Organic-inorganic hybrid polyolefin composite and method for producing the same

Abstract

The present disclosure relates to an organic-inorganic hybrid polyolefin composite and a method for preparing the same.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2020-0159261, filed on November 24, 2020, and Korean Patent Application No. 10-2021-0161559, filed on November 22, 2021, the disclosures of which are incorporated herein by reference in their entirety.

[0003] This disclosure relates to an organic-inorganic hybrid polyethylene composite material and its preparation method. Background Technology

[0004] Lithium-ion battery separators (LiBS) are one of the key materials that play a role in determining the battery's lifespan, efficiency, and stability.

[0005] In particular, as it is an important material that makes a significant contribution to battery performance, it requires a variety of desirable properties, with representative desirable properties being chemical stability, thickness, porosity, pore size, mechanical strength, wettability, dimensional stability, shutdown, and thermal shrinkage.

[0006] Generally, LiBS is manufactured by appropriately blending inexpensive polyethylene and polypropylene that meet certain chemical stability and mechanical properties. However, due to the limitations of olefin polymers, it is difficult to meet the required properties such as wettability, dimensional stability, shut-off properties, and thermal shrinkage. To address this issue, various inorganic materials and additives are added during the manufacture of LiBS, but it remains difficult to resolve the deterioration of physical properties over time due to mixing, dispersion, and migration of olefin polymers.

[0007] Therefore, in the manufacture of lithium-ion battery separators (LiBS), there is a continuous need to develop a polyolefin material that can solve the problems of mixing and dispersing inorganic materials and olefin polymers, as well as migration problems, while controlling excellent mechanical properties, wettability, dimensional stability, shut-off properties, and low thermal shrinkage. Summary of the Invention

[0008] Technical issues

[0009] This disclosure provides an organic-inorganic hybrid polyolefin composite material and a method for preparing the same.

[0010] Technical solution

[0011] In one embodiment of this disclosure, an organic-inorganic hybrid polyolefin composite material is provided, comprising a polyolefin and a non-porous inorganic material bonded to at least a portion of the polyolefin, wherein the content of the non-porous inorganic material is 0.4% by weight or more based on the total weight of the organic-inorganic hybrid polyolefin composite material.

[0012] In another embodiment of this disclosure, a method for preparing an organic-inorganic hybrid polyolefin composite material according to the above embodiments is provided.

[0013] In another embodiment of this disclosure, a membrane material is provided that is manufactured using an organic-inorganic hybrid polyolefin composite material according to the above embodiments.

[0014] The terminology used herein is for describing specific implementations only and is not intended to limit the invention.

[0015] Unless the context clearly indicates otherwise, the singular form also includes the plural form.

[0016] In this disclosure, the terms “comprising,” “including,” or “having” are used to describe the features, numbers, steps, components, or combinations thereof, and do not exclude the addition of one or more other features, numbers, steps, components, or combinations thereof.

[0017] The terms “about” or “substantially” are intended to mean close to a specified value or range with permissible error, and are intended to prevent the accurate or absolute values ​​disclosed for the purpose of understanding the invention from being used illegally or unfairly by any unreasonable third party.

[0018] Additionally, as used herein, when referring to a layer or element being formed “on” a layer or element, the layer or element may be formed directly on said layer or element, or other layers or elements may be formed separately between layers, on the body, or on the substrate.

[0019] Furthermore, in this statement, (co)polymer is intended to include homopolymers and copolymers.

[0020] Unless otherwise defined herein, “copolymer” can mean block copolymer, random copolymer, graft copolymer or alternating copolymer, and “polymer” means block copolymer, random copolymer, graft copolymer or alternating copolymer.

[0021] Furthermore, as used herein, “parts by weight” refers to a relative concept of the weight ratio of the remaining materials to the weight of a particular material. For example, in a mixture containing 50 grams of material A, 20 grams of material B, and 30 grams of material C, based on 100 parts by weight of material A, the amounts of materials B and C are 40 parts by weight and 60 parts by weight, respectively.

[0022] Meanwhile, "wt%" refers to an absolute concept that expresses the weight of a specific material as a percentage based on the total weight. In the above mixture, based on 100% of the total weight of the mixture, the contents of materials A, B, and C are 50 wt%, 20 wt%, and 30 wt%, respectively.

[0023] Since this invention can be modified and has various forms, specific embodiments are shown by way of example and will be described in detail. However, it is not intended to limit the invention to the specific forms disclosed, and it should be understood that the invention includes all modifications, equivalents, and substitutions within the spirit and scope of the invention.

[0024] The present invention will now be described in detail.

[0025] According to one aspect of this disclosure, an organic-inorganic hybrid polyolefin composite material is provided, which can solve the problems of mixing and dispersion of inorganic materials and olefin polymers as well as migration problems, while controlling mechanical properties, wettability, dimensional stability, shut-off properties, low thermal shrinkage rate and other functions when manufacturing lithium-ion battery separators (LiBS).

[0026] In particular, the organic-inorganic hybrid polyolefin composite material comprises a polyolefin and a non-porous inorganic material bonded to at least a portion of the polyolefin, wherein the content of the non-porous inorganic material is 0.4% by weight or more, or 0.4% by weight to 12% by weight, based on the total weight of the organic-inorganic hybrid polyolefin composite material.

[0027] Specifically, the polyolefin can be a homopolymer or copolymer of olefin monomers selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. For example, it can be a homopolymer of olefin monomers, such as a homopolymer of ethylene or propylene, i.e., polyethylene or polypropylene. More preferably, it can be polyethylene.

[0028] Furthermore, polyethylene includes low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), etc., and may be one or a mixture of two or more of them. In particular, the polyethylene is preferably high-density polyethylene with high crystallinity and high melting point. However, if necessary, the polyethylene may be a mixture of high-density polyethylene and low-density polyethylene.

[0029] The organic-inorganic hybrid polyolefin composite material disclosed herein comprises a nonporous inorganic material bonded to at least a portion of a polyolefin, and the aforementioned polyolefin.

[0030] Specifically, based on the total weight of the organic-inorganic hybrid polyolefin composite material, the content of the non-porous inorganic material is 0.4% by weight or more. Preferably, the content of the non-porous inorganic material can be 0.42% by weight or more, 0.43% by weight or more, 0.44% by weight or more, 0.45% by weight or more, 0.46% by weight or more, 0.47% by weight or more, 0.48% by weight or more, 0.49% by weight or more, or 0.5% by weight or more. When the content of the non-porous inorganic material is less than 0.4% by weight, it cannot function as a filler for bonding with the polyolefin, nor can it compensate for the mechanical properties of the polyolefin. However, in order to prevent the deterioration of the mechanical properties of the organic-inorganic hybrid polyolefin composite material, the content of the non-porous inorganic material can be 12% by weight or less. Preferably, the content is 10% by weight or less, 9.8% by weight or less, 9.5% by weight or less, 9% by weight or less, 8.8% by weight or less, 8.6% by weight or less, 8.5% by weight or less, 8.4% by weight or less, 8.3% by weight or less, 8.2% by weight or less, 8.1% by weight or less, or 8% by weight or less. For example, when the content of the non-porous inorganic material is too high, such as exceeding 12% by weight, it acts as an impurity rather than a filler in the organic-inorganic hybrid polyolefin composite material, thereby preventing the formation of the polymer matrix and thus reducing mechanical properties. Therefore, in order to ensure the excellent mechanical properties of the organic-inorganic hybrid polyolefin composite material to be prepared, the content of the non-porous inorganic material is preferably within the above-mentioned range.

[0031] In particular, the inorganic materials disclosed herein can be non-porous materials with smooth surfaces completely free of pores, or materials with some irregularities (which cannot be considered as pores on the surface). The specific surface area of ​​the non-porous inorganic material can be 100 m². 2 / g or less, or 2 m 2 / g to 100 m 2 / g. Specific surface area is a value calculated using the well-known Brunauer-Emmett-Teller (BET) equation and can also be a value measured according to ISO 9277 of the International Organization for Standardization.

[0032] Specifically, the specific surface area of ​​non-porous inorganic materials can be 95 m². 2 / g or less, 85 m 2 / g or less, 80 m 2 / g or less, 70 m 2 / g or less, 60 m 2 / g or less, 55 m 2 / g or less, 50 m 2 / g or less, 45 m 2 / g or less, 40 m 2 / g or less, 35m2 / g or less, 30 m 2 / g or less, 25 m 2 / g or less, 20 m 2 / g or less or 18 m 2 / g or less. In particular, non-porous inorganic materials can meet the above-mentioned specific surface area requirements to ensure excellent mechanical properties, while being included in polyolefin composites within the above-mentioned content range without cracking during olefin polymerization. However, considering the actual porosity of inorganic materials, the specific surface area can be 2 m². 2 / g or more, 4 m 2 / g or more, 6 m 2 / g or more, 8 m 2 / g or more, 10 m 2 / g or more or 12m 2 / g or more.

[0033] In addition, nonporous inorganic materials can be fine particles with a size of 30 nm to 2 μm, specifically, particles with a size of 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, or 100 nm or more, and less than 1.8 μm, less than 1.5 μm, less than 1.2 μm or less.

[0034] Furthermore, nonporous inorganic materials can have uniform particle size and spherical or round shapes.

[0035] Specifically, the nonporous inorganic material may contain one or more hydroxyl or siloxane groups on its surface, preferably highly reactive hydroxyl and siloxane groups on the surface. For example, the amount of hydroxyl groups on the surface of the inorganic material is preferably from about 0.1 mmol / g to about 10 mmol / g, more preferably from about 0.5 mmol / g to about 5 mmol / g.

[0036] Furthermore, the non-porous inorganic material can be one or a mixture of two or more of the following: alumina, magnesium oxide, zirconium oxide, zeolite, and silica. For example, the non-porous inorganic material can be silica, silica-alumina, or silica-magnesium oxide, preferably silica.

[0037] For example, when the non-porous inorganic material is silica, it can be synthesized using the Stover method (Stober, W. and A. Fink, Bohn, Journal of Colloid and Interface Science, 1986, 26, 62). According to this method, tetraethyl orthosilicate (TEOS), a silica precursor, is hydrolyzed in a water-alkaline solvent with an added alkaline catalyst to form silica nanoparticles. Ammonia (NH3), sodium hydroxide (NaOH), etc., can be used as catalysts here.

[0038] Furthermore, in the organic-inorganic hybrid polyolefin composite material disclosed herein, the non-porous inorganic material is chemically bonded to at least a portion of the aforementioned polyolefin. Specifically, at least one of covalent and coordinate bonds can be formed. Here, a covalent bond is a bond formed when two atoms share an electron pair, while a coordinate bond is a bond formed when the lone pair of electrons of one atom is shared with another atom.

[0039] Specifically, the aforementioned chemical bonds can be formed by substituents such as hydroxyl or siloxane groups present on the surface of nonporous inorganic materials.

[0040] In the organic-inorganic hybrid polyolefin composite material disclosed herein, the non-porous inorganic material can be directly bonded to at least a portion of the aforementioned polyolefin, or bonded through at least one of the catalytically active component and a co-catalyst from the polymerization process. For example, the non-porous inorganic material can form chemical bonds with at least one of the catalytically active component and the co-catalyst through substituents such as hydroxyl or siloxane present on its surface, and then directly form chemical bonds with at least a portion of the aforementioned polyolefin. For example, in the organic-inorganic hybrid polyolefin composite material, chemical bonds can be formed with the co-catalyst on the surface of the non-porous inorganic material, chemical bonds can be formed between the co-catalyst and the catalytically active component, and covalent bonds can be formed through coordination bonds and the polymerization reaction of the catalytically active component with the olefin monomer (such as ethylene).

[0041] On the other hand, the ability to mold organic-inorganic hybrid polyolefin composites into sheets is not critical, but for applications requiring strong physical properties, such as lithium-ion battery separators (LiBS), high molecular weight is preferred. In this regard, the weight-average molecular weight of the organic-inorganic hybrid polyolefin composite can be approximately 300,000 g / mol or higher, or approximately 300,000 g / mol to approximately 1,500,000 g / mol. More preferably, the weight-average molecular weight of the organic-inorganic hybrid polyolefin composite can be approximately 300,500 g / mol or higher, approximately 300,800 g / mol or higher, approximately 301,000 g / mol or higher, or approximately 301,300 g / mol or higher. However, in terms of actual processability, if molded into sheets, the weight average molecular weight of organic-inorganic hybrid polyolefin composites can be less than about 1,400,000 g / mol, less than about 1,250,000 g / mol, less than about 1,100,000 g / mol, less than about 1,000,000 g / mol, less than about 800,000 g / mol, less than about 600,000 g / mol, or less than about 500,000 g / mol.

[0042] Furthermore, the number average molecular weight of the organic-inorganic hybrid polyolefin composite material can be about 85,000 g / mol or more, or about 85,000 g / mol to about 150,000 g / mol, preferably about 86,000 g / mol or more, about 86,500 g / mol or more, about 87,000 g / mol or more, or about 87,500 g / mol or more. Additionally, the number average molecular weight of the organic-inorganic hybrid polyolefin composite material can be about 140,000 g / mol or less, about 125,000 g / mol or less, about 110,000 g / mol or less, about 105,000 g / mol or less, about 100,000 g / mol or less, about 98,000 g / mol or less, or about 95,000 g / mol.

[0043] Furthermore, the molecular weight distribution (Mw / Mn) of the organic-inorganic hybrid polyolefin composite material can be from 2.5 to 4.5, specifically 2.7 or more, 2.85 or more, 3 or more, or 3.2 or more, and 4.3 or less, 4.0 or less, 3.8 or less, or 3.5 or less. In particular, when preparing the organic-inorganic hybrid polyolefin composite material as a lithium-ion battery separator (LiBS), it is preferable to keep the molecular weight distribution within the above range in order to ensure excellent mechanical properties.

[0044] The weight-average molecular weight, number-average molecular weight, and molecular weight distribution of organic-inorganic hybrid polyolefin composites can be obtained by measuring the weight-average molecular weight, number-average molecular weight, and molecular weight distribution of polystyrene conversion using the GPC method.

[0045] For example, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of organic-inorganic hybrid polyolefin composites can be measured by gel permeation chromatography (GPC) and calculated by the polystyrene conversion method described below. Furthermore, the molecular weight distribution (Mw / Mn) of organic-inorganic hybrid polyolefin composites can be obtained by dividing the weight-average molecular weight by the number-average molecular weight.

[0046] Specifically, a Waters PL-GPC220 gel permeation chromatograph can be used as the instrument, employing a Polymer Laboratories PLgel MIX-B 300 mm column. The evaluation temperature can be 160 °C, 1,2,4-trichlorobenzene can be used as the solvent, and the flow rate is 1 mL / min. Each organic-inorganic hybrid polyolefin composite sample can be pretreated by dissolving it in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160 °C for 10 hours using a GPC analyzer (PL-GP220), providing a sample at a concentration of 10 mg / 10 mL in 200 μL increments. Mw and Mn can be obtained using a calibration curve derived from polystyrene standards. Nine polystyrene standards with molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, and 10000000 g / mol can be used.

[0047] Furthermore, when measured according to ASTM D 638 of the American Society for Testing and Materials, the Young's modulus of organic-inorganic hybrid polyolefin composites can be above approximately 250 MPa, above approximately 280 MPa, above approximately 285 MPa, above approximately 290 MPa, above approximately 295 MPa, above approximately 300 MPa, or above approximately 305 MPa. Conversely, the Young's modulus can be below approximately 800 MPa, below approximately 750 MPa, below approximately 700 MPa, below approximately 650 MPa, below approximately 600 MPa, below approximately 550 MPa, or below approximately 500 MPa. In particular, for applications requiring strong physical properties, such as lithium-ion battery separators (LiBS), organic-inorganic hybrid polyolefin composites preferably have a high Young's modulus. In this regard, the Young's modulus can be above 285 MPa, above 290 MPa, above 295 MPa, above 300 MPa, or above 305 MPa.

[0048] Furthermore, organic-inorganic hybrid polyolefin composites can exhibit wettability, meaning a water contact angle (degrees, °) of less than 45°, or between 15° and 45°, as measured by ASTM D 5946 of the American Society for Testing and Materials. Preferably, the water contact angle can be less than 44°, less than 43°, less than 42°, or less than 40°. As mentioned above, organic-inorganic hybrid polyolefin composites have a low contact angle, which means good wettability to water. This is advantageous because, when applied to lithium-ion battery separators (LiBS), the electrolyte can easily penetrate. In terms of wettability, a lower water contact angle is better. However, it can be greater than 18°, greater than 20°, greater than 25°, or greater than 30°, depending on the water-repellent properties of the polymer membrane itself.

[0049] Furthermore, organic-inorganic hybrid polyolefin composites exhibit excellent dimensional stability, with a heat shrinkage rate (90°C, 60 minutes) of less than 5% or less than 3%. For example, according to ASTM D 5946 of the American Society for Testing and Materials, membrane specimens were prepared using organic-inorganic hybrid polyolefin composites. Then, when the membrane specimens were placed at 140°C for 1 hour and the area before and after placement was measured, the area of ​​the membrane specimen after placement was likely to be more than 95%, 96%, or 97% of the area before placement.

[0050] According to another embodiment of this disclosure, a method for preparing the above-described organic-inorganic hybrid polyethylene composite material is provided.

[0051] In particular, in this disclosure, when manufacturing lithium-ion battery separators (LiBS), the olefin polymer is prepared by combining a catalyst with inorganic materials. This solves the problems of mixing and dispersing inorganic materials and olefin polymers, as well as migration issues, and allows for the preparation of organic-inorganic hybrid polyethylene composite materials with controllable mechanical properties, wettability, dimensional stability, shut-off properties, and low thermal shrinkage, depending on the content of the inorganic material.

[0052] The method for preparing the organic-inorganic hybrid polyethylene composite material disclosed herein includes the step of polymerizing olefin monomers in the presence of a catalyst composition, wherein the catalyst composition comprises a catalytically active component consisting of at least one first metallocene compound represented by the following chemical formula 1 and at least one second metallocene compound selected from compounds represented by the following chemical formula 2, which is incorporated into a nonporous inorganic material.

[0053] [Chemical Formula 1]

[0054] (Cp 1 R a ) n (Cp 2 R b M 1 Q1 3-n

[0055] In chemical formula 1,

[0056] M 1 It is a group 4 transition metal;

[0057] Cp 1 and Cp 2 They may be identical or different from each other, and each independently is selected from any one of the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl; wherein they are unsubstituent or have C-substituted groups. 1-20 hydrocarbon;

[0058] R a and R b They may be the same or different from each other, and each is independently hydrogen or carbon. 1-20 Alkyl, C 1-20 Alkoxy, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 6-20 aryloxy group, C 2-20 alkenyl, C 7-40 Alkyl, C 7-40 Aryl alkyl, C 8-40 Aryl or C 2-10 Alkyne group, condition is R a and R b At least one of them is not hydrogen;

[0059] Q 1 It is halogen, C 1-20 Alkyl, C 2-20 alkenyl, C 7-40 Alkyl, C 7-40 Aryl alkyl, C 6-20 Aryl, C with or without substituents 1-20 Alkyl groups, amino groups with or without substituents, C 2-20 Alkoxyalkyl, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy; and

[0060] n is 1 or 0;

[0061] [Chemical Formula 2]

[0062]

[0063] In chemical formula 2,

[0064] R 1 To R 17 They may be the same or different from each other, and each is independently hydrogen, halogen, or carbon.1-20 Alkyl, C 2-20 alkenyl, C 6-20 Aryl, C 7-20 alkylaryl or C 7-20 Aryl groups;

[0065] L is C 1-10 Straight-chain or branched alkylene groups;

[0066] D is -O-, -S-, -N(R)-, or -Si(R)(R')-, where R and R' are the same or different from each other, and are independently hydrogen, halogen, or carbon. 1-20 Alkyl, C 2-20 alkenyl or C 6-20 Aryl;

[0067] A represents hydrogen, halogens, and C. 1-20 Alkyl, C 2-20 alkenyl, C 6-20 Aryl, C 7-20 Alkyl, C 7-20 Aryl alkyl, C 1-20 Alkoxy, C 2-20 Alkoxyalkyl, C 2-20 Heterocyclic alkyl or C 5-20 Mixed aromatics;

[0068] Q is carbon, silicon, or germanium;

[0069] M 2 It is a Group 4 transition metal; and

[0070] X 1 and X 2 They may be the same as or different from each other, and each is independently a halogen, C 1-20 Alkyl, C 2-20 alkenyl, C 6-20 Aryl, nitro, amide, C 1-20 Alkyl silyl, C 1-20 Alkoxy or C 1-20 Sulfonic acid group.

[0071] These substituents are described in more detail below.

[0072] A hydrocarbon group is a monovalent functional group that removes hydrogen from a hydrocarbon compound, and can include alkyl, alkenyl, alkynyl, aryl, aralkyl, aryl-alkenyl, arylynyl, alkylaryl, alkenylaryl, alkynylaryl, etc. C 1-30 The hydrocarbon group can be C 1-20 Or C 1-10 Hydrocarbon group. For example, the hydrocarbon group can be a straight-chain, branched, or cyclic alkyl group. More specifically, C 1-30The hydrocarbon group can be a straight-chain, branched, or cyclic alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and cyclohexyl; or an aryl group, such as phenyl, biphenyl, naphthyl, anthraceneyl, phenanthrene, or fluorenyl. Furthermore, it can be an alkylaryl group, such as methylphenyl, ethylphenyl, methylbiphenyl, and methylnaphthyl, or an arylalkyl group, such as benzyl, phenethyl, biphenylmethyl, and naphthylmethyl. It can also be an alkenyl group, such as allyl, vinyl, propenyl, butenyl, and pentenyl.

[0073] The hydroxyl group is the functional group in which the hydrocarbon group is bonded to oxygen. Specifically, C 1-30 The hydroxyl group can be C 1-20 Or C 1-10 Hydroxyl group. For example, the hydroxyl group can be a straight-chain, branched, or cyclic alkyl group. More specifically, C 1-30 The hydrocarbon group can be a straight-chain, branched, or cyclic alkoxy group, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, and cyclohexoxy; or an aryloxy group, such as phenoxy and naphthoxy.

[0074] An alkyl group is a functional group in which at least one hydrogen atom of a hydrocarbon group is replaced by at least one alkyl oxygen atom. Specifically, C 2-30 The hydrocarbon group can be C 2-20 Or C 2-15 Hydroxyl group. For example, the hydroxyl group can be a straight-chain, branched, or cyclic alkyl group. More specifically, C 2-30 The alkyl group can be an alkoxyalkyl group, such as methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl and tert-butoxyhexyl; or an aryloxyalkyl group, such as phenoxyhexyl.

[0075] Hydrocarbon (oxy)silyl groups are functional groups in which one to three hydrogens of -SiH3 are replaced by one to three hydrocarbon groups or hydrocarbon oxygen groups. Specifically, C 1-30 Hydrocarbon (oxy)silyl groups can be C 1-20 C 1-15 C 1-10 Or C 1-5 Hydrocarbon (oxy)silyl group. More specifically, C 1-30 The alkyl(oxy)silyl group can be an alkylsilyl group, such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl; an alkoxysilyl group, such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; or an alkoxyalkylsilyl group, such as methoxydimethylsilyl, dimethoxymethylsilyl or dimethoxypropylsilyl.

[0076] C 1-20 A silyl hydrocarbon group is a functional group in which at least one hydrogen atom of the hydrocarbon group is replaced by a silyl group. This silyl group can be -SiH3 or a hydrocarbon (oxy)silyl group. Specifically, C 1-20 The silyl group can be C 1-15 Or C 1-10 Silicylalkyl group. More specifically, C 1-20 The silyl group can be silylalkyl, such as -CH2-SiH3; alkylsilylalkyl, such as methylsilylmethyl, methylsilylethyl, dimethylsilylmethyl, trimethylsilylmethyl, dimethylpropylsilylmethyl, diethylsilylmethyl, or dimethylpropylsilylmethyl; or alkoxysilylalkyl, such as dimethylethoxysilylpropyl.

[0077] Halogens can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0078] C 1-20 Alkyl groups can be straight-chain, branched, or cyclic. Specifically, C 1-20 Alkyl groups can be C 1-20 Straight-chain alkyl; C 1-15 Straight-chain alkyl; C 1-5 Straight-chain alkyl; C 3-20 Branched or cyclic alkyl groups; C 3-15 Branched or cyclic alkyl groups; or C 3-10 Branched or cyclic alkyl groups. More specifically, C 1-20 The alkyl group can be methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., but is not limited to these.

[0079] C 2-20 Alkenes can be straight-chain, branched, or cyclic. Specifically, they can be allyl, vinyl, propenyl, butenyl, pentenyl, etc., but are not limited to these.

[0080] C 1-20 Alkoxy groups can be methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, cyclohexyloxy, etc., but are not limited to these.

[0081] C 2-20 Alkoxyalkyl refers to a functional group in which at least one hydrogen atom is replaced by an alkoxy group. It can be an alkoxyalkyl group, such as methoxymethyl, methoxyethyl, ethoxymethyl, isopropoxyethyl, isopropoxypropyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl, but is not limited to these.

[0082] C 1-20 Alkyl silyl or C 1-20 Alkoxysilyl is a functional group in which one to three hydrogens of -SiH3 are replaced by one to three alkyl or alkoxy groups as described above. It can be alkylsilyl, such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl; alkoxysilyl, such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; or alkoxysilyl, such as methoxydimethylsilyl, diethoxymethylsilyl or dimethoxypropylsilyl; and so on, but is not limited thereto.

[0083] C 1-20 Silyyl group refers to a functional group in which at least one hydrogen atom is replaced by a silyl group. It can be -CH2-SiH3, methylsilylmethyl, or dimethylethoxysilylpropyl, etc., but is not limited to these.

[0084] In addition, C 1-20 The alkylene or alkylidene group is the same as the alkyl group mentioned above, except that it is a divalent substituent. It can be methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, etc., but is not limited to these.

[0085] C 6-20 The aryl group can be a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon. For example, C 6-20 The aryl group can be phenyl, biphenyl, naphthyl, anthracene, phenanthryl, fluorene, etc., but is not limited to these.

[0086] C 7-20 Alkyl groups can refer to substituents in which at least one hydrogen atom of the aromatic ring is replaced by the aforementioned alkyl group. For example, C 7-20 The alkylaryl group can be methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, etc., but is not limited to these.

[0087] C 7-20 Aryl groups can refer to substituents in which at least one hydrogen atom of the alkyl group is replaced by the aforementioned aryl group. For example, C 7-20 Aryl groups can be benzyl, phenethyl, biphenylmethyl, naphthylmethyl, etc., but are not limited to these.

[0088] In addition, C 6-20 The arylene or alkylidene group is the same as the aryl group mentioned above, except that it is a divalent substituent. It can be phenylene, biphenylene, naphthylene, anthracene, phenanthrene, fluorene, etc., but is not limited to these.

[0089] C 6-40The aryloxy group can be phenoxy, biphenyloxy, naphthoxy, etc., but is not limited to these.

[0090] C 7-40 Aryloxyalkyl refers to a functional group in which one or more hydrogen atoms of the above-mentioned alkyl group are replaced by aryloxy groups. These can be phenoxymethyl, phenoxyethyl, phenoxyhexyl, etc., but are not limited to these.

[0091] Group 4 transition metals can be titanium (Ti), zirconium (Zr), hafnium (Hf), or... (Rf), specifically it can be titanium (Ti), zirconium (Zr), or hafnium (Hf). More specifically, it can be zirconium (Zr) or hafnium (Hf), but this disclosure is not limited thereto.

[0092] Furthermore, the Group 13 elements can be boron (B), aluminum (Al), gallium (Ga), indium (In) or thallium (Tl), specifically boron (B) or aluminum (Al), but this disclosure is not limited thereto.

[0093] The above-mentioned substituents may optionally be replaced by one or more substituents selected from the group consisting of: hydroxyl; halogen; hydrocarbon group; hydroxyl group; hydrocarbon group or hydroxyl group containing at least one heteroatom of group 14 to 16; silyl group; hydrocarbon (oxy)silyl group; phosphine group; phosphide group; sulfonic acid group; and sulfone group, all of which are within the range that exhibit the same or similar effects as the desired effects.

[0094] Furthermore, in the method for preparing the organic-inorganic hybrid polyolefin composite material disclosed herein, the catalyst composition includes a first metallocene compound with low comonomer incorporation and a second metallocene compound with high comonomer incorporation as catalytically active components during olefin polymerization. Therefore, it exhibits high activity and excellent process stability in olefin polymerization. In addition, due to the high bonding performance between the catalytically active component and the non-porous inorganic material, this catalyst composition can be used to prepare polyolefin composite materials with excellent mechanical properties.

[0095] Specifically, in chemical formula 1, M 1 It can be zirconium (Zr) or hafnium (Hf), with zirconium (Zr) being preferred.

[0096] Furthermore, in chemical formula 1, Cp 1 and Cp 2 Each of them can be cyclopentadienyl, indenyl, or fluorenyl, and preferably, Cp 1 and Cp 2 At least one of them is cyclopentadienyl or indenyl. More preferably, Cp 1 and Cp 2 Both can be cyclopentadienyl groups.

[0097] Cp 1 and Cp 2It may not have substituents or may have at least one C substituent. 1-20 Hydrocarbons. For example, Cp 1 and Cp 2 It can replace C 1-10 hydrocarbon group, C 1-10 Hydroxyl group or C 1-10 One or more of the alkyl oxyalkyl groups. Specifically, they may replace one or more of methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, tert-butoxyhexyl, butenyl, phenylpropyl, phenylhexyl or phenyl.

[0098] More specifically, in first metallocene compounds, Cp 1 and Cp 2 They can be the same or different from each other, with Cp being preferred. 1 and Cp 2 They are identical to each other and can contain the same substituents to form a symmetrical structure.

[0099] In addition, R a and R b They can each be hydrogen or carbon. 1-6 Straight-chain or branched alkyl groups, C 2-6 alkynyl group, C 1-6 alkoxy-substituted C 1-6 Alkyl, C 6-12 aryl-substituted C 1-6 Alkyl, or C 6-12 aryl, condition R a and R b At least one of them is not hydrogen. In particular, R a and R b They can be the same or different from each other; preferably, R a and R b They can be identical to each other and can take the form of chemical formula 1 with a symmetrical structure. For example, R a and R b Each of these components can be hydrogen, methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy (t-Bu-O)hexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl (Ph). Preferably, R... a and R bAt least one of them can be tert-butoxyhexyl, and the others can be hydrogen, methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy(t-Bu-O)hexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl (Ph). More preferably, R a and R b At least one of them can be tert-butoxyhexyl, and the rest can be hydrogen.

[0100] Furthermore, in chemical formula 1, each Q 1 It can be halogens, especially chlorine.

[0101] In chemical formula 1, n is 1 or 0, preferably 1.

[0102] Meanwhile, the first metallocene compound can be represented by any one of the following chemical formulas 1-1 to 1-5.

[0103] [Chemical Formula 1-1]

[0104]

[0105] [Chemical Formula 1-2]

[0106]

[0107] [Chemical Formulas 1-3]

[0108]

[0109] [Chemical Formulas 1-4]

[0110]

[0111] [Chemical Formulas 1-5]

[0112]

[0113] In chemical formulas 1-1 to 1-5, M 1 and Q 1 As defined in chemical formula 1.

[0114] R' and R" may be the same as or different from each other, and each is independently hydrogen or C. 1-20 Alkyl, C 1-20 Alkoxy, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 6-20 aryloxy group, C 2-20 alkenyl, C 7-40 Alkyl, C 7-40 Aryl alkyl, C8-40 Arylene, or C 2-10 Alkyne group, provided that at least one of R' and R' is not hydrogen.

[0115] Each m1 is an independent integer from 1 to 8; and

[0116] Each m2 is an independent integer from 1 to 6.

[0117] More preferably, the first metallocene compound may be represented by chemical formula 1-1.

[0118] Furthermore, in chemical formulas 1-1 to 1-5, R' and R" can each be hydrogen or C. 1-6 Straight-chain or branched alkyl groups, C 2-6 Alkynes, C 1-6 alkoxy-substituted C 1-6 Alkyl, C 6-12 aryl-substituted C 1-6 Alkyl or C 6-12 The aryl group is defined as follows: at least one of R′ and R″ is not hydrogen. Specifically, at least one of R′ and R″ can be methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy(t-Bu-O)hexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl (Ph), and the remainder can be hydrogen. More specifically, at least one of R′ and R″ can be tert-butoxy(t-Bu-O)hexyl, and the remainder can be hydrogen.

[0119] Furthermore, in chemical formulas 1-1 to 1-5, each of m1 and m2 is an integer from 1 to 4, preferably 1 or 2.

[0120] Specifically, the first metallocene compound can be represented by one of the following structural formulas.

[0121]

[0122] The first metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and more detailed synthetic methods are described in the examples.

[0123] Meanwhile, in the method for preparing the organic-inorganic hybrid polyolefin composite material disclosed herein, the catalyst composition comprises a second metallocene compound represented by chemical formula 2 and the aforementioned first metallocene compound.

[0124] Specifically, in chemical formula 2, M 2 It can be zirconium (Zr) or hafnium (Hf), with zirconium (Zr) being preferred. Alternatively, Q can be silicon (Si).

[0125] In addition, R 1 To R 17 They can each be hydrogen or carbon. 1-8 Alkyl, C 2-8 alkenyl or C 6-12 Aryl, and preferably methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, or phenyl, but this disclosure is not limited thereto. Specifically, R 1 To R 16 It can be hydrogen or C 1-8 Alkyl, C 1-5 Alkyl or C 1-3 Alkyl groups, while R 17 It can be C 1-8 Alkyl, C 1-5 Alkyl or C 1-3 Alkyl group. More specifically, R 1 To R 16 It could be hydrogen, and R 17 It can be methyl.

[0126] Furthermore, L is more preferably C 4-8 Straight-chain or branched alkylene groups, but not limited thereto. Furthermore, the alkylene group may be unsubstituent or substituted with C groups. 1-20 Alkyl, C 2-20 alkenyl or C 6-20 Aryl. Specifically, L can be C 5-7 Straight-chain or branched alkylene groups. Preferably, L can be hexanediol.

[0127] Furthermore, D can be -O-.

[0128] In addition, A can be hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, C 2-12 Alkoxyalkyl or C 5-12 The group can be heteroaryl, but is not limited to this. Specifically, A can be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, methoxymethyl, tert-butoxymethyl, 1-ethoxyethyl, 1-methyl-methoxyethyl, tetrahydropyranyl, or tetrahydrofuranyl. Preferably, A can be tert-butyl.

[0129] In addition, X 1 and X 2 Each of them can be a halogen. For example, it can be chlorine (Cl), bromine (Br), or iodine (I), preferably chlorine (Cl).

[0130] Specifically, the compound represented by chemical formula 2 can be, for example, a compound represented by the following structural formula, but is not limited thereto.

[0131]

[0132] The second metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and more detailed synthetic methods are described in the examples.

[0133] In the catalyst composition disclosed herein, a first metallocene compound and a second metallocene compound may be incorporated in a molar ratio of about 1:9 to about 9:1. When the first and second metallocene compounds are included in the above molar ratio, excellent loading performance, catalytic activity, and high comonomer incorporation rate are exhibited. In particular, when polyolefins are prepared by a slurry process under a catalyst with such a catalyst composition, process stability is improved, and fouling problems that have occurred in the past can be prevented. Specifically, when the loading ratio of the first metallocene compound to the second metallocene compound exceeds about 9:1, only the first metallocene compound plays a dominant role, and the incorporation of comonomers may decrease. Furthermore, when the loading ratio is less than about 1:9, only the second metallocene compound plays a dominant role, and it may be difficult to reproduce the ideal molecular structure of the polymer.

[0134] Specifically, preferably, the catalyst composition comprises a first metallocene compound and a second metallocene compound in a molar ratio of about 1:5 to about 5:1, or a molar ratio of about 1:4 to about 4:1, about 1:3 to about 3:1, about 1:1.5 to about 2.8:1, about 1:1.8 to about 2.6:1, about 1:2 to about 2.5:1, about 1:2 to about 2.4:1, or about 1:21 to about 2.3:1, to produce polyolefins with improved mechanical properties due to the incorporation of excellent comonomers while exhibiting high activity in polyolefin polymerization. More specifically, the molar ratio of the first metallocene compound and the second metallocene compound may be about 1:2 to about 2.5:1, more preferably about 1:2 to about 2.4:1, or about 1:21 to about 2.3:1.

[0135] In other words, when the catalyst composition contains the first metallocene compound and the second metallocene compound in the above molar ratio, the membrane properties of polyolefins can be further improved due to the interaction of the two or more catalysts.

[0136] Meanwhile, the method for preparing the organic-inorganic hybrid polyolefin composite material disclosed herein is characterized in that the olefin monomers are polymerized in the presence of a catalyst composition described below, wherein a catalytically active component comprising at least one first metallocene compound and at least one second metallocene compound is combined with a nonporous inorganic material, wherein, based on the total weight of the organic-inorganic hybrid polyolefin composite material, the content of the nonporous inorganic material is about 0.4% by weight or more, or about 0.4% by weight to about 12% by weight.

[0137] The content of nonporous inorganic material can be adjusted by changing the ratio of the nonporous inorganic material used in the catalyst composition to the olefin monomers added during polymerization, or by changing the proportion of polyolefins produced according to the polymerization conditions. For example, even if the content of nonporous inorganic material in the catalyst composition is the same as the content of olefin monomers during polymerization, the content of nonporous inorganic material based on the total weight of the organic-inorganic hybrid polyolefin composite to be prepared can be optimized within the above range by changing the temperature, pressure, and reaction time, which are the polymerization conditions.

[0138] Specifically, based on the total weight of the olefin monomer and the non-porous inorganic material, catalytically active component, and co-catalyst contained in the catalyst composition, the content of the non-porous inorganic material is about 0.4% by weight or more, preferably about 0.42% by weight or more, about 0.43% by weight or more, about 0.44% by weight or more, about 0.45% by weight or more, about 0.46% by weight or more, about 0.47% by weight or more, about 0.48% by weight or more, about 0.49% by weight or more, or about 0.5% by weight or more. When the content of the non-porous inorganic material is less than 0.4% by weight, it does not function as a filler bound to the polyolefin, nor can it compensate for the mechanical properties of the polyolefin. However, based on the total weight of the olefin monomers and inorganic materials, the content of the non-porous inorganic material can be less than about 12% by weight, preferably less than about 10% by weight, less than about 9.8% by weight, less than about 9.5% by weight, less than about 9% by weight, less than about 8.8% by weight, less than about 8.6% by weight, less than about 8.5% by weight, less than about 8.4% by weight, less than about 8.3% by weight, less than about 8.2% by weight, less than about 8.1% by weight, or less than about 8% by weight, thereby preventing the deterioration of the mechanical properties of the organic-inorganic hybrid polyolefin composite material. For example, when the content of the non-porous inorganic material is too high, such as exceeding about 12% by weight, it acts as an impurity rather than a filler in the organic-inorganic hybrid polyolefin composite material, thereby preventing the formation of the polymer matrix and reducing the mechanical properties. Therefore, in order to ensure the excellent mechanical properties of the organic-inorganic hybrid polyolefin composite material to be prepared, the content of the non-porous inorganic material is preferably included within the above-mentioned range.

[0139] In particular, the inorganic materials disclosed herein can be non-porous materials, having a smooth surface completely free of pores, or materials with some irregularity (which cannot be considered as pores on the surface). The properties of non-porous inorganic materials are the same as those described above concerning organic-inorganic hybrid polyolefin composites, and therefore a detailed description thereof will be omitted.

[0140] Furthermore, in the catalyst composition disclosed herein, based on 1 gram of the aforementioned non-porous inorganic material, the total amount of the catalytically active component comprising at least one first metallocene compound and at least one second metallocene compound can be 0.001 mmol / g or more, 0.003 mmol / g or more, 0.005 mmol / g or more, or 0.008 mmol / g or more, and is less than 1 mmol / g, less than 0.99 mmol / g, less than 0.98 mmol / g, or less than 0.95 mmol / g. In other words, considering the contribution of the metallocene compound to the catalyst, it is preferable to control the total amount of the catalytically active component within the aforementioned range.

[0141] Simultaneously, the combination of the catalytically active component and the inorganic material can be confirmed from the ICP analysis results of the transition metals, with the transition metal concentrations below 0.1 ppm or 0.01 ppm. Here, during the preparation of the catalyst composition, the filtrate obtained during the filtration process to finally obtain the solid catalyst composition is subjected to ICP analysis.

[0142] In the method for preparing the organic-inorganic hybrid polyolefin composite material disclosed herein, the catalyst composition may include a co-catalyst compound along with the catalytically active component and the inorganic material, comprising at least one first metallocene compound and at least one second metallocene compound. The co-catalyst can be any co-catalyst used for olefin polymerization in the presence of a general metallocene catalyst. This co-catalyst enables the hydroxyl groups in the inorganic material to bond with a Group 13 transition metal. Furthermore, since the co-catalyst exists only on the surface of the inorganic material, it can promote the realization of the inherent properties of the catalyst composition of this disclosure without causing scaling phenomena such as polymer particles agglomerating with or clumping against the reactor wall.

[0143] Furthermore, the catalyst composition disclosed herein may further comprise at least one co-catalyst selected from the group of compounds represented by the following chemical formulas 3 to 5.

[0144] [Chemical Formula 3]

[0145] -[Al(R 31 )-O] c -

[0146] In chemical formula 3,

[0147] R 31 Each is independently a halogen, C 1-20 Alkyl or C 1-20 Halogenated alkyl groups, and

[0148] c is an integer of 2 or higher.

[0149] [Chemical Formula 4]

[0150] D(R 41 )3

[0151] In chemical formula 4,

[0152] D is aluminum or boron, and

[0153] R 41 Each is independently hydrogen, halogen, C 1-20 Hydrocarbon group or C substituted with halogen 1-20 Hydrocarbon group.

[0154] [Chemical Formula 5]

[0155] [LH] + [Q(E)4] - Or [L] + [Q(E)4] -

[0156] In chemical formula 5,

[0157] L is a neutral or cationic Lewis base;

[0158] Q is B 3+ Or Al 3+ ,as well as

[0159] E is C independently. 6-40 Aryl or C 1-20 Alkyl group, without substituents or with substituents selected from halogens, C 1-20 Alkyl, C 1-20 Alkoxy and C 6-40 Substituents of aryloxy groups.

[0160] Specifically, in chemical formula 5, [LH] + It is Brønsted acid.

[0161] The compound represented by chemical formula 3 can be an alkylaluminoxane, such as methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc.

[0162] The alkyl metal compound represented by chemical formula 4 can be trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, dimethylisobutylaluminum, dimethylethylaluminum, diethylaluminum chloride, triisopropylaluminum, tritert-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylborane, triethylborane, triisobutylborane, tripropylborane, tributylborane, etc.

[0163] The compound represented by chemical formula 5 can be triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, N,N-diethylphenylammonium tetraphenylboron, N,N-diethylphenylammonium tetra(pentafluorophenyl)boron, diethylammonium tetra(pentafluorophenyl)boron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, tripropylammonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, tripropylammonium tetraphenylboron, triethylammonium tetraphenylboron, triethylammonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, triethylammonium tetraphenylboron ... Ammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetra(pentafluorophenyl)aluminum, N,N-diethylphenylammonium tetraphenylaluminum, N,N-diethylphenylammonium tetra(pentafluorophenyl)aluminum, diethylammonium tetra(pentafluorophenyl)aluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbium tetra(p-trifluoromethylphenyl)boron, or triphenylcarbium tetra(pentafluorophenyl)boron, etc.

[0164] Furthermore, the catalyst composition may contain a co-catalyst and a first metallocene compound in a molar ratio of about 1:1 to about 1:10000, preferably about 1:1 to about 1:1000, more preferably about 1:10 to about 1:100.

[0165] Furthermore, the catalyst composition may contain a co-catalyst and a second metallocene compound in a molar ratio of about 1:1 to about 1:10000, preferably about 1:1 to about 1:1000, more preferably about 1:10 to about 1:100.

[0166] At this point, when the molar ratio is less than about 1, the metal content of the co-catalyst is too low, so the catalytically active species cannot form well, resulting in low activity. When the molar ratio exceeds about 10,000, the metal of the co-catalyst may act as a poison for the catalyst.

[0167] Based on 1 gram of inorganic material, a co-catalyst can be loaded in amounts of approximately 5 millimoles to approximately 20 millimoles.

[0168] Meanwhile, the catalyst composition can be prepared by a method including the following steps: supporting a co-catalyst on an inorganic material; supporting a first metallocene compound on the inorganic material supporting the co-catalyst; and supporting a second metallocene compound on the inorganic material supporting the co-catalyst and the first metallocene compound.

[0169] Alternatively, the catalyst composition can be prepared by a method comprising the following steps: supporting a co-catalyst on an inorganic material; supporting a second metallocene compound on the inorganic material supporting the co-catalyst; and supporting a first metallocene compound on the inorganic material supporting the co-catalyst and the second metallocene compound.

[0170] Alternatively, the catalyst composition can be prepared by a method comprising the following steps: loading a first metallocene compound onto an inorganic material; loading a co-catalyst onto the inorganic material loaded with the first metallocene compound; and loading a second metallocene compound onto the inorganic material loaded with the co-catalyst and the first metallocene compound.

[0171] In the above method, there are no particular limitations on the loading conditions, and the loading step can be carried out within a range well known to those skilled in the art. For example, the loading step can be carried out appropriately at high and low temperatures. For example, the loading temperature can be in the range of about -30°C to about 150°C, preferably in the range of about 50°C to about 98°C, or about 55°C to about 95°C. The loading time can be appropriately controlled according to the amount of the first metallocene compound to be loaded. After removing the reaction solvent by filtration or vacuum distillation, or if necessary by Soxhlet filtration with an aromatic hydrocarbon (such as toluene), the loaded catalyst after the reaction can be used without further treatment.

[0172] The catalyst can be prepared with or without a solvent. When a solvent is used, it may include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, chlorinated hydrocarbon solvents such as dichloromethane, ether solvents such as diethyl ether or tetrahydrofuran (THF), and common organic solvents such as acetone or ethyl acetate. Hexane, heptane, toluene, or dichloromethane are preferred. The solvent used herein is preferably used after removing trace amounts of water or air that may adversely affect the catalyst by treatment with a small amount of alkylaluminum.

[0173] Meanwhile, the preparation method of the organic-inorganic hybrid polyolefin composite material includes the step of polymerizing olefin monomers in the presence of the above-mentioned catalyst composition.

[0174] Specifically, the olefin monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Preferably, ethylene or propylene may be used for homopolymerization or copolymerization.

[0175] For the polymerization reaction of olefin monomers, various polymerization processes known as olefin monomer polymerization reactions can be used, such as continuous solution polymerization, batch polymerization, suspension polymerization, slurry polymerization or emulsion polymerization. More specifically, the polymerization reaction can be carried out in a semi-batch reactor.

[0176] Furthermore, in the polymerization reactor for olefin monomer polymerization, the polymerization reaction can be carried out in the presence of an inert gas such as nitrogen. The inert gas can prolong the reactivity of the metallocene compounds contained in the catalyst composition by suppressing the rapid reaction of the metallocene compounds, which are the catalytically active components, at the beginning of the polymerization reaction.

[0177] Furthermore, hydrogen can be used in polymerization reactions to control the molecular weight and molecular weight distribution of polyolefins.

[0178] Polymerization can be carried out at temperatures ranging from about 50°C to about 110°C, from about 60°C to about 105°C, from about 70°C to about 100°C, from about 72°C to about 90°C, or from about 75°C to about 83°C. When the polymerization temperature is too low, the polymerization rate and productivity may decrease. Conversely, when the polymerization temperature is too high, scaling may occur in the reactor.

[0179] Furthermore, the polymerization pressure can be from about 1 bar to about 100 bar, from about 2 bar to about 80 bar, from about 3 bar to about 50 bar, from about 4 bar to about 40 bar, from about 5 bar to about 30 bar, or from about 8 bar to about 25 bar, to achieve economic feasibility by ensuring optimal productivity. The polymerization pressure can be above about 1 bar to prevent blockage due to overproduction of high molecular weight monomers and to optimize productivity, while the polymerization pressure can be below about 100 bar, taking into account the reduction in polymerization reaction units of olefin monomers under high-pressure polymerization conditions.

[0180] In the method for preparing the organic-inorganic hybrid polyolefin composite material according to this disclosure, the polymerization time of the olefin monomers can vary depending on the temperature and pressure conditions described above, and also depending on the amount of olefin monomers undergoing the polymerization reaction. However, compared to polymerization reactions of olefin monomers generally known, i.e., polymerization reactions of polyolefins using olefin monomers without bonding with non-porous inorganic materials, the polymerization reaction time is shorter. Therefore, non-porous inorganic materials can serve as fillers for bonding with polyolefins and can compensate for the mechanical properties of polyolefins. Specifically, polymerization can be carried out in a short time, which is about 20% or less of the polymerization time of olefin monomer polymerization in the presence of a catalyst composition using porous inorganic materials instead of non-porous inorganic materials, preferably within about 17%, about 15%, about 14%, about 13%, about 12.5%, about 12%, about 11.7%, or about 5% to 11.7%. For example, assuming that the polymerization time of the olefin monomer is 1 hour in the presence of a catalyst composition using porous inorganic materials but not non-porous inorganic materials, the polymerization process can be carried out in a time of less than about 12 minutes, preferably less than about 10 minutes, less than about 8.5 minutes, less than about 8 minutes, less than about 7.5 minutes, less than about 7 minutes, or from about 3 minutes to about 7 minutes.

[0181] For example, polymerization can be carried out at a temperature of about 50°C to 110°C and a pressure of about 1 bar to 100 bar for about 120 minutes or less, or about 1 minute to about 120 minutes, provided that, based on the total weight of the organic-inorganic hybrid polyethylene composite, the non-porous inorganic material and olefin monomer used in the catalyst composition are more than 0.4% by weight, or 0.4% to 12% by weight. Preferably, polymerization can be carried out for about 120 minutes or less, or about 1 minute to about 120 minutes, preferably about 100 minutes or less, about 80 minutes or less, about 60 minutes or less, about 55 minutes or less, about 50 minutes or less, about 45 minutes or less, about 40 minutes or less, about 35 minutes or less, about 30 minutes or less, about 28 minutes or less, about 25 minutes or less, about 22 minutes or less, about 20 minutes or less, about 18 minutes or less, about 15 minutes or less, about 12 minutes or less, about 10 minutes or less, about 9 minutes or less, about 8 minutes or less, or about 7 minutes or less. When polymerization time is prolonged, the excessive formation of high molecular weight polymers renders the non-porous inorganic material ineffective as a filler for bonding with the polyolefin, failing to compensate for the polyolefin's mechanical properties. In this regard, polymerization can proceed for approximately 120 minutes or less. However, for the productivity of producing polyolefins through the polymerization of olefin monomers, polymerization times can be approximately 1 minute or more, preferably approximately 2 minutes or more, or approximately 3 minutes or more. As mentioned above, polymerization time can vary depending on the amount of olefin monomer added and polymerization conditions, such as polymerization temperature, pressure, and whether hydrogen is added.

[0182] For example, the process can be carried out at a temperature of about 75°C to about 83°C and a pressure of about 8 bar to 25 bar for about 1 minute to about 12 minutes, about 2 minutes to about 10 minutes, about 2 minutes to about 8.5 minutes, about 3 minutes to about 8 minutes, about 3 minutes to about 7.5 minutes, or about 3 minutes to about 7 minutes, provided that the content of nonporous inorganic material and olefin monomer used in the catalyst composition is 0.5% to 2.2% by weight based on the total weight of the organic-inorganic hybrid polyethylene composite material.

[0183] Meanwhile, in another embodiment of this disclosure, a membrane material manufactured using an organic-inorganic hybrid polyolefin composite material according to this embodiment is provided.

[0184] Preferably, the material used for the separator can be a lithium-ion battery separator (LiBS).

[0185] As described above, the membrane material of this disclosure is prepared by polymerizing olefin monomers after combining the catalytically active component with inorganic materials in a specified amount. This process ensures good dispersion of the material without migration. Therefore, the physical properties do not deteriorate over time, and production can be tailored to the inorganic content, thereby effectively controlling the desired physical properties, such as excellent mechanical properties, wettability, dimensional stability, turn-off properties, and low thermal shrinkage.

[0186] Beneficial effects

[0187] According to this disclosure, after combining a catalytically active component with a non-porous inorganic material, a polymerization process of olefin monomers is carried out, thereby effectively mixing and dispersing the non-porous inorganic material and the olefin polymer. Therefore, an organic-inorganic hybrid polyolefin composite material is provided that solves the problem of physical property degradation over time due to olefin polymer migration, while achieving excellent mechanical properties, wettability, dimensional stability, turn-off properties, and low thermal shrinkage. Attached Figure Description

[0188] Figure 1 A photograph of the catalyst composition of Preparation Example 1, obtained by transmission electron microscopy (TEM), is shown.

[0189] Figure 2 The images shown are obtained using transmission electron microscopy (TEM) after sampling at each reaction time during the polymerization process in Example 1.

[0190] Figure 3 A schematic diagram showing the measurement results of the water contact angle of the polymer film surface obtained in Examples 1 to 3 and Comparative Examples 1 to 2 is displayed.

[0191] Figure 4 Photographs of membrane samples before and after being placed at 140°C for 1 hour are shown when evaluating the dimensional stability of the polymer membranes obtained in Examples 1 to 3 and Comparative Examples 1 to 2.

[0192] Figure 5 Photographs of membrane samples before and after being placed at 150°C for 1 hour when evaluating the shut-off function of the polymer membranes obtained in Examples 1 to 3 and Comparative Examples 1 to 2 are shown. Detailed Implementation

[0193] The embodiments of the present invention will be described in more detail in the following examples. However, the following examples are provided to illustrate the embodiments of the present invention, and the content of the present invention is not limited to the following examples.

[0194] [Example]

[0195] <Preparation of Catalyst Precursors>

[0196] Synthesis Example 1: Preparation of a First Metallocene Compound

[0197]

[0198] Following the method in Tetrahedron Lett. 2951 (1988), tert-butyl-O-(CH2)6-Cl was prepared from 6-chlorohexanol and reacted with sodium cyclopentadiene (NaCp) to give tert-butyl-O-(CH2)6-C5H5 (yield 60%, bp 80). ℃ / 0.1 mmHg).

[0199] Furthermore, tert-butyl-O-(CH2)6-C5H5 was dissolved in tetrahydrofuran (THF) at -78 °C, and n-butyllithium (n-BuLi) was slowly added. The mixture was then heated to room temperature and reacted for 8 hours. At -78 °C, the synthesized lithium salt solution was slowly added to a suspension of ZrCl4(THF)2 (170 g, 4.50 mmol) / THF (30 mL), and the reaction was further carried out at room temperature for approximately 6 hours. All volatiles were dried under vacuum, and the resulting oily liquid was obtained by filtration with the addition of hexane. The filtered solution was dried under vacuum, and n-hexane was added, yielding a precipitate at low temperature (-20 °C). The precipitate was filtered at low temperature to give [tert-butyl-O-(CH2)6-C5H4]2ZrCl2 as a white solid (92% yield).

[0200] 1 H-NMR (300 MHz, CDCl3, ppm): δ 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J=8 Hz), 1.7 – 1.3 (m, 8H), 1.17 (s,9H)

[0201] 13 C-NMR (300 MHz, CDCl3, ppm): δ 135.09, 116.66, 112.28, 72.42, 61.52,30.66, 30.31, 30.14, 29.18, 27.58, 26.00

[0202] Synthesis Example 2: Preparation of Second Metallocene Compounds

[0203]

[0204] A 1.0 mol solution of tert-butyl-O-(CH2)6MgCl (Grignard reagent) was obtained by reacting tert-butyl-O-(CH2)6Cl with Mg(O) in THF solvent. The prepared Grignard reagent was added to a flask containing (CH3)SiCl3 compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at -30 °C. The mixture was stirred at room temperature for at least 8 hours, and the filtered solution was dried under vacuum to obtain tert-butyl-O-(CH2)6Si(CH3)Cl2 compound (92% yield).

[0205] Fluorene (Flu, 3.33 g, 20 mmol), n-hexane (100 mL), and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) were added to a reactor at -20 °C, and 8 mL of n-BuLi (2.5 M, in n-hexane) was slowly added. The mixture was then stirred at room temperature for 6 hours. After stirring, the reactor temperature was cooled to -30 °C. Then, at -30 °C, the prepared fluorene-lithium solution was slowly added over 1 hour to a solution of tert-butyl-O-(CH2)6Si(CH3)Cl2 (2.7 g, 10 mmol) dissolved in hexane (100 mL). After stirring at room temperature for at least 8 hours, water was added for extraction and evaporation to obtain (tert-butyl-O-(CH2)6)(CH3)Si(9-C)Cl2. 13 H 10 Compound (5.3 g, 100% yield). The structure of this ligand was determined by... 1 H-NMR confirmed the results.

[0206] 1 H NMR (500 MHz, CDCl3, ppm): δ -0.35 (CH3Si, 3H, s), 0.26 (Si-CH2,2H, m), 0.58 (CH2, 2H, m), 0.95 (CH2, 4H, m), 1.17 (tert-butyl-O, 9H, s), 1.29(CH2,2H, m), 3.21(tert-butyl-O-CH2, 2H, t), 4.10(Flu-9H, 2H, s), 7.25(Flu-H, 4H, m), 7.35(Flu-H, 4H, m), 7.40(Flu-H, 4H, m), 7.85(Flu-H, 4H, d)

[0207] At -20°C, the (tert-butyl-O-(CH2)6)(CH3)Si(9-C) group is formed. 13 H 104.8 mL of n-BuLi (2.5 M, in n-hexane) was slowly added to a ZrCl4(THF)2 (3.18 g, 6 mmol) / MTBE (20 mL) solution and reacted for at least 8 hours while the temperature was raised to room temperature. Subsequently, the prepared dilithium salt slurry was slowly added to a ZrCl4(THF)2 (2.26 g, 6 mmol) / hexane (20 mL) slurry at -20 °C, and then reacted further at room temperature for 8 hours. The precipitate was filtered and washed several times with n-hexane to obtain tert-butyl-O-(CH2)6)(CH3)Si(9-C) 13 The compound H9)2ZrCl2 is a red solid (4.3 g, yield 94.5%).

[0208] 1 H NMR(500 MHz, C6D6, ppm): δ 1.15(tert-butyl-O, 9H, s), 1.26 (CH3Si, 3H,s), 1.58 (Si-CH2, 2H, m), 1.66 (CH2, 4H, m), 1.91(CH2, 4H, m), 3.32(tert-butyl-O-CH2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15 (Flu-H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64(Flu-H, 2H, d), 7.77(Flu-H, 2H, d)

[0209] <Preparation of Catalyst Composition>

[0210] Preparation Example 1

[0211] 50 mL of toluene was placed in a 300 mL glass reactor, and 10 g of non-porous silica (SiO2) was added. The reactor was stirred while the temperature was raised to 40 °C. Under these conditions, the specific surface area of ​​the non-porous silica was 15 m², as measured by ISO 9277 of the International Organization for Standardization. 2 / g. Non-porous silica was prepared by the Stover method (Stober, W. and A. Fink, Bohn, Journal of Colloid and Interface Science, 1986, 26, 62) using tetraethyl orthosilicate (TEOS) hydrolysis in an aqueous solvent with added NaOH catalyst.

[0212] Subsequently, 60 mL of a 10% by weight methylaluminoxane (MAO) / toluene solution (prepared by Albermarle) was added, and the temperature was raised to 60 °C, followed by stirring at 200 rpm for 12 hours. After the reactor temperature decreased to 40 °C, stirring was stopped and the mixture was allowed to settle for 10 minutes. The reaction mixture was then decanted. 100 mL of toluene was added and stirred for 10 minutes, after which stirring was stopped and the mixture was allowed to settle for 10 minutes. The toluene solution was then decanted.

[0213] Subsequently, 50 mL of toluene, the metallocene compound prepared in Synthesis Example 2 (0.0055 mmol / g SiO2), and 10 mL of toluene were added to the reactor, and the mixture was stirred at 200 rpm for 1 hour. Then, the metallocene compound prepared in Synthesis Example 1 (0.0025 mmol / g SiO2) and 10 mL of toluene were added to the reactor, and the mixture was stirred at 200 rpm for 2 hours. Here, the molar ratio of the metallocene compound in Synthesis Example 1 to the metallocene compound in Synthesis Example 2 was 1:2.2. Then, 30 mL of toluene was added and stirred for 10 minutes, stirring was stopped, and the mixture was allowed to precipitate for 30 minutes. Afterward, the toluene solution was decanted.

[0214] 30 mL of hexane was added to the reactor, and the hexane slurry was transferred to a drying filter and filtered to obtain the hexane solution. The resulting solid was then dried under reduced pressure at 40 °C for 4 hours to prepare the hybrid supported catalyst composition.

[0215] Meanwhile, as a result of ICP analysis of the filtrate obtained after filtration, the content of the transition metal (Zr) remaining in the filtrate was found to be less than 0.1 ppm.

[0216] Figure 1 The image shows a photograph of the catalyst composition prepared in this way, obtained by transmission electron microscopy (TEM). In particular, Figure 1 (a) Showing the surface of an inorganic material, Figure 1 (b) is a photograph of a catalyst supported on an inorganic material. Figure 1 (c) is a photograph of an inorganic material after a cocatalyst has been loaded and subsequently a metallocene compound has been loaded. Figure 1 (d) is Figure 1 (c) Enlarged photograph. According to Figure 1 This confirms that metallocene compounds are bound to the surface of inorganic materials.

[0217] Comparative Preparation Example 1

[0218] The hybrid supported catalyst composition was prepared in the same manner as in Preparation Example 1, except that porous silica (SP9, manufactured by WR Grace) was used instead of non-porous silica (SiO2). In this case, the specific surface area of ​​the porous silica was 300 m², as measured by ISO 9277 of the International Organization for Standardization. 2 / g.

[0219] Preparation of Organic-Inorganic Hybrid Polyolefin Composites

[0220] Example 1

[0221] Two mL of triethylaluminum (TEAL, 1.0 M hexane), the hybrid supported catalyst composition of Preparation Example 1, and hexane were placed in a vial and then placed in a 2 L autoclave reactor. 0.8 kg of hexane was added, and the temperature was raised to 80°C while stirring at 500 rpm. When the internal temperature of the reactor reached 78°C, ethylene gas was introduced, and the reaction was carried out at 9 bar and 500 rpm with stirring. The content of the hybrid supported catalyst composition and ethylene gas was adjusted so that the silica content was 0.5% by weight relative to the total weight of the organic-inorganic hybrid polyethylene composite. Furthermore, polymerization was carried out over 20 minutes by varying the polymerization time to 1 minute, 3 minutes, 5 minutes, 7 minutes, and 20 minutes. Hexane was first removed from the polymer obtained after the reaction by filtering, and then the polymer was washed with hexane. Hexane was then removed again by filtering, and the resulting polymer was dried in a vacuum furnace at 80°C for 4 hours to obtain an organic-inorganic hybrid polyethylene composite containing powdered ethylene homopolymer.

[0222] In particular, the organic-inorganic hybrid polyethylene composite material obtained by performing the above polymerization for 3 to 7 minutes was used as the final product, and its physical properties were evaluated according to the following test examples.

[0223] at the same time, Figure 2 The images shown are obtained using transmission electron microscopy (TEM) after sampling at each reaction time during the polymerization process described above. Figure 2 As shown, it can be confirmed how the polymer grows at (a) 1 minute, (b) 3 minutes, (c) 5 minutes and (d) 20 minutes after the start of the polymerization reaction, respectively, and it can also be confirmed that the polymer grows from a metallocene compound bonded to a non-porous inorganic material.

[0224] Examples 2 to 3

[0225] An organic-inorganic hybrid polyethylene composite containing powdered ethylene homopolymer was prepared in the same manner as in Example 1, except that the ethylene polymerization reaction was carried out in the presence of the above-mentioned hybrid supported catalyst composition, such that the total weight of the organic-inorganic hybrid polyethylene composite and the silica content were 2.2% by weight and 8.0% by weight, respectively, as described in Table 1 below, and then washed and dried.

[0226] Comparative Example 1

[0227] Organic-inorganic hybrid polyethylene composites containing powdered ethylene homopolymers were prepared in the same manner as in Example 1, except that the polymerization process was carried out using the hybrid supported catalyst composition of Comparative Preparation Example 1 instead of the hybrid supported catalyst composition of Preparation Example 1, followed by washing and drying.

[0228] In particular, the polymerization process of Comparative Example 1 was carried out under the same conditions as in Example 1, but the hybrid supported catalyst composition containing porous silica instead of non-porous silica, as in Comparative Example 1, was used. Therefore, due to the breakage of the porous silica during ethylene polymerization, the amount of ethylene polymerized increased instantaneously, and the silica content decreased relatively sharply. Thus, as shown in Table 1 below, based on the total weight of the organic-inorganic hybrid polyethylene composite material, the silica content was less than 0.01% by weight.

[0229] Comparative Example 2

[0230] An organic-inorganic hybrid polyethylene composite containing powdered ethylene homopolymer was prepared in the same manner as in Example 1, except that the ethylene polymerization reaction was carried out in the presence of the above-mentioned hybrid supported catalyst composition, such that the silica content was 0.3% by weight based on the total weight of the organic-inorganic hybrid polyethylene composite as shown in Table 1 below, and then the composite was washed and dried.

[0231] <Test Example: Evaluating the Physical Properties of Organic-Inorganic Hybrid Polyolefin Composites>

[0232] The physical properties of the organic-inorganic hybrid polyethylene composites prepared in the examples and comparative examples were measured as follows, and the results are shown in Table 1 below.

[0233] 1) Young's modulus and yield strength

[0234] According to ASTM D 638 of the American Society for Testing and Materials, film specimens were prepared from polymers obtained in the examples and comparative examples, and Young's modulus and yield strength were measured using a UTM (Universal Tensile Machine) according to the same method.

[0235] 2) Wettability (contact angle)

[0236] According to ASTM D 5946, a polymer membrane specimen was prepared from examples and comparative examples. Water was dropped onto the surface of the membrane specimen, and the water contact angle (in degrees) of the polymer membrane surface was measured. o The wettability was confirmed. The contact angle measuring instrument used was the KRUSS DSA 100.

[0237] Figure 3 A schematic diagram showing the measurement results of the water contact angle of the polymer membrane surface obtained in the examples and comparative examples is presented. It was confirmed that the water contact angle of the organic-inorganic hybrid polyethylene composites prepared in Examples 1 to 3 was significantly lower than that of the organic-inorganic hybrid polyethylene composites prepared in Comparative Examples 1 and 2. Since a low contact angle implies good wettability to water, it can be seen that the electrolyte can easily permeate when used as a separator in lithium-ion batteries (LiB).

[0238] 3) Dimensional stability

[0239] To check dimensional stability, membrane samples prepared in the same manner as the wettability test were placed at 140°C for 1 hour. Shrinkage was confirmed by measuring the area before and after placement.

[0240] Here, as described above, the membrane is placed at 140°C for 1 hour to cause thermal shrinkage. When the area after placing the membrane sample is more than 95% of the area before placement, it is indicated as "good", when it is more than 90% but less than 95%, it is indicated as "average", and when it is less than 90%, it is indicated as "poor".

[0241] When evaluating dimensional stability, photographs of the membrane specimen before and after placement are shown. Figure 4 As can be seen, the dimensional stability of the organic-inorganic hybrid polyethylene composites prepared in Examples 1 to 3 is significantly better than that of the organic-inorganic hybrid polyethylene composites prepared in Comparative Examples 1 and 2.

[0242] 4) Shutdown function

[0243] To check the shutdown function, a membrane sample prepared in the same manner as the wettability test was placed on filter paper and placed at 150°C for 1 hour to confirm the extent to which the membrane could maintain its original shape when it melted.

[0244] Here, when the membrane was placed at 150°C for 1 hour as described above, the phenomenon of membrane melting was observed. When the membrane sample retains its initial shape before placement after being placed under high temperature conditions, it is indicated as "good"; when it retains the outline of its initial shape before placement, it is indicated as "average"; and when it is difficult to check the outline of its initial shape before placement, it is indicated as "poor".

[0245] Photographs of the membrane specimens before and after placement during the evaluation of the shut-off function are shown in the image. Figure 5 As can be seen, in Comparative Examples 1 and 2, the membrane shape could hardly be maintained, and the membrane sample melted into the filter paper, while in Examples 1 to 3, the membrane sample melted appropriately into the filter paper while maintaining the initial shape of the membrane.

[0246] 5) Molecular weight (Mw, Mn) and molecular weight distribution (PDI, polydispersity index)

[0247] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers obtained in the examples and comparative examples were measured by gel permeation chromatography (GPC, Water Corporation), and the molecular weight distribution (PDI, Mw / Mn) was calculated by dividing the weight-average molecular weight by the number-average molecular weight.

[0248] Specifically, a Waters PL-GPC220 gel permeation chromatography (GPC) instrument was used, along with a Polymer Laboratories PLgel MIX-B 300 mm column. The evaluation temperature was 160 °C, 1,2,4-trichlorobenzene was used as the solvent, and the flow rate was 1 mL / min. Using the GPC analyzer (PL-GP220), each polyethylene sample was pretreated at 160 °C in 1,2,4-trichlorobenzene containing 0.0125% BHT (2,6-bis(1,1-dimethylethyl)-4-methylphenol) for 10 hours, and then applied in 200 μL at a concentration of 10 mg / 10 mL. Mw and Mn were obtained using calibration curves formed using polystyrene standards. Nine polystyrene standards were used, with molecular weights of 2000 g / mol, 10000 g / mol, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, and 10000000 g / mol.

[0249] Table 1

[0250]

[0251] Referring to Table 1 above, the organic-inorganic hybrid polyethylene composite materials of Examples 1 to 3 of this invention are prepared by ethylene polymerization after incorporating metallocene compounds onto non-porous silica with a specific inorganic material content. Therefore, the effective mixing and dispersion of inorganic materials and olefin polymers can achieve excellent mechanical properties, wettability, dimensional stability, shut-off properties, and low thermal shrinkage, and can solve the problem of physical property degradation over time due to the migration of olefin polymers.

Claims

1. An organic-inorganic hybrid polyolefin composite material, said organic-inorganic hybrid polyolefin composite material comprising a polyolefin and a non-porous inorganic material chemically bonded to at least a portion of said polyolefin, in, The BET specific surface area of the non-porous inorganic material is 100 m 2 / g or less when measured according to ISO 9277 of the International Organization for Standardization. Wherein, based on the total weight of the organic-inorganic hybrid polyolefin composite material, the content of the non-porous inorganic material is from 0.4% to 12% by weight, and The non-porous inorganic material has one or more hydroxyl or siloxane groups on its surface.

2. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, The polyolefin is a homopolymer or copolymer of an olefin monomer selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

3. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, The BET specific surface area of the non-porous inorganic material is below 80 m 2 / g when measured according to ISO 9277 of the International Organization for Standardization.

4. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, The non-porous inorganic material is selected from at least one of the group consisting of alumina, magnesium oxide, zirconium oxide, zeolite, and silicon dioxide.

5. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, The nonporous inorganic material is chemically bonded to at least a portion of the polyolefin by at least one of covalent and coordination bonds.

6. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, The weight average molecular weight of the organic-inorganic hybrid polyolefin composite material is above 300,000 g / mol.

7. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, The molecular weight distribution (Mw / Mn) of the organic-inorganic hybrid polyolefin composite material is 2.5 to 4.

5.

8. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, When measured according to ASTM D 638 of the American Society for Testing and Materials, the Young's modulus of the organic-inorganic hybrid polyolefin composite material is greater than 250 MPa.

9. The organic-inorganic hybrid polyolefin composite material according to claim 1, wherein, When measured according to ASTM D 5946 of the American Society for Testing and Materials, the water contact angle of the organic-inorganic hybrid polyolefin composite is less than 45°.

10. A method for preparing the organic-inorganic hybrid polyolefin composite material according to claim 1, the method comprising the following steps: In the presence of a catalyst composition, polymerize olefin monomers, wherein the catalyst composition comprises at least one first metallocene compound represented by the following chemical formula 1 and at least one second metallocene compound selected from compounds represented by the following chemical formula 2, the catalytically active component being bonded to a non-porous inorganic material. Wherein, based on the total weight of the organic-inorganic hybrid polyolefin composite material, the content of the non-porous inorganic material is from 0.4% to 12% by weight: [Chemical Formula 1] (Cp 1 R a ) n (Cp 2 R b )M 1 Q 1 3-n In chemical formula 1, M 1 is a group 4 transition metal; Cp 1 and Cp 2 They may be identical or different from each other, and each independently is selected from any one of the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl; wherein they are unsubstituent or have C-substituted groups. 1-20 hydrocarbon; R a and R b They may be the same or different from each other, and each is independently hydrogen or carbon. 1-20 Alkyl, C 1-20 Alkoxy, C 2-20 Alkoxyalkyl, C 6-20 Aryl, C 6-20 aryloxy group, C 2-20 alkenyl, C 7-40 Alkyl, C 7-40 Aryl alkyl, C 8-40 Aryl or C 2-10 Alkyne group, condition is R a and R b At least one of them is not hydrogen; Q 1 It is halogen, C 1-20 Alkyl, C 2-20 alkenyl, C 7-40 Alkyl, C 7-40 Aryl alkyl, C 6-20 Aryl, C with or without substituents 1-20 Alkyl groups, amino groups with or without substituents, C 2-20 Alkoxyalkyl, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy; and n is 1 or 0; [Chemical Formula 2] In chemical formula 2, R 1 To R 17 They may be the same or different from each other, and each is independently hydrogen, halogen, or carbon. 1-20 Alkyl, C 2-20 alkenyl, C 6-20 Aryl, C 7-20 alkylaryl or C 7-20 Aryl groups; L is C 1-10 Straight-chain or branched alkylene groups; D is -O-, -S-, -N(R)-, or -Si(R)(R')-, where R and R' are the same as or different from each other and are independently hydrogen, halogen, or carbon. 1-20 Alkyl, C 2-20 alkenyl or C 6-20 Aryl; A represents hydrogen, halogens, and C. 1-20 Alkyl, C 2-20 alkenyl, C 6-20 Aryl, C 7-20 Alkyl, C 7-20 Aryl alkyl, C 1-20 Alkoxy, C 2-20 Alkoxyalkyl, C 2-20 Heterocyclic alkyl or C 5-20 Mixed aromatics; Q is carbon, silicon, or germanium; M 2 It is a Group 4 transition metal; and X 1 and X 2 They may be the same as or different from each other, and each is independently a halogen, C 1-20 Alkyl, C 2-20 alkenyl, C 6-20 Aryl, nitro, amide, C 1-20 Alkyl silyl, C 1-20 Alkoxy or C 1-20 Sulfonic acid group.

11. The method for preparing the organic-inorganic hybrid polyolefin composite material according to claim 10, wherein, The olefin monomer is selected from at least one group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

12. The method for preparing the organic-inorganic hybrid polyolefin composite material according to claim 10, wherein, The molar ratio of the first metallocene compound to the second metallocene compound is 1:9 to 9:

1.

13. A membrane material manufactured using the organic-inorganic hybrid polyolefin composite material according to any one of claims 1 to 9.

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