylic acid is replaced by Mg-cis-1,2-cyclohexanedicarboxylic acid.

[0260] like Figure 8 As can be seen, the FT-IR spectrum shows that -1 、1550cm -1 、1600cm -1 、1690cm -1 There is a peak at 2850cm -1 Up to 2975cm -1 The peak in the range of 2850 cm -1 Up to 2975cm -1 The range begins to be associated with asymmetric and symmetric CH stretching of cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid. 1690 cm -1 Related to the amount of water in the LDH interlayer. 1600cm -1 and 1550cm -1 1480cm-1 is the peak of the carboxylate group of cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid. -1 The peaks are the vibrations of olefin hydrogen. The presence of these peaks indicates that cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid have reacted with LDH to form carboxylate groups rather than carboxylic acid groups, which should be at 1720 cm -1 To 1706cm -1 and 1440cm -1 Up to 1395cm -1 In addition, the material prepared according to the first method seems to be more inclined to have a peak at 1550cm -1 The carboxylic acid ester is formed at 1600 cm -1 A carboxylic acid ester is formed.

[0261] It should be noted that Figure 8, line A refers to untreated LDH, line B refers to cis-1,2-cyclohexanedicarboxylic acid-modified LDH synthesized using the first method, line C refers to cis-1,2-cyclohexanedicarboxylic acid-modified LDH synthesized using the second method, line D refers to bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH synthesized using the first method, and line E refers to bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH synthesized using the second method.

[0262] Figure 9 shows an SEM image of the surface treated material compared to the untreated material. Figure A shows an untreated sample, and no additional crystals are attached to the surface. Figure B is a cis-1,2-cyclohexanedicarboxylic acid modified LDH synthesized according to the first method, and a small amount of crystals are shown on the surface of the LDH. The cis-1,2-cyclohexanedicarboxylic acid modified LDH synthesized according to the second method shows more crystals, which can also be expected based on the XRD spectrum. In addition, unlike cis-1,2-cyclohexanedicarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid does not show any crystals after treatment according to the first method, but has crystals on the surface after treatment according to the second method. In addition, the XRD spectrum of bicyclo[2.2.1]heptane-2,3-dicarboxylic acid shows crystals newly formed by the second method. These crystals cannot be observed in the XRD spectrum of the first method. The combination of SEM and XRD confirmed that the surface of LDH was modified by the crystals of magnesium salts of cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, but not by a mixture of the salts and LDH.

[0263] Therefore, it can be concluded that cis-1,2-cyclohexanedicarboxylic acid-modified LDH and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid-modified LDH were successfully synthesized, in which the surface of LDH was modified with acid.

[0264] In a further experiment, the nucleation behavior of the (surface) modified LDH according to the present invention was shown. The LDH tested was a LDH modified with cis-1,2-cyclohexanedicarboxylic acid according to the present invention. The particles were synthesized using the second method of the previously described experiment. The results are shown in Table 6.

[0265] Table 6: Nucleation behavior results.

[0266]

[0267] The most significant difference in Tc is caused by the change in temperature. Compared to the LDH-free PP, which has a Tc of about 120°C, a small increase of about 2°C in Tc is observed for the sample produced at 20°C. This is already an additional increase of 1°C when the temperature is increased to 60°C during the reaction, and once the reaction is carried out at 80°C, this is already an increase of about 7°C.

[0268] Furthermore, powder or slurry of the starting LDH had no significant effect on Tc, and stirring also had no significant effect on Tc. Spray drying had an increased effect on Tc compared to samples dried in a static oven.

[0269] Fig.10 The XRD patterns of the samples mentioned in Table 6 are shown. It is noteworthy that the peak at 6.8 2θ indicative of Mg-cis-1,2-cyclohexanedicarboxylic acid is better defined for the samples showing higher Tc, while for the samples showing little or no increase in Tc, the peak is poorly defined or even absent. This indicates that a well-defined peak at 6.8 2θ leads to a higher Tc.

[0270] Fig.11 The FT-IR spectra of the samples mentioned in Table 6 are shown. -1 and 1600cm -1 The peak at 1600 cm-1 is Mg-cis-1,2-cyclohexanedicarboxylic acid on the LDH surface. The same observation was made for XRD, with higher Tc showing a peak at 1600 cm-1. -1 Samples H and I have sharp peaks and have the highest Tc compared to the other samples. For example, sample F has a peak at 1600 cm -1 There is a smaller peak at 1550cm -1 There is a (slightly) larger peak at 1550cm -1 The peak is larger, but this does not lead to a higher Tc. Therefore, it can be concluded that especially at 1600 cm -1 The peak at provides an indication of the nucleation of the material.

[0271] Therefore, it can be concluded that the modified LDH according to the present invention has a nucleating effect.

[0272] In further experiments, modified LDH particles were synthesized and analyzed using wide angle X-ray diffraction (WAXD).

[0273] WAXD is used to characterize the effects of various LDH particles according to the invention in the synthesis of polymers such as polypropylene, and if the particles contain alpha nucleating agents and / or beta nucleating agents. It should be noted that the alpha nucleating agent form is a monoclinic (square) crystal, and the beta nucleating form is a hexagonal crystal.

[0274] WAXD analysis of polypropylene comprising LDH according to the invention was carried out using a Panalytical X-pert powder spectrometer with a PIXcal1D-Medipix3 collaborative RTMS detector using a scanning line detector. For these measurements, Cu Kα radiation was used. The goniometer step size was 0.026261° 2θ, the counting time was 7.14 s, the scan range was 5.000-69.9949, and the number of points was 2475. The spectra were recorded at 45 kV and 40 mA. The focal length was 12.0 mm, the width was 0.4 mm, and the emission angle was 6.0°. The thickness of the nickel beta filter was 0.020 mm. The Soller slit was 0.02 radians. The fixed incident beam mask was 15 mm and had a width of 11.60 mm. The antiscatter slit was a fixed slit 1 / 2° with a height of 0.76 mm. The divergence slit was a fixed slit 1 / 4° with a height of 0.38 mm.

[0275] Table 7 shows various LDH particles according to the present invention.

[0276] Table 7: List of molecules tested and reacted with LDH.

[0277] acid Code Tc average value (℃) none N / A ±120 <![CDATA[DHT TM -4V]]> N / A 119.85 benzoic acid Benzoic 120.05 cis-1,2-cyclohexanedicarboxylic acid HHPA 125.35 2,6-Naphthalenedicarboxylic acid NAP 122.50 Bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (2,3-norbornanedicarboxylic acid) NOR 126.20 Pimelic acid PIM 123.50 Phenylphosphonic acid PPA 125.75 Benzene-1,3,5-tricarboxylic acid (Trimesic acid) TRI 121.90 1,3,5-Triazine-2,4,6-triol (cyanuric acid) CYAN 121.35 4-Aminobenzoic acid PABA 121.20 1,4-Cyclohexanedicarboxylic acid CDA 121.85 2-Carboxyethyl(phenyl)phosphinic acid CEPPA 120.65 4-Propylcyclohexanecarboxylic acid PCCA 120.85 Butylphosphonic acid BPA 120.20 4-Toluenesulfonic acid TSA 120.10

[0278] It should be noted that DHT TM -4V is a hydrotalcite used as an acid scavenger in the conventional synthesis of polypropylene.

[0279] Fig.12 XRD patterns of seven molecules with nucleation effects are shown. All patterns, except for pimelic acid and 1,4-cyclohexanedicarboxylic acid, show a newly introduced crystal, which is also observed for cis-1,2-cyclohexanedicarboxylic acid-modified LDH. In addition to the carbonate groups inserted into the LDH particles, the peaks of 003, 006 and 009 do not appear to repeat. Therefore, it can be concluded that no molecules are inserted.

[0280] In addition, it was found that pimelic acid and 1,4-cyclohexanedicarboxylic acid showed nucleation. It is expected that LDH is coated with an organic layer of pimelic acid or 1,4-cyclohexanedicarboxylic acid rather than being covered by Mg crystals because Fig.13 The FT-IR spectra in F and H show the presence of organic molecules. In addition, the FT-IR spectrum shows -1 or 1600cm -1 There are carboxylate groups at the locations of the untreated material and the PPA treated material (PPA is a phosphonic acid derivative and refers to phenylphosphonic acid) with a phosphate peak at about 1150 cm -1 (See Fig.13 ).

[0281] Table 8 shows the results of PSD, BET, molecular concentration on the LDH surface and the acid scavenging function of the material. After modification with organic acid, no significant changes occurred in terms of PSD. After modification with organic acid, the BET of all materials increased, indicating that the surface was modified due to the reaction. The residual amount of organic acid or derivative on the surface of LDH according to the present invention is shown in Table 8, and in many cases is less than 10% of the initial amount added to the reaction. This indicates that not all organic acids are used during the reaction, or not all organic acids or derivatives are attached to the surface. For phenylphosphonic acid and benzene-1,3,5-tricarboxylic acid, it was found that the surface treatment reaction was basically completed.

[0282] In addition, the nucleation effect of the LDH particles according to the present invention as well as their acid scavenging function are retained. Once modified with an organic acid, the acid scavenging titration results in a decrease in function from 2.4 mol chloride / mol LDH to 1.86 mol chloride / mol LDH. It was found that the LDH particles according to the present invention can scavenge at least 1.86 mol chloride / mol LDH and therefore have an acid scavenging function. Compared with commercially available DHT, which is widely used as an acid scavenger, TM Compared to -4V, the modified LDH particles according to the invention lose up to 15% of their acid scavenging function, in exchange for which they also have a nucleating effect.

[0283] Table 8: Summary of specifications of modified LDH.

[0284]

[0285] *The concentration of PIM decreases over time, which has been tested by overnight analysis. Therefore, the actual concentration of PIM is expected to be higher than the measured value.

[0286] The WAXD spectra of LDH modified with cis-1,2-cyclohexanedicarboxylic acid and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid were Fig.14 . This analysis shows that polypropylene without LDH contains a small amount of β-nucleation and a majority of α-nucleation. Adding cis-1,2-cyclohexanedicarboxylic acid modified LDH to polypropylene reduces β-nucleation and increases α-nucleation, and thus cis-1,2-cyclohexanedicarboxylic acid modified LDH can be considered an α-nucleator. Bicyclo[2.2.1]heptane-2,3-dicarboxylic acid modified LDH additives even further reduce β-nucleation, but increase α-nucleation, also like cis-1,2-cyclohexanedicarboxylic acid. Thus bicyclo[2.2.1]heptane-2,3-dicarboxylic acid modified LDH can also be considered an α-nucleator.

[0287] It was found that the Tc of the polypropylene containing the modified LDH according to the present invention was increased by at least 1.5°C compared to the Tc of the polypropylene containing the untreated LDH. In addition, it was found that the modified LDH according to the present invention has acid scavenging and nucleating effects. In further experiments, LDH particles with different specifications were used. The modified LDH particles were synthesized according to a previously disclosed method. In the method, LDH particles were synthesized to have zinc, different magnesium aluminum ratios, BET and PSD or aspect ratios.

[0288] The specific surface area of ​​the samples was determined using a Quantachrome Monosorb surface area analyzer. 2 The sample was prepared by degassing at 90°C for 15 minutes under a (30 / 70) flow. After degassing, the sample holder was immersed in liquid nitrogen for several minutes. Subsequently, the sample holder was heated to room temperature by an on-board heater. The desorbed He / N 2 The amount of thermal conductivity is measured by a thermal conductivity detector, and the signal intensity is converted into specific surface area / sample mass (unit: m 2 g -1 ).

[0289] In addition, the particle size distribution (PSD) was determined using Microtrac S3500. The sample was dispersed in ultrapure water and methanol and homogenized by ultrasound with Cole Palmer at 38% amplitude for 5 minutes, and then about 1 mL was added to the sample chamber.

[0290] LDH particles with different specifications were reacted with cis-1,2-cyclohexanedicarboxylic acid. The DSC of various samples is provided in Table 9.

[0291] Table 9: Summary of results.

[0292]

[0293] It can be concluded that the above modified LDH particles show nucleation as well as acid scavenging properties, wherein the modified LDH particle sample with high BET and low PSD shows improved nucleation.

[0294] Furthermore, it can be concluded that the modified LDH particles according to the present invention provide efficient and effective nucleation and acid scavenging functions.

[0295] The invention is in no way limited to the preferred embodiments and / or experiments thereof described above. The rights sought for protection are defined by the appended claims, within the scope of which numerous modifications are contemplated.

Claims

1. A modified layered double hydroxide (LDH) according to 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 ： M 1 and M 2 Each is independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; in particular, each is independently a divalent metal selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M 3 is a trivalent metal such as Al and / or Fe; in particular Al; and A n- is one or more intercalated n-valent anions, where m, x, y, and z are values ​​in the range represented by: 0≤m<2 0<x≤0.5 0.5≤y+z≤1, Also included is a modified outer layer, wherein the outer layer is modified with an organic acid derivative or a salt thereof.

2. The modified LDH according to claim 1, wherein the organic acid derivative or its salt is one or more selected from the group consisting of: monocarboxyl C 1-12 Alkyl or dicarboxyl C 1-12 Alkyl, C 1-12 Alkylsulfonyl hydroxide, C 1-12 Alkylphosphonic acid, di-C 1-12 Alkylphosphonates, N-substituted isocyanurates, monocarboxylic C 3-8 Cycloalkanes, dicarboxyl C 3-8 Cycloalkanes or tricarboxyl C 3-8 Cycloalkanes, organic acid derivatives according to formula (II), in: k is an integer from 1 to 3; n is an integer from 0 to 5; A represents a cycloalkyl group, an aryl group or a heteroaryl group; L represents a direct bond or NH; R 1 are independently selected from hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amide, C 1-6 One or more of alkyl, hydroxyphosphoryl, Het or Ar; Ar represents an aryl group; Het represents a heterocycle; R 2 Indicates C or P or S; Where R 3 is a hydroxyl group and is present when L represents a direct bond, or wherein R 3 is hydroxyl or, when L represents NH, is C 1-6 Alkyl; and Where R 4 Is hydroxyl or C 1-6 alkylcarbonyl, and when R 2 It exists when P is expressed, or when R 4 is a double bond oxygen and when R 2 Indicates that S exists.

3. The modified LDH according to claim 2, wherein formula II is represented by formula III, The modified LDH according to claim 2 , wherein A is independently selected from an aryl group or a heteroaryl group.

5. The modified LDH according to any one of the preceding claims, 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, (1R,2S)-2-methoxycarbonylcyclohexanecarboxylic acid, 1,3,5-tris(2,2-dimethylpropionylamino)benzene, 2,6-naphthalene dicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxy Pyrimidine-4-carboxylic acid, 4-pyridinecarboxylic acid, benzene-1,3,5-tricarboxylic acid, 4-(benzoylamino)benzoic acid, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthoic 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.

6. The modified LDH according to any one of the preceding claims, 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-naphthalene dicarboxylic acid.

7. The modified LDH according to any one of the preceding claims, wherein the organic acid derivative or salt thereof is cis-1,2-cyclohexanedicarboxylic acid. 8 . The modified LDH according to claim 7 , wherein the modified LDH comprises an X-ray diffraction peak in the range of 4° 2θ to 9° 2θ. 9 . The modified LDH according to claim 1 or 2 , wherein the organic acid derivative or the salt thereof comprises 1,3,5-triazine-2,4,6-triol.

10. The modified LDH according to claim 1 or 2, wherein the organic acid derivative or its salt comprises monocarboxycyclohexane, dicarboxycyclohexane or tricarboxycyclohexane, preferably wherein the monocarboxycyclohexane, dicarboxycyclohexane or tricarboxycyclohexane is 1,4-cyclohexanedicarboxylic acid and / or 4-propylcyclohexanecarboxylic acid.

11. A modified LDH according to any one of the preceding claims, wherein A n- It is one or more selected from the group consisting of carbonate ion, nitrate ion, sulfate ion or a combination thereof.

12. A modified LDH according to any one of the preceding claims, wherein A n- It is the carbonate ion.

13. Particles comprising a modified LDH according to any one of the preceding claims.

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

15. A resin composition comprising a resin and the particles according to claim 13 or 14, the particles being in the range of 1 ppm to 10000 ppm, preferably 50 ppm to 5000 ppm, more preferably 100 ppm to 3000 ppm. 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 a liquid and particles according to claim 13 or 14 in the range of 1 ppm to 10000 ppm, preferably 50 ppm to 5000 ppm, more preferably 100 ppm to 3000 ppm.

18. A method for producing a modified LDH according to any one of claims 1 to 12, comprising contacting a layered double hydroxide according to formula (I) with an organic acid derivative or a salt thereof, [[[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 ： M 1 and M 2 Each is independently a divalent metal selected from the group consisting of Mg, Zn, Ca, Sr, Cu, Fe, Mn, Co, Ni, Sn, Pb, Cd and Ba; in particular, each is independently a divalent metal selected from the group consisting of Mg, Zn, Cu, Fe, Mn, Co, Ni and Cd; M 3 is a trivalent metal such as Al and / or Fe; in particular Al; and A n- is one or more intercalated n-valent anions, where m, x, y, and z are values ​​in the range represented by: 0≤m<2 0<x≤0.5 0.5≤y+z≤1.

19. The method according to claim 18, wherein the organic acid derivative or its salt is one or more selected from the group consisting of: monocarboxyl C 1-12 Alkyl or dicarboxyl C 1-12 Alkyl, C 1-12 Alkylsulfonyl hydroxide, C 1-12 Alkylphosphonic acid, di-C 1-12 Alkylphosphonates, organic acid derivatives according to formula (II), in: k is an integer from 1 to 3; n is an integer from 0 to 5; A represents a cycloalkyl group, an aryl group or a heteroaryl group; L represents a direct bond or NH; R 1 are independently selected from hydroxyl, carboxyl, C 1-6 Alkoxycarbonyl, arylcarbonylamino, amino, amide, C 1-6 One or more of alkyl, hydroxyphosphoryl, Het or Ar; Ar represents an aryl group; Het represents a heterocycle; R 2 Indicates C or P or S; Where R 3 is a hydroxyl group and is present when L represents a direct bond, or wherein R 3 is hydroxyl or, when L represents NH, is C 1-6 Alkyl; and Where R 4 Is hydroxyl or C 1-6 alkylcarbonyl, and when R 2 It exists when P is expressed, or when R 4 is a double bond oxygen and when R 2 Indicates that S exists.

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

21. The method according to any one of claims 19 to 20, wherein the organic acid derivative is one or more 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-naphthalene dicarboxylic acid, benzoic acid, pimelic acid, phenylphosphonic acid, 2,6-dihydroxypyrimidine 4-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, benzene-1,3,5-tricarboxylic acid, 4-(benzoylamino)benzoic acid, disodium malonate, sodium acetate, 1-octanesulfonic acid, 2,3-pyridinedicarboxylic acid, 2-carboxyethyl(phenyl)phosphinic acid, 2-naphthoic 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.

22. Use of the modified 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 in the polymer industry, wherein the polymer industry includes the synthesis of polymers, the production of polymer compositions, and the conversion of polymer compositions into consumables.

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

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

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

27. The use according to any one of claims 26, wherein the increased crystallization temperature is increased by 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, most preferably at least 5°C according to EN ISO 11357-3:2018.

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, most preferably at least 125°C.

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