KR102692427B1 - Organic-inorgaic hybrid polyolefin composite and preparation method thereof - Google Patents

Abstract

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

Description

Organic-inorganic hybrid polyolefin composite and method for producing the same {ORGANIC-INORGAIC HYBRID POLYOLEFIN COMPOSITE AND PREPARATION METHOD THEREOF}

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

Lithium-ion battery separator (LiBS, Li-ion battery separator) is one of the important materials that determines the lifespan, efficiency, and stability of a battery.

In particular, as it is an important material that contributes highly to battery performance, it requires a variety of required properties, including chemical stability, thickness, porosity, pore size, and mechanical strength. ), wettability, dimensional stability, thermal runaway shutdown, and thermal shrinkage are the representative required properties.

In general, LiBS is made by appropriately mixing polyethylene and polypropylene, which are inexpensive and satisfy chemical stability and mechanical properties, but due to the limitations of olefin polymer, wettability, dimensional stability, thermal runaway barrier properties, thermal shrinkage, etc. It is difficult to satisfy the required properties. To solve this problem, various inorganic materials and additives are added when manufacturing LiBS, but it is difficult to solve the problem of deterioration of physical properties over time due to mixing and dispersion and migration of olefin polymer. there is.

Accordingly, it is possible to solve the mixing, dispersion and migration problems of inorganic materials and olefin polymers when manufacturing lithium-ion battery separators (LiBS), and to control functions such as excellent mechanical properties, wettability, dimensional stability, thermal runaway barrier properties, and low thermal shrinkage rate. The development of polyolefin materials that can be used continues to be required.

The present invention is to provide an organic-inorganic hybrid polyolefin composite and a method for producing the same.

One embodiment of the present invention includes polyolefin and a non-porous inorganic material combined with at least a portion of the polyolefin, wherein the non-porous inorganic material is contained in an amount of 0.4% by weight or more based on the total weight of the organic-inorganic hybrid polyolefin composite. An organic-inorganic hybrid polyolefin composite is provided.

Additionally, in another embodiment of the present invention, a method for producing an organic-inorganic hybrid polyolefin composite according to the above embodiment is provided.

In addition, in another embodiment of the present invention, a material for a separator manufactured using the organic-inorganic hybrid polyolefin composite according to the above embodiment is provided.

The terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention.

Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as “comprise,” “comprise,” or “have” are used to describe implemented features, numbers, steps, components, or combinations thereof, and include one or more other features, numbers, or steps. , does not exclude the possibility of components, combinations or additions thereof.

In addition, the terms "about", "substantially", etc. used throughout this specification are used to mean at or close to that value when manufacturing and material tolerances inherent in the stated meaning are presented, and are used herein to To facilitate understanding, precise or absolute figures are mentioned and are used to prevent unscrupulous infringers from taking unfair advantage of the disclosure.

Additionally, in this specification, when each layer or element is referred to as being formed “on” or “on” each layer or element, it means that each layer or element is formed directly on each layer or element, or other This means that layers or elements can be additionally formed between each layer, on the object, or on the substrate.

Additionally, in the present invention, (co)polymer includes both homo-polymer and co-polymer.

Unless otherwise defined herein, “copolymerization” may mean block copolymerization, random copolymerization, graft copolymerization, or alternating copolymerization, and “copolymer” may mean block copolymer, random copolymer, graft copolymer, or alternating copolymerization. It can mean merging.

Additionally, in this specification, “part by weight” refers to a relative concept expressed as a ratio of the weight of the remaining material based on the weight of a certain material. For example, in a mixture containing 50 g of substance A, 20 g of substance B, and 30 g of substance C, the amounts of substance B and substance C would each be 40 parts by weight based on 100 parts by weight of substance A. parts by weight and 60 parts by weight.

Meanwhile, “% by weight” refers to an absolute concept expressed as a percentage of the weight of a certain material out of the total weight. In the above example mixture, the contents of material A, material B, and material C out of 100% of the total weight of the mixture are 50% by weight, 20% by weight, and 30% by weight, respectively.

Since the present invention can make various changes and take various forms, specific embodiments will be illustrated and described in detail below. However, this does not limit the present invention to the specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, the problems of mixing, dispersion, and migration of inorganic materials and olefin polymers can be solved when manufacturing a lithium-ion battery separator (LiBS), and mechanical properties can be improved depending on the content of inorganic materials. An organic-inorganic hybrid polyolefin composite that can control functions such as wettability, dimensional stability, thermal runaway shutdown, and low thermal shrinkage is provided.

In particular, the organic-inorganic hybrid polyolefin composite includes polyolefin and a non-porous inorganic material combined with at least a portion of the polyolefin, and 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. or 0.4% to 12% by weight.

Specifically, the polyolefin is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -It may be a homopolymer or copolymer of an olefin monomer selected from the group consisting of hexadecene, 1-octadecene, and 1-eicocene. For example, it may be a homopolymer of an olefin monomer, for example, a homopolymer of ethylene or propylene, that is, polyethylene or polypropylene, and more preferably, it may be polyethylene.

In addition, the polyethylene includes low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE), and may be one or a mixture of two or more of these. In particular, the polyethylene is preferably high-density polyethylene, which has a high crystallinity and a high melting point of the resin. However, if necessary, the polyethylene may be a blend of high-density polyethylene and low-density polyethylene.

The organic-inorganic hybrid polyolefin composite of the present invention includes the above-described polyolefin and a non-porous inorganic material combined with at least a portion of the polyolefin.

Specifically, the content of the non-porous inorganic material is 0.4% by weight or more, preferably 0.42% by weight or more, or 0.43% by weight, or 0.44% by weight or more, or 0.45% by weight, based on the total weight of the organic-inorganic hybrid polyolefin composite. % or more, or at least 0.46 weight %, or at least 0.47 weight %, or at least 0.48 weight %, or at least 0.49 weight %, or at least 0.5 weight %. When the content of the non-porous inorganic material is less than 0.4% by weight, it does not function as a filler to bind polyolefin and does not complement the mechanical properties of polyolefin. However, in order to prevent the mechanical properties of the organic-inorganic hybrid polyolefin composite from deteriorating, the content of the non-porous inorganic material may be 12% by weight or less, preferably 10% by weight or less, or 9.8% by weight or less, or 9.5% by weight. % or less, or 9% or less, or 8.8% or less, or 8.6% or less, or 8.5% or less, or 8.4% or less, or 8.3% or less, or 8.2% or less, or 8.1% or less, by weight , or may be 8% by weight or less. For example, if the content of the non-porous inorganic material is included in an excessive amount, for example, exceeding 12% by weight, it acts as an impurity rather than a filler in the organic-inorganic hybrid polyolefin composite, thereby interfering with the creation of a polymer matrix, thereby deteriorating the mechanical properties. There may be a tendency to deteriorate. Accordingly, the content of the non-porous inorganic material is preferably included in the above-mentioned range in terms of securing excellent mechanical properties of the resulting organic-inorganic hybrid polyolefin composite.

In particular, the inorganic material of the present invention may be a non-porous material with a smooth surface without any pores, or a material with slight irregularities on the surface that cannot be considered pores. . These non-porous inorganic materials may have a specific surface area of 100 m ² /g or less or 2 m ² /g to 100 m ² /g. The specific surface area is a value calculated using the generally known BET (Brunauer-Emmett-Teller) equation, and may be a value measured according to the International Organization for Standardization ISO 9277 method.

Specifically, the specific surface area of the non-porous inorganic material is 95 m ² /g or less, or 85 m ² /g or less, or 80 m ² /g or less, or 70 m ² /g or less, or 60 m ² /g or less, or 55 m ² /g or less, or 50 m ² /g or less, or 45 m ² /g or less, or 40 m ² /g or less, or 35 m ² /g or less, or 30 m It may be ² /g or less, or 25 m ² /g or less, or 20 m ² /g or less, or 18 m ² /g or less. In particular, the non-porous inorganic material is not broken during the olefin polymerization process and is included in the above-described content range in the polyolefin composite, and can satisfy the above-mentioned specific surface area in terms of securing excellent mechanical properties. However, considering the actual air gap characteristics of an inorganic material, it is 2 m ² /g or more, or 4 m ² /g or more, or 6 m ² /g or more, or 8 m ² /g or more, or 10 m ² /g or more. , or may be more than 12 m ² /g.

In addition, the non-porous inorganic material may be fine particles with a size of 30 nm to 2 ㎛, and specifically, the particle size is 50 nm or more, or 60 nm or more, or 70 nm or more, or 80 nm or more, or 100 nm or more. And, it may be 1.8 ㎛ or less, or 1.5 ㎛ or less, or 1.2 ㎛ or less, or 1.0 ㎛ or less.

Additionally, the non-porous inorganic material may have uniform particle size and may have a spherical or circular shape.

Specifically, the non-porous inorganic material may contain one or more of hydroxy groups or siloxane groups on the surface, and may preferably contain highly reactive hydroxy groups and siloxane groups on the surface. For example, the amount of hydroxyl groups on the surface of the inorganic material is preferably about 0.1 mmol/g to about 10 mmol/g, and more preferably about 0.5 mmol/g to about 5 mmol/g.

Additionally, the non-porous inorganic material may be one or more selected from the group consisting of alumina, magnesia, zirconia, zeolite, and silica, or a mixture of two or more. For example, the non-porous inorganic material may be silica, silica-alumina, or silica-magnesia, and is preferably silica.

For example, if the non-porous inorganic material is silica, it may be synthesized by the Stober method (Stober, W. and A. Fink, Bohn, Journal of Colloid and Interface Science, 1986, 26, 62). According to this method, silica nanoparticles are formed as tetraethyl orthosilicate (TEOS), a silica precursor, is hydrolyzed in an aqueous-alkaline solvent to which an alkaline catalyst is added. Here, ammonia water (NH ₃ ), sodium hydroxide (NaOH), etc. can be used as a catalyst.

Additionally, in the organic-inorganic hybrid polyolefin composite of the present invention, the non-porous inorganic material is chemically bonded to at least some of the polyolefins described above. Specifically, it may form one or more chemical bonds, such as a covalent bond or a coordinate bond. Here, a covalent bond refers to a bond created by two atoms sharing an electron pair, and a coordination bond refers to a bond created by sharing a lone pair of electrons of one atom with the other atom.

Specifically, the above-mentioned chemical bond may be formed through a substituent such as a hydroxy group or siloxane group present on the surface of the non-porous inorganic material.

In the organic-inorganic hybrid polyolefin composite of the present invention, the non-porous inorganic material may be directly bonded to at least some of the above-described polyolefins or bonded through one or more of a catalytically active component and a cocatalyst derived from a polymerization process. For example, the non-porous inorganic material forms a chemical bond with one or more of the catalytically active ingredient and the cocatalyst through a substituent such as a hydroxy group or a siloxane group present on the surface, and then directly with at least some of the above-described polyolefins. It may be that a chemical bond has been formed. For example, in the organic-inorganic hybrid polyolefin composite, a chemical bond is formed with a co-catalyst on the surface of the non-porous inorganic material described above, a chemical bond is formed with the co-catalyst and the catalytically active component, and the catalytically active component and ethylene are formed. A covalent bond may be formed through a coordination and polymerization reaction with an olefin monomer.

Meanwhile, the organic-inorganic hybrid polyolefin composite is not very important as long as it can be molded into a sheet shape, but for applications that require strong physical properties, such as lithium-ion battery separators (LiBS), the larger the molecular weight, the better. In this respect, the weight average molecular weight of a preferred organic-inorganic hybrid polyolefin composite may be about 300,000 g/mol or more, or about 300,000 g/mol to about 1,500,000 g/mol. More preferably, the weight average molecular weight of the organic-inorganic hybrid polyolefin composite may be about 300,500 g/mol or more, or about 300,800 g/mol or more, or about 301,000 g/mol or more, or about 301,300 g/mol or more. However, in terms of practical processability, such as by molding into a sheet shape, the weight average molecular weight of the organic-inorganic hybrid polyolefin composite is about 1,400,000 g/mol or less, or about 1,250,000 g/mol or less, or about 1,100,000 g/mol or less, or about It may be less than or equal to 1,000,000 g/mol, or less than or equal to about 800,000 g/mol, or less than or equal to about 600,000 g/mol, or less than or equal to about 500,000 g/mol.

In addition, the number average molecular weight of the organic-inorganic hybrid polyolefin composite may be about 85,000 g/mol or more, or about 85,000 g/mol to about 150,000 g/mol, and preferably about 86,000 g/mol or more, or about 86,500 g/mol. mol or more, or about 87,000 g/mol or more, or 87,500 g/mol or more. In addition, the number average molecular weight of the organic-inorganic hybrid polyolefin composite is about 140,000 g/mol or less, or about 125,000 g/mol or less, or about 110,000 g/mol or less, or about 105,000 g/mol or less, or about 100,000 g/mol. or less, or less than or equal to about 98,000 g/mol or less than or equal to about 95,000 g/mol.

In addition, the organic-inorganic hybrid polyolefin composite may have a molecular weight distribution (Mw/Mn) of 2.5 to 4.5, specifically 2.7 or more, or 2.85 or more, or 3 or more, or 3.2 or more, and 4.3 or less, or 4.0 or less, or It may be 3.8 or less, or 3.5 or less. In particular, when manufacturing the organic-inorganic hybrid polyolefin composite into a lithium-ion battery separator (LiBS), it is desirable to maintain the above-mentioned range in terms of securing excellent mechanical properties.

The weight average molecular weight, number average molecular weight, and molecular weight distribution of the organic-inorganic hybrid polyolefin composite may be polystyrene conversion weight average molecular weight, number average molecular weight, and molecular weight distribution measured by GPC method, and the specific measurement method is a test example described later. You can refer to it.

As an example, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the organic-inorganic hybrid polyolefin composite were measured using gel permeation chromatography (GPC, manufactured by Water), and as described later, polystyrene It can be calculated using the conversion method. In addition, the molecular weight distribution (Mw/Mn) of the organic-inorganic hybrid polyolefin composite can be obtained by dividing the weight average molecular weight measured in this way by the number average molecular weight.

Specifically, as a gel permeation chromatography (GPC) device, a Waters PL-GPC220 device can be used, and a Polymer Laboratories PLgel MIX-B 300 mm long column can be used. At this time, the measurement temperature is 160 ^o C, 1,2,4-trichlorobenzene can be used as a solvent, and the flow rate can be applied at 1 mL/min. Samples of the organic-inorganic hybrid polyolefin composite were pretreated by melting them in 1,2,4-Trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 ^o C for 10 hours using a GPC analysis device (PL-GP220). It can be measured by preparing it at a concentration of 10 mg/10 mL and then supplying it in an amount of 200 μL. Additionally, the values of Mw and Mn can be derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of polystyrene standard specimens is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g. Nine types of /mol can be used.

Meanwhile, the organic-inorganic hybrid polyolefin composite has an elastic modulus (Young's modulus) measured according to the American Society for Testing and Materials standard ASTM D 638 method of about 250 MPa or more, or about 280 MPa or more, or about 285 MPa or more, or about 290 MPa or more. MPa or greater, or about 295 MPa or greater, or about 300 MPa or greater, or about 305 MPa or greater. Additionally, the elastic modulus (Young's modulus) may be about 800 MPa or less, or about 750 MPa or less, or about 700 MPa or less, or about 650 MPa or less, or about 600 MPa or less, about 550 MPa or less, or about 500 MPa or less. there is. In particular, the organic-inorganic hybrid polyolefin composite has a larger elastic modulus (Young's modulus) for applications that require strong physical properties, such as lithium-ion battery separators (LiBS). In this aspect, the elastic modulus (Young's modulus) may be 285 MPa or more, or 290 MPa or more, or 295 MPa or more, or 300 MPa or more, or 305 MPa or more.

In addition, the organic-inorganic hybrid polyolefin composite has a wettability characteristic (Wettability) measured according to the American Society for Testing and Materials standard ASTM D 5946 method, that is, a contact angle with water (Degree, ^o ) of 45 ^o or less or 15 ^o to 45 ^o. It can be. Preferably, the contact angle with water may be 44 ^o or less, or 43 ^o or less, or 42 ^o or less, or 40 ^{o or} less. As described above, the organic-inorganic hybrid polyolefin composite has a low contact angle, which means it has good wettability by water, and has the advantage that electrolyte can easily penetrate when applied to a lithium-ion battery separator (LiBS). In terms of wettability, the lower the contact angle for water, the better, but depending on the water-repellent characteristics of the polymer film itself, it may be 18 ^o or more, or 20 ^o or more, or 25 ^o or more, or 30 ^o or more.

In addition, the organic-inorganic hybrid polyolefin composite may have excellent dimensional stability with a thermal shrinkage (90 ^o C, 60 min) of 5% or less, or 3% or less. As an example, using the organic-inorganic hybrid polyolefin composite, a film specimen was manufactured according to the American Society for Testing and Materials standard ASTM D 5946 test method, the film specimen was left at 140 ^o C for 1 hour, and the film specimen was left before and after leaving. When measuring the area, the area of the film specimen after being left may be 95% or more, 96% or more, or 97% or more of the area before leaving.

Meanwhile, according to another embodiment of the invention, a method for producing the above-described organic-inorganic hybrid polyolefin composite is provided.

In particular, in the present invention, when manufacturing a lithium ion battery separator (LiBS), an olefin polymer is produced after combining a catalyst with an inorganic material. In this way, the mixing, dispersion, and migration problems of inorganic materials and olefin polymers can be solved, and the mechanical properties, wettability, and dimensional stability can be improved depending on the content of the inorganic material. ), it is possible to manufacture an organic-inorganic hybrid polyolefin composite that can control functions such as thermal runaway shutdown, low thermal shrinkage, etc.

The method for producing an organic-inorganic hybrid polyolefin composite of the present invention includes at least one first metallocene compound represented by the following formula (1); and polymerizing the olefin monomer in the presence of a catalyst composition in which a catalytically active component containing at least one second metallocene compound selected from the compounds represented by the following formula (2) is bonded to a non-porous inorganic material.

[Formula 1]

(Cp ¹ R ^a ) _n (Cp ² R ^b )M ¹ Q ¹ _3-n

In Formula 1,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical. one, and they are substituted or unsubstituted with C _1-20 hydrocarbons;

R ^a and R ^b are the same or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ^a and R ^b is not hydrogen;

Q ¹ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene, substituted or unsubstituted amino group, C _2-20 alkoxyalkyl, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

n is 1 or 0;

[Formula 2]

In Formula 2,

R ¹ to R ¹⁷ are the same as or different from each other, and are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 is arylalkyl;

L is C _1-10 straight or branched chain alkylene;

D is -O-, -S-, -N(R)- or -Si(R)(R')-, where R and R' are the same or different from each other and are each independently hydrogen, halogen, C _{1 -20} alkyl, C _2-20 alkenyl, or C _6-20 aryl;

A is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxy alkyl, C _2-20 heterocycloalkyl, or C _5-20 heteroaryl;

Q is carbon, silicon or germanium;

M ² is a Group 4 transition metal;

_X ^{1 and} _{​ ​ ​ 1-20} alkoxy, or C _1-20 sulfonate group.

The substituents are described in more detail as follows.

Hydrocarbyl group is a monovalent functional group obtained by removing a hydrogen atom from hydrocarbon, and includes alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, aralkenyl group, aralkynyl group, alkylaryl group, alkenylaryl group, and alkyl group. It may include a nylaryl group, etc. And, the C _1-30 hydrocarbyl group may be a C _1-20 or C _1-10 hydrocarbyl group. As an example, the hydrocarbyl group may be straight chain, branched chain, or cyclic alkyl. More specifically, the hydrocarbyl group of C _1-30 is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hexyl group. Straight-chain, branched-chain, or cyclic alkyl groups such as actual group, n-heptyl group, and cyclohexyl group; Alternatively, it may be an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. Additionally, it may be alkylaryl such as methylphenyl, ethylphenyl, methylbiphenyl, and methylnaphthyl, and may also be arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, and naphthylmethyl. Additionally, it may be alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, and pentenyl.

A hydrocarbyloxy group is a functional group in which a hydrocarbyl group is bonded to oxygen. Specifically, the C _1-30 hydrocarbyloxy group may be a C _1-20 or C _1-10 hydrocarbyloxy group. For example, the hydrocarbyloxy group may be straight chain, branched chain, or cyclic alkyl. More specifically, the hydrocarbyloxy group of C _1-30 is methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group. , straight-chain, branched-chain, or cyclic alkoxy groups such as n-hexoxy group, n-heptoxy group, and cyclohexoxy group; Alternatively, it may be an aryloxy group such as a phenoxy group or a naphthalenoxy group.

Hydrocarbyloxyhydrocarbyl group is a functional group in which one or more hydrogens of the hydrocarbyl group are replaced with one or more hydrocarbyloxy groups. Specifically, the C _2-30 hydrocarbyloxyhydrocarbyl group may be a C _2-20 or C _2-15 hydrocarbyloxyhydrocarbyl group. For example, the hydrocarbyloxyhydrocarbyl group may be straight chain, branched chain, or cyclic alkyl. More specifically, the hydrocarbyloxyhydrocarbyl group of C _2-30 is methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-part Alkoxyalkyl groups such as toxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group; Or it may be an aryloxyalkyl group such as a phenoxyhexyl group.

Hydrocarbyl (oxy)silyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are replaced with 1 to 3 hydrocarbyl groups or hydrocarbyloxy groups. Specifically, the C _1-30 hydrocarbyl (oxy) silyl group may be a C _1-20 , C _1-15 , C _1-10 , or C _1-5 hydrocarbyl (oxy) silyl group. More specifically, the hydrocarbyl (oxy)silyl group of C _1-30 is an alkyl group such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group, or dimethylpropylsilyl group. silyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; It may be an alkoxyalkyl silyl group such as methoxydimethylsilyl group, diethoxymethylsilyl group, or dimethoxypropylsilyl group.

Additionally, a silylhydrocarbyl group having 1 to 20 carbon atoms (C _1-20 ) is a functional group in which one or more hydrogens of the hydrocarbyl group are replaced with a silyl group. The silyl group may be -SiH ₃ or a hydrocarbyl (oxy)silyl group. Specifically, the C _1-20 silylhydrocarbyl group may be a C _1-15 or C _1-10 silylhydrocarbyl group. More specifically, the C _1-20 silylhydrocarbyl group is a silylalkyl group such as -CH ₂ -SiH ₃ ; Alkylsilylalkyl groups such as methylsilylmethyl group, methylsilylethyl group, dimethylsilylmethyl group, trimethylsilylmethyl group, dimethylethylsilylmethyl group, diethylmethylsilylmethyl group, or dimethylpropylsilylmethyl group; Or it may be an alkoxysilylalkyl group such as dimethylethoxysilylpropyl group.

Halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

Alkyl having 1 to 20 carbon atoms (C _1-20 ) may be straight-chain, branched-chain, or cyclic alkyl. Specifically, alkyl having 1 to 20 carbon atoms includes straight chain alkyl having 1 to 20 carbon atoms; Straight-chain alkyl having 1 to 15 carbon atoms; Straight-chain alkyl having 1 to 5 carbon atoms; Branched chain or cyclic alkyl having 3 to 20 carbon atoms; Branched chain or cyclic alkyl having 3 to 15 carbon atoms; Alternatively, it may be branched chain or cyclic alkyl having 3 to 10 carbon atoms. For example, the alkyl having 1 to 20 carbon atoms (C _1-20 ) is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl. , cyclohexyl, cycloheptyl, cyclooctyl, etc., but is not limited thereto.

Alkenyl having 2 to 20 carbon atoms (C _2-20 ) includes straight or branched chain alkenyl, and specifically includes allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, etc. It is not limited to this.

Alkoxy groups having 1 to 20 carbon atoms (C _1-20 ) include methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, and cyclohexyloxy group, but are not limited thereto. .

The alkoxyalkyl group having 2 to 20 carbon atoms (C _2-20 ) is a functional group in which one or more hydrogens of the above-mentioned alkyl are replaced with alkoxy, and specifically, methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, Alkoxyalkyl such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl may be mentioned. It is not limited to this.

The alkylsilyl group having 1 to 20 carbon atoms (C _1-20 ) or the alkoxysilyl group having 1 to 20 carbon atoms (C _1-20 ) is a group in which 1 to 3 hydrogens of -SiH ₃ are replaced with 1 to 3 alkyl or alkoxy as described above. It is a substituted functional group, and specifically, alkylsilyl such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl, or dimethylpropylsilyl; Alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl, or dimethoxyethoxysilyl; Alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl may be included, but is not limited thereto.

Silylalkyl having 1 to 20 carbon atoms (C _1-20 ) is a functional group in which one or more hydrogens of the above-described alkyl are replaced with silyl, and specifically, examples thereof include, but are not limited to, -CH ₂ -SiH ₃ , methylsilylmethyl, or dimethylethoxysilylpropyl.

In addition, alkylene or alkylidene having 1 to 20 carbon atoms (C _1-20 ) is the same as the alkyl described above except that it is a divalent substituent, and specifically includes methylene, ethylene, propylene, butylene, pentylene, and hexylene. , heptylene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, etc., but is not limited thereto.

Aryl having 6 to 20 carbon atoms (C _6-20 ) may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. For example, the aryl having 6 to 20 carbon atoms (C _6-20 ) includes phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, etc., but is not limited thereto.

Alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may refer to a substituent in which one or more hydrogens of the aromatic ring are replaced by the above-mentioned alkyl. For example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) includes methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, etc., but is not limited thereto.

The arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may refer to a substituent in which one or more hydrogens of the alkyl described above are replaced by the aryl described above. For example, the arylalkyl having 7 to 20 carbon atoms (C _7-20 ) includes phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl, etc., but is not limited thereto.

In addition, arylene or arylidene having 6 to 20 carbon atoms (C _6-20 ) is the same as the aryl described above except that it is a divalent substituent, and is specifically phenylene, biphenylene, naphthylene, and anthracenylene. , phenanthrenylene, fluorenylene, etc., but is not limited thereto.

Aryloxy having 6 to 40 carbon atoms (C _6-40 ) includes phenoxy, biphenoxy, naphthoxy, etc., but is not limited thereto.

The aryloxyalkyl group having 7 to 40 carbon atoms (C _7-40 ) is a functional group in which one or more hydrogens of the above-mentioned alkyl are substituted with aryloxy, and specific examples include phenoxymethyl, phenoxyethyl, and phenoxyhexyl. , but is not limited to this.

And, the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherphodium (Rf), and specifically, titanium (Ti), zirconium (Zr), or hafnium (Hf). It may be, and more specifically, it may be zirconium (Zr) or hafnium (Hf), but it is not limited thereto.

Additionally, the Group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and may specifically be boron (B) or aluminum (Al). and is not limited to this.

The above-mentioned substituents are optionally hydroxy groups within the range of having the same or similar effect as the desired effect; halogen; hydrocarbyl group; hydrocarbyloxy group; A hydrocarbyl group or hydrocarbyloxy group containing one or more heteroatoms from groups 14 to 16; silyl group; Hydrocarbyl (oxy)silyl group; Phosphine group; phosphide group; Sulfonate group; and may be substituted with one or more substituents selected from the group consisting of a sulfone group.

Meanwhile, in the method for producing an organic-inorganic hybrid polyolefin composite of the present invention, the catalyst composition includes a low copolymerizability first metallocene compound and a second metallocene compound having high molecular weight characteristics during ethylene polymerization as catalytically active ingredients. Therefore, it exhibits high activity along with excellent process stability in olefin polymerization, and has characteristics useful for manufacturing polyolefin composites with excellent mechanical properties due to high bonding characteristics between catalytically active ingredients and non-porous inorganic materials.

Specifically, in Formula 1, M ¹ may be zirconium (Zr) or hafnium (Hf), and preferably zirconium (Zr).

And, in Formula 1, Cp ¹ and Cp ² may each be cyclopentadienyl, indenyl, or fluorenyl, and preferably at least one of Cp ¹ and Cp ² is cyclopentadienyl or indenyl. . More preferably, both Cp ¹ and Cp ² may be cyclopentadienyl.

Cp ¹ and Cp ² may be unsubstituted or substituted with at least one C _1-20 hydrocarbon. For example, Cp ¹ and Cp ² may be substituted with one or more of a C _1-10 hydrocarbyl group, a C _1-10 hydrocarbyloxy group, or a C _1-10 hydrocarbyloxyhydrocarbyl group, Specifically, it may be substituted with one or more of methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, tert-butoxyhexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl. there is.

More specifically, in the first metallocene compound, Cp ¹ and Cp ² may be the same or different from each other, and preferably, Cp ¹ and Cp ² may be the same as each other and include the same substituents, thereby forming a symmetrical structure.

And, R ^a and R ^b are each hydrogen, C _1-6 straight-chain or branched alkyl, C _2-6 alkynyl, C _1-6 alkoxy substituted C _1-6 alkyl, C _6-12 Aryl may be substituted C _1-6 alkyl, or C _6-12 aryl, provided that at least one of R ^a and R ^b is not hydrogen. In particular, R ^a and R ^b may be the same or different from each other, preferably the same as each other, and Formula 1 may have a symmetrical structure. For example, R ^a and R ^b are each hydrogen, methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (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 It may be phenyl (Ph). Preferably, at least one of R ^a and R ^b is tert-butoxyhexyl, and the others are hydrogen, methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (i- Pr), n-butyl (n-Bu), tert-butyl (t-Bu), n-pentyl (n-Pt), n-hexyl (n-Hex), tert-butoxy (t-Bu-O) It may be hexyl, butenyl, phenylpropyl, phenylhexyl, or phenyl (Ph). More preferably, at least one of each of R ^a and R ^b may be tert-butoxyhexyl, and the remainder may be hydrogen.

And, in Formula 1, Q ¹ may each be a halogen, and specifically, may be chlorine.

And, in Formula 1, n is 1 or 0, and preferably n is 1.

Meanwhile, the first metallocene compound may be represented by any one of the following formulas 1-1 to 1-5.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 to 1-5, M ¹ and Q ¹ are as defined in Formula 1,

R' and R" are the same or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R At least one of ' and R" is not hydrogen;

m1 is each independently an integer from 1 to 8.

m2 is each independently an integer from 1 to 6.

More preferably, the first metallocene compound may be represented by Chemical Formula 1-1.

And, in the above formulas 1-1 to 1-5, R' and R" are each hydrogen, C _1-6 linear or branched alkyl, C _2-6 alkynyl, C _1-6 alkoxy substituted C It may be _1-6 alkyl, C _6-12 aryl substituted C _1-6 alkyl, or C _6-12 aryl, provided that at least one of R' and R" is not hydrogen. Specifically, at least one of R' and R" is methyl (Me), ethyl (Et), n-propyl (n-Pr), iso-propyl (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 may be hydrogen. More specifically, at least one of R' and R" may be tert-butoxy(t-Bu-O)hexyl, and the remainder may be hydrogen. may be hydrogen.

And, in the above formulas 1-1 to 1-5, m1 and m2 are each integers of 1 to 4, and are preferably 1 or 2, respectively.

Specifically, the first metallocene compound may be represented by one of the following structural formulas.

.

.

The first metallocene compounds represented by the above structural formulas can be synthesized by applying known reactions, and the examples can be referred to for more detailed synthesis methods.

Meanwhile, in the method for producing an organic-inorganic hybrid polyolefin composite of the present invention, the catalyst composition is characterized in that it includes a second metallocene compound represented by the formula (2) together with the first metallocene compound described above.

Specifically, in Formula 2, M ² may be zirconium (Zr) or hafnium (Hf), and preferably may be zirconium (Zr). Additionally, Q may be silicon (Si).

In addition, R ¹ to R ¹⁷ may each be hydrogen, C _1-8 alkyl, C _2-8 alkenyl, or C _6-12 aryl, and are preferably methyl, ethyl, propyl, isopropyl, n-butyl, It may be tert-butyl, pentyl, hexyl, heptyl, octyl, or phenyl, but is not limited thereto. Specifically, R ¹ to R ¹⁶ may be hydrogen, C _1-8 alkyl, C _1-5 alkyl, or C _1-3 alkyl, and R ¹⁷ may be C _1-8 alkyl, C _1-5 alkyl, or It may be C _1-3 alkyl. More specifically, R ¹ to R ¹⁶ may be hydrogen, and R ¹⁷ may be methyl.

Additionally, L is more preferably a C _4-8 straight or branched alkylene, but is not limited thereto. Additionally, the alkylene group may be substituted or unsubstituted with C _1-20 alkyl, C _2-20 alkenyl, or C _6-20 aryl. Specifically, L may be a C _5-7 straight or branched chain alkylene. Preferably, L may be hexylene.

Also, D may be -O-.

Additionally, A may be hydrogen, C _1-6 alkyl, C _1-6 alkoxy, C _2-12 alkoxyalkyl, or C _5-12 heteroaryl, but is not limited thereto. Specifically, A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, 1-ethoxyethyl group, 1-methyl-1- It may be a methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group. Preferably, A may be a tert-butyl group.

Additionally, X ¹ and X ² may each be a halogen, for example, chlorine (Cl), bromine (Br), or iodine (I), and preferably chlorine (Cl).

Specifically, the compound represented by Formula 2 may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The second metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and the examples can be referred to for more detailed synthesis methods.

In the catalyst composition of the present invention, the first metallocene compound and the second metallocene compound may be included in a molar ratio of about 1:9 to about 9:1. By including the first and second metallocene compounds in the above mixing molar ratio, excellent supporting performance, catalytic activity, and high copolymerization properties can be exhibited. In particular, when polyolefin is manufactured in a slurry process using this catalyst composition, process stability is improved and fouling problems that have occurred in the past can be prevented. In particular, if the support ratio of the first metallocene compound and the second metallocene compound exceeds about 9:1, only the first metallocene compound plays a dominant role, and copolymerization may be reduced. In addition, if the support ratio is less than about 1:9, only the second metallocene compound plays a dominant role, making it difficult to reproduce the molecular structure of the desired polymer.

Specifically, the first metallocene compound and the second metallocene compound have a molar ratio of about 1:5 to about 5:1, or a molar ratio of about 1:4 to about 4:1, or about A molar ratio of 1:3 to about 3:1, or from about 1:1.5 to about 2.8:1, or from about 1:1.8 to about 2.6:1, or from about 1:2 to about 2.5:1, or from about 1:2 to about 1:2. A catalyst composition containing a molar ratio of about 2.4:1, or about 1:21 to about 2.3:1, is preferred for producing polyolefin with improved mechanical properties due to excellent copolymerization 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 It may be about 1:21 to about 2.3:1.

That is, in the case of a catalyst composition containing the first metallocene compound and the second metallocene compound in the molar ratio, the film properties of polyolefin can be further improved due to the interaction of two or more catalysts.

In the method for producing a plate, an organic-inorganic hybrid polyolefin composite of the present invention, a catalytically active component containing at least one first metallocene compound and at least one first metallocene compound described later is bonded to a non-porous inorganic material. Characterized in that olefin monomers are polymerized in the presence of a catalyst composition, and the content of the non-porous inorganic material is about 0.4% by weight or more or about 0.4% by weight to about 12% by weight based on the total weight of the organic-inorganic hybrid polyolefin composite. .

The content of this non-porous inorganic material can be adjusted by varying the content ratio of the non-porous inorganic material used in the catalyst composition and the olefin monomer added to the polymerization process, or by varying the ratio of polyolefin produced according to the polymerization reaction conditions. . For example, even when the content of the non-porous inorganic material in the catalyst composition and the content of the olefin monomer in the polymerization process are applied the same, the temperature, pressure, and reaction time are varied according to the polymerization process conditions, compared to the total weight of the final organic-inorganic hybrid polyolefin composite produced. The content of non-porous inorganic material can be optimized to the above-mentioned range.

Specifically, the content of the non-porous inorganic material is about 0.4% by weight or more based on the total weight of the olefin monomer, non-porous inorganic material, catalytic active ingredient, and cocatalyst included in the catalyst composition, and is preferably added. is at least about 0.42% by weight, or at least about 0.43% by weight, or at least about 0.44% by weight, or at least about 0.45% by weight, or at least about 0.46% by weight, or at least about 0.47% by weight, or at least about 0.48% by weight, or It can be added in an amount of 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 to bind polyolefin and does not complement the mechanical properties of polyolefin. However, in order to prevent the mechanical properties of the organic-inorganic hybrid polyolefin composite from being deteriorated, the content of the non-porous inorganic material may be about 12% by weight or less based on the total weight of the olefin monomer and the inorganic material, and is preferably about 12% by weight or less. 10 wt% or less, or about 9.8 wt% or less, or about 9.5 wt% or less, or about 9 wt% or less, or about 8.8 wt% or less, or about 8.6 wt% or less, or about 8.5 wt% or less, or about 8.4 wt% or less. It may be less than or equal to about 8.3 weight percent, or less than or equal to about 8.2 weight percent, or less than or equal to about 8.1 weight percent, or less than or equal to about 8 weight percent. For example, when the content of the non-porous inorganic material is included in too much, for example, exceeding about 12% by weight, it acts as an impurity rather than a filler in the organic-inorganic hybrid polyolefin composite, preventing the creation of a polymer matrix. As a result, mechanical properties may tend to deteriorate. Accordingly, the content of the non-porous inorganic material is preferably included in the above-mentioned range in terms of securing excellent mechanical properties of the resulting organic-inorganic hybrid polyolefin composite.

In particular, the inorganic material of the present invention may be a non-porous material with a smooth surface without any pores, or a material with slight irregularities on the surface that cannot be considered pores. . The characteristics of this non-porous inorganic material are the same as previously described in relation to the organic-inorganic hybrid polyolefin composite, and detailed description will be omitted.

Additionally, in the catalyst composition of the present invention, the total amount of catalytically active ingredients including at least one type of the first metallocene compound and at least one type of the second metallocene compound is 1 g of the above-described non-porous inorganic material. Based on 0.001 mmol/g or more, or 0.003 mmol/g or more, or 0.005 mmol/g or more, or 0.008 mmol/g or more, and 1 mmol/g or less, or 0.99 mmol/g or less, or 0.98 mmol/g or less. , or may be 0.95 mmol/g or less. That is, it is desirable to control the amount to fall within the above-mentioned range, taking into account the contribution effect of the metallocene compound as a catalyst.

Meanwhile, the combination of the catalytically active ingredient and the inorganic material is such that the ICP analysis result of the transition metal is 0.1 ppm or less, or 0.01 ppm or less, for the filtrate obtained in the filter process for finally obtaining the solid catalyst composition during the manufacturing process of the catalyst composition. This can be confirmed.

In the method for producing an organic-inorganic hybrid polyolefin composite of the present invention, the catalyst composition includes a catalytically active ingredient and an inorganic material comprising at least one type of the first metallocene compound and one or more types of the second metallocene compound It may include a co-catalyst compound. The cocatalyst may be any cocatalyst used when polymerizing olefins under a general metallocene catalyst. This co-catalyst causes a bond to be created between the hydroxyl group in the inorganic material and the Group 13 transition metal. In addition, since the cocatalyst exists only on the surface of the inorganic material, it can contribute to securing the unique characteristics of the catalyst composition of the present invention without fouling phenomenon in which polymer particles stick to the reactor wall or each other.

In addition, the catalyst composition of the present invention may further include one or more cocatalysts selected from the group consisting of compounds represented by the following formulas 3 to 5.

[Formula 3]

-[Al(R ³¹ )-O] _c -

In Formula 3 above,

R ³¹ is each independently halogen, C _1-20 alkyl, or C _1-20 haloalkyl,

c is an integer greater than or equal to 2,

[Formula 4]

D(R ⁴¹ ) ₃

In Formula 4 above,

D is aluminum or boron,

R ⁴¹ is each independently hydrogen, halogen, C _1-20 hydrocarbyl, or C _1-20 hydrocarbyl substituted with halogen,

[Formula 5]

[LH] ⁺ [Q(E) ₄ ] ^- or [L] ⁺ [Q(E) ₄ ] ^-

In Formula 5 above,

L is a neutral or cationic Lewis base,

Q is B ³⁺ or Al ³⁺ ,

E is each independently C _6-40 aryl or C _1-20 alkyl, wherein the C _6-40 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, C _1-20 alkoxy, and C _6-40 aryloxy.

Specifically, in Formula 5, [LH] ⁺ is Bronsted acid.

The compound represented by Formula 3 may be, for example, an alkyl aluminoxane such as methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, etc.

The alkyl metal compound represented by the formula 4 is, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloroaluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro. Aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl It may be aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc.

Compounds represented by Formula 5 include, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (p- Tolyl) boron, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N, N-dimethylanilinium tetraphenyl boron, N, N -Diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenyl Boron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium 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 Tetrapentafluorophenyl Aluminum, N,N-Dimethylanilinium Tetraphenyl Aluminum, N,N-Diethylanilinium Tetraphenyl Aluminum, N,N-Diethylanilinium Tetrapentafluorophenyl Aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarbonium It may be umtetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, etc.

In addition, the catalyst composition may include the cocatalyst and the first metallocene compound at a molar ratio of about 1:1 to about 1:10000, preferably at a molar ratio of about 1:1 to about 1:1000. It can be done, and more preferably, it can be included in a molar ratio of about 1:10 to about 1:100.

In addition, the catalyst composition may also include the cocatalyst and the second metallocene compound at a molar ratio of about 1:1 to about 1:10000, preferably at a molar ratio of about 1:1 to about 1:1000. It can be done, and more preferably, it can be included in a molar ratio of about 1:10 to about 1:100.

At this time, if the molar ratio is less than about 1, the metal content of the cocatalyst is too small and catalytic active species are not formed well, which may lower activity. If the molar ratio exceeds about 10,000, there is a risk that the metal in the cocatalyst may act as a catalyst poison. there is.

The amount of this co-catalyst may be from about 5 mmol to about 20 mmol based on 1 g of the inorganic material.

Meanwhile, the catalyst composition includes the steps of supporting a cocatalyst on an inorganic material; Supporting a first metallocene compound on an inorganic material supporting the cocatalyst; and supporting a second metallocene compound on an inorganic material supporting the cocatalyst and the first metallocene compound.

Alternatively, the catalyst composition may include the steps of supporting a cocatalyst on an inorganic material; Supporting a second metallocene compound on the inorganic material supporting the cocatalyst; and supporting the first metallocene compound on an inorganic material supporting the cocatalyst and the second metallocene compound.

Alternatively, the catalyst composition may include the steps of supporting a first metallocene compound on an inorganic material; Supporting a cocatalyst on an inorganic material supporting the first metallocene compound; and supporting a second metallocene compound on an inorganic material supporting the cocatalyst and the first metallocene compound.

In the above method, the loading conditions are not particularly limited and can be performed within a range well known to those skilled in the art. For example, high-temperature loading and low-temperature loading can be appropriately used. For example, the loading temperature may range from about -30 ^o C to about 150 ^o C, and preferably from about 50 ^o C to about 98 o C. ^o C, or about 55 ^o C to about 95 ^o C. The loading time can be appropriately adjusted depending on the amount of the first metallocene compound to be loaded. The reacted supported catalyst can be used as is by removing the reaction solvent by filtration or distillation under reduced pressure. If necessary, it can be used after Soxhlet filtering with an aromatic hydrocarbon such as toluene.

In addition, the preparation of the catalyst composition may be performed under a solvent or without a solvent. If a solvent is used, acceptable solvents include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with a chlorine atom such as dichloromethane, diethyl ether or tetrahydrofuran (THF). ), ether-based solvents such as acetone, and most organic solvents such as ethyl acetate, and hexane, heptane, toluene, or dichloromethane are preferred. At this time, by treating the solvent with a small amount of alkyl aluminum, etc., a small amount of water or air that may adversely affect the catalyst can be removed in advance.

Meanwhile, the method for producing an organic-inorganic hybrid polyolefin composite of the present invention includes the step of polymerizing olefin monomers in the presence of the catalyst composition described above.

Specifically, the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, It may be one or more selected from the group consisting of 1-hexadecene, 1-octadecene, and 1-eicocene. Preferably, homopolymerization or copolymerization can be performed using ethylene or propylene.

For the polymerization reaction of the olefin monomer, various polymerization processes known as the polymerization reaction of the olefin monomer, such as a continuous solution polymerization process, bulk polymerization process, suspension polymerization process, slurry polymerization process, or emulsion polymerization process, can be employed. More specifically, , the polymerization reaction can be carried out in a semi-batch reactor.

Additionally, in the polymerization reaction of the olefin monomer, the polymerization may proceed in the presence of an inert gas such as nitrogen in a polymerization reactor. The inert gas can play a role in maintaining the reaction activity of the metallocene compound contained in the catalyst composition for a long time by suppressing the rapid reaction of the metallocene compound, which is a catalytically active component, at the beginning of the polymerization reaction.

In addition, in the polymerization reaction, hydrogen gas may be used for the purpose of controlling the molecular weight and molecular weight distribution of polyolefin.

The polymerization reaction temperature may be about 50°C to about 110°C, or about 60°C to about 105°C, or about 70°C to about 100°C, or about 72°C to about 90°C, or about 75°C, or about 83°C. there is. If the polymerization reaction temperature is too low, it is not appropriate in terms of polymerization speed and productivity, and conversely, if the polymerization reaction temperature is higher than necessary, a fouling phenomenon within the reactor may be caused.

In addition, the polymerization reaction pressure is about 1 bar to about 100 bar, or about 2 bar to about 80 bar, or about 3 bar to about 50 bar, or about 4 bar to about 4 bar to realize catalyst economy by securing optimal productivity. 40 bar, or about 5 bar to about 30 bar, or about 8 bar to about 25 bar. The polymerization reaction pressure may be about 1 bar or more in terms of preventing blocking due to excessive production of high molecular weight and optimizing productivity, and may be about 100 bar or less in consideration of the decrease in polymerization reaction units of olefin monomers under high pressure polymerization conditions. You can.

In the method for producing an organic-inorganic hybrid polyolefin composite according to the present invention, the polymerization reaction time of the olefin monomer may vary depending on the temperature and pressure conditions as described above, and may vary depending on the input amount of the olefin monomer to perform the polymerization reaction. . However, the polymerization reaction is performed in a shorter time than the commonly known olefin monomer polymerization reaction, that is, the polyolefin polymerization reaction consisting of olefin monomers without bonding to a non-porous inorganic material, so that the non-porous inorganic material acts as a filler to which the polyolefin is bonded. As its role is fully fulfilled, it can complement the mechanical properties of polyolefin. Specifically, the polymerization process is performed in a short time of less than about 20% of the polymerization reaction time for polymerizing olefin monomers in the presence of a catalyst composition using a porous inorganic material without using a non-porous inorganic material, or preferably about 17%. or within about 15%, or within about 14%, or within about 13%, or within about 12.5%, or within about 12%, or within about 11.7%, or within about 5% to 11.7% of the polymerization reaction time. A polymerization process can be performed. For example, assuming that the polymerization reaction time for polymerizing olefin monomers in the presence of a catalyst composition using a porous inorganic material instead of a non-porous inorganic material in the above-described catalyst composition is 1 hour, the polymerization process can be performed in a short time of about 12 minutes or less. The polymerization process may be performed, or preferably within about 10 minutes, or within about 8.5 minutes, or within about 8 minutes, or within about 7.5 minutes, or within about 7 minutes, or within about 3 minutes to about 7 minutes. .

As an example, the polymerization reaction is performed at a temperature of about 50 ℃ to 110 ℃ and a pressure of about 1 bar to 100 bar, and the content of the non-porous inorganic material and olefin monomer used in the catalyst composition is 0.4 weight based on the total weight of the organic-inorganic hybrid polyolefin composite. Under the conditions of adding % or more or 0.4% to 12% by weight, the polymerization reaction time can be performed at about 120 minutes or less or about 1 minute to about 120 minutes. Preferably, the polymerization reaction time may be about 120 minutes or less, or about 1 minute to about 120 minutes, and preferably about 100 minutes or less, or about 80 minutes or less, or about 60 minutes or less, or about 55 minutes or less. , or about 50 minutes or less, or about 45 minutes or less, or about 40 minutes or less, or about 35 minutes or less, or about 30 minutes or less, or about 28 minutes or less, or about 25 minutes or less, or about 22 minutes or less, or It can be about 20 minutes or less, or about 18 minutes or less, or about 15 minutes or less, or about 12 minutes or less, or about 10 minutes or less, or about 9 minutes or less, or about 8 minutes or less, or about 7 minutes or less. When the polymerization reaction time is extended for a long time, the non-porous inorganic material does not function as a filler to which polyolefin is bonded due to excessive production of high molecular weight and does not complement the mechanical properties of polyolefin. In this respect, the polymerization reaction time can be performed at about 120 minutes or less. However, in terms of productivity of polyolefin through the polymerization reaction of the olefin monomer, the polymerization reaction time may be about 1 minute or more, and preferably about 2 minutes or more or about 3 minutes or more. As described above, the polymerization reaction time may vary depending on polymerization reaction conditions such as the amount of olefin monomer added, polymerization reaction temperature, pressure, and whether or not hydrogen gas is added.

For example, the polymerization reaction is performed at a temperature of about 75 ° C. or about 83 ° C. and a pressure of about 8 bar to about 25 bar, and the content of the non-porous inorganic material and olefin monomer used in the catalyst composition is based on the total weight of the organic-inorganic hybrid polyolefin composite. Under conditions of adding 0.5 to 2.2 wt%, the polymerization reaction time is about 1 minute to about 12 minutes, or about 2 minutes to about 10 minutes, or about 2 minutes to about 8.5 minutes, or about 3 minutes to about It can be performed in less than 8 minutes, or in about 3 minutes to about 7.5 minutes, or in about 3 minutes to about 7 minutes.

Meanwhile, in another embodiment of the present invention, a material for a separator manufactured using the organic-inorganic hybrid polyolefin composite according to the above embodiment is provided.

Preferably, the material for the separator may be a lithium-ion battery separator (LiBS).

As described above, the separator material of the present invention has good material dispersion and migration by combining an inorganic material with a catalytically active component, performing a polymerization process of olefin monomer, and specifying the content of the inorganic material. Not only does it not deteriorate physical properties over time, but it can be manufactured according to inorganic content, providing excellent mechanical properties, wettability, dimensional stability, and thermal runaway shutoff, as well as low thermal shrinkage. Required properties such as shrinkage can be effectively controlled.

According to the present invention, by combining a non-porous inorganic material with a catalytically active component and then performing a polymerization process of olefin monomer, mixing and dispersion of the non-porous inorganic material and olefin polymer is effectively achieved, and excellent mechanical properties and wettability are achieved. In addition to ensuring low thermal shrinkage along with wettability, dimensional stability, and thermal runaway shutdown, it is also possible to address the problem of physical property deterioration over time due to migration of olefin polymer. It is possible to effectively manufacture an organic-inorganic hybrid polyolefin composite that can solve the problem.

Figure 1 shows a photograph of the catalyst composition of Preparation Example 1 measured with a transmission electron microscope (TEM).
Figure 2 is a photograph of samples collected at each reaction time during the polymerization process of Example 1 and measured using a transmission electron microscope (TEM).
Figure 3 shows a schematic diagram of the results of measuring the contact angle with water on the surface of the polymer film obtained in Examples to 3 and Comparative Examples 1 to 2.
Figure 4 shows photographs of film specimens before and after being left at 140 ^o C for 1 hour when evaluating the dimensional stability of the polymer films obtained in Examples to 3 and Comparative Examples 1 to 2.
Figure 5 shows photographs of film specimens before and after being left at 150 ^o C for 1 hour when evaluating the thermal runaway function (Shutdown function) of the polymer films obtained in Examples to 3 and Comparative Examples 1 to 2.

Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

[Example]

<Manufacture of catalyst precursor>

Synthesis Example 1: Preparation of the first metallocene compound

t-butyl-O-(CH ₂ ) ₆ -Cl was prepared using 6-chlorohexanol by the method described in Tetrahedron Lett. 2951 (1988), and cyclopentadienyl sodium (NaCp) was added to it. By reaction, t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80 ^o C/0.1 mmHg).

In addition, t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in tetrahydrofuran (THF) at -78 ^o C, n-butyllithium (n-BuLi) was slowly added, and the temperature was raised to room temperature. Afterwards, it was reacted for 8 hours. The synthesized lithium salt solution was slowly added to the suspension solution of ZrCl ₄ (THF) ₂ (170 g, 4.50 mmol)/THF (30 mL) at -78 ^o C and reacted at room temperature for another 6 hours. I ordered it. All volatile substances were removed by vacuum drying, and hexane was added to the obtained oily liquid material and filtered. After vacuum drying the filter solution, hexane was added to induce precipitate at low temperature (-20 ^o C). The obtained precipitate was filtered at low temperature to obtain [t-butyl-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ ] in the form of a white solid (92% yield).

¹ H-NMR (300 MHz, CDCl ₃ , ppm): δ 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J=8 Hz), 1.7 - 1.3 (m, 8H), 1.17 (s, 9H).

¹³ C-NMR (300 MHz, CDCl ₃ , ppm): δ 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.31, 30.14, 29.18, 27.58, 26.00.

Synthesis Example 2: Preparation of a second metallocene compound

From the reaction between tert-butyl-O-(CH ₂ ) ₆ Cl compound and Mg(0) in THF solvent, 1.0 mole of tert-butyl-O-(CH ₂ ) ₆ MgCl solution, a Grignard reagent, was obtained. The prepared Grignard compound was added to a flask containing (CH ₃ )SiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at -30 ^o C, and stirred at room temperature for more than 8 hours. The filtered solution was vacuum dried to obtain the compound tert-butyl-O-(CH ₂ ) ₆ Si(CH ₃ )Cl ₂ (yield 92%).

Fluorene (Flu, 3.33 g, 20 mmol), hexane (100 mL), and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) were added to the reactor at -20 ^o C, and 8 mL of n-BuLi (2.5 M in Hexane) was slowly added and stirred at room temperature for 6 hours. After the stirring was terminated, the reactor temperature was cooled to -30 ^o C, and tert-butyl-O-(CH ₂ ) ₆ Si(CH ₃ )Cl ₂ (2.7) dissolved in hexane (100 mL) at -30 ^o C. g, 10 mmol) The fluorenyl lithium solution prepared above was slowly added to the solution over 1 hour. After stirring at room temperature for more than 8 hours, water was added, extracted, and dried (evaporation) to obtain (tert-butyl-O-(CH ₂ ) ₆ )(CH ₃ )Si(9-C ₁₃ H ₁₀ ) ₂ compound. Obtained (5.3g, yield 100%). The structure of the ligand was confirmed through ¹ H-NMR.

¹ H NMR (500 MHz, CDCl ₃ , ppm): δ -0.35 (CH ₃ Si, 3H, s), 0.26 (Si-CH ₂ , 2H, m), 0.58 (CH ₂ , 2H, m), 0.95 ( CH ₂ , 4H, m), 1.17(tert-butyl-O, 9H, s), 1.29(CH ₂ , 2H, m), 3.21(tert-butyl-O-CH ₂ , 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 ).

4.8 mL of n in a solution of (tert-butyl-O-(CH ₂ ) ₆ )(CH ₃ )Si(9-C ₁₃ H ₁₀ ) ₂ (3.18 g, 6 mmol)/MTBE (20 mL) at -20 ^o C. -BuLi (2.5 M in Hexane) was slowly added and reacted for more than 8 hours while raising the temperature to room temperature. Then ^, the dilithium salts slurry solution prepared above was mixed with ZrCl ₄ (THF) ₂ (2.26 g, A slurry solution of 6 mmol)/hexane (20 mL) was slowly added and reacted at room temperature for further 8 hours. The precipitate was filtered and washed several times with hexane to obtain (tert-butyl-O-(CH ₂ ) ₆ ) (CH ₃ )Si(9-C ₁₃ H ₉ ) ₂ ZrCl ₂ compound in the form of a red solid (4.3 g). , yield 94.5%).

¹ H NMR (500 MHz, C ₆ D ₆ , ppm): δ 1.15 (tert-butyl-O, 9H, s), 1.26 (CH ₃ Si, 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).

<Preparation of catalyst composition>

Manufacturing Example 1

50 mL of toluene was added to a 300 mL glass reactor, 10 g of non-porous silica (SiO ₂ ) was added, and the reactor temperature was raised to 40 ^o C while stirring. At this time, the non-porous silica had a specific surface area measured according to the International Organization for Standardization ISO 9277 method of 15 m ² /g. The non-porous silica is NaOH catalyst using tetraethyl orthosilicate (TEOS) by the Stober method (Stober, W. and A. Fink, Bohn, Journal of Colloid and Interface Science, 1986, 26, 62). It was prepared through a hydrolysis process under aqueous solvent conditions with the addition of .

Afterwards, 60 mL of 10 wt% methylaluminoxane (MAO)/toluene solution (Albermarle) was added, the temperature was raised to 60 ^o C, and the mixture was stirred at 200 rpm for 12 hours. After lowering the reactor temperature to 40 ^o C, stirring was stopped and allowed to settle for 10 minutes, and then the reaction solution was decantated. 100 mL of toluene was added and stirred for 10 minutes, then stirring was stopped and allowed to stand for 10 minutes, and then the toluene solution was decantated.

Then, 50 mL of toluene, 0.0055 mmol/gSiO ₂ of the metallocene compound prepared in Synthesis Example 2, and 10 mL of toluene were added to the reactor, and stirred at 200 rpm for 1 hour. Afterwards, a solution of 0.0025 mmol/gSiO ₂ and 10 mL of toluene of the metallocene compound prepared in Synthesis Example 1 was added to the reactor and stirred at 200 rpm for 2 hours. At this time, the ratio between the metallocene compound of Synthesis Example 1 and the metallocene compound of Synthesis Example 2 was 1:2.2 based on the molar ratio. Afterwards, 30 mL of toluene was added, and the mixture was stirred for 10 minutes. Then, the stirring was stopped, the mixture was left to stand for 30 minutes, and the toluene solution was decantated.

30 mL of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. Afterwards, the solid content obtained after filtering was dried under reduced pressure at 40 ^o C for 4 hours to prepare a hybrid supported catalyst composition.

Meanwhile, as a result of performing ICP analysis on the filtrate obtained after filtering, the content of transition metal (Zr) remaining in the filtrate was analyzed to be less than 0.1 ppm.

A photograph of the catalyst composition prepared in this way measured with a transmission electron microscope (TEM) is shown in Figure 1. In particular, Figure 1 (a) shows the surface of an inorganic material, and Figure 1 (b) is a photograph when a cocatalyst is supported on an inorganic material. Figure 1(c) is a photograph after supporting a cocatalyst on an inorganic material and then supporting a metallocene compound, and Figure 1(d) is an enlarged photograph of Figure 1(c). According to Figure 1, it can be seen that the metallocene compound is bound to the surface of the inorganic material.

Comparative Manufacturing Example 1

A hybrid supported catalyst composition was prepared in the same manner as Preparation Example 1, except that porous silica (SP9 product from WRGrace) was used instead of non-porous silica (SiO ₂ ). At this time, the specific surface area of the porous silica measured according to the International Organization for Standardization ISO 9277 method was 300 m ² /g.

<Manufacture of organic-inorganic hybrid polyolefin composite>

Example 1

In a 2 L capacity autoclave reactor, 2 mL (1.0 M hexane) of triethylaluminum (TEAL), the hybrid supported catalyst composition of Preparation Example 1, and hexane were placed in a vial and placed into the reactor, and 0.8 kg of hexane was added. Then, the temperature was raised to 80 ^o C while stirring at 500 rpm. When the temperature inside the reactor reached 78 ^o C, ethylene gas was introduced, and the reaction was performed under 9 bar and stirring at 500 rpm. At this time, the hybrid supported catalyst composition and ethylene gas were added by adjusting the silica content to 0.5% by weight based on the total weight of the organic-inorganic hybrid polyethylene composite. Additionally, the polymerization reaction was performed within 20 minutes at different times of 1 minute, 3 minutes, 5 minutes, 7 minutes, and 20 minutes, respectively. After completion of the reaction, the polymer obtained was first removed from hexane through a filter, then washed with hexane, removed again of hexane through a filter, and dried in a vacuum oven at 80 ^o C for 4 hours to form a powder containing ethylene homopolymer. An organic-inorganic hybrid polyethylene composite was obtained.

In particular, the organic-inorganic hybrid polyethylene composite obtained by performing the above-mentioned polymerization reaction time of 3 to 7 minutes was used as the final product, and physical properties were evaluated as in the test examples below.

Meanwhile, when performing the above-described polymerization process, samples were collected at each reaction time and a photograph measured using a transmission electron microscope (TEM) is shown in FIG. 2. As shown in Figure 2, it can be seen what shape the polymer grows into (a) 1 minute, (b) 3 minutes, (c) 5 minutes, and (d) 20 minutes, respectively, after the start of the polymerization reaction, and the non-porous inorganic It can be confirmed that the polymer grows from the metallocene compound bound to the material.

Examples 2 to 3

Ethylene was prepared in the same manner as in Example 1, but in the presence of the hybrid supported catalyst composition described above so that the silica content was 2.2% by weight and 8.0% by weight, respectively, based on the total weight of the organic-inorganic hybrid polyethylene composite, as shown in Table 1 below. A polymerization reaction was performed, washed and dried to obtain an organic-inorganic hybrid polyethylene composite containing ethylene homopolymer in powder form.

Comparative Example 1

It was prepared in the same manner as Example 1, except that the polymerization process was performed using the hybrid supported catalyst composition of Comparative Preparation Example 1 instead of the hybrid supported catalyst composition of Preparation Example 1, and then washed and dried to produce ethylene homogenate in the form of powder. An organic-inorganic hybrid polyethylene composite containing a polymer was obtained.

In particular, the polymerization process of Comparative Example 1 was performed under the same conditions as Example 1, but the hybrid supported catalyst composition of Comparative Preparation Example 1 containing porous silica rather than non-porous silica was applied, so that the porous silica broke during ethylene polymerization, As the amount of ethylene polymerization instantly increased and the silica content relatively decreased, the silica content became less than 0.01% by weight based on the total weight of the organic-inorganic hybrid polyethylene composite, as shown in Table 1 below.

Comparative Example 2

It was prepared in the same manner as in Example 1, but the ethylene polymerization reaction was performed in the presence of the hybrid supported catalyst composition described above so 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. , washed and dried to obtain an organic-inorganic hybrid polyethylene composite containing ethylene homopolymer in powder form.

<Test example: Evaluation of physical properties of organic-inorganic hybrid polyolefin composite>

The physical properties of the organic-inorganic hybrid polyethylene composites prepared in the above Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

1) Young's modulus and yield strength

Film specimens were manufactured from the polymers obtained in Examples and Comparative Examples in accordance with the American Society for Testing and Materials standard ASTM D 638 test method, and the elastic modulus (Young's modulus) and Yield strength was measured.

2) Wetability (Contact Angle)

Film specimens were manufactured from the polymers obtained in Examples and Comparative Examples in accordance with the American Society for Testing and Materials standard ASTM D 5946 test method, and water was dropped on the surface of the film specimens to determine the contact angle (Degree, ^o ) of the polymer film surface with water. was measured, and wettability was confirmed. DSA 100 from KRUSS was used as a contact angle meter.

A schematic diagram of the results of measuring the contact angle with water of the surface of the polymer film obtained in these Examples and Comparative Examples is shown in Figure 3, and the contact angle with water of the organic-inorganic hybrid polyethylene composite prepared in Examples 1 to 3 is shown in Comparative Examples. It can be seen that the contact angle with water of the organic-inorganic hybrid polyethylene composite prepared in 1 and 2 is significantly lower than that of the water. A low contact angle means good wettability by water, and when applied as a separator for a lithium-ion battery (LiB), it can be seen that the electrolyte can easily penetrate.

3) Dimensional stability

In order to check dimensional stability, film specimens prepared in the same manner as in the previous wettability test were left at 140 ^o C for 1 hour. The shrinkage rate was confirmed by measuring the area before and after leaving.

Here, as described above, when heat shrinkage of the film occurs when left at 140 ^o C for 1 hour, if the area of the film specimen after leaving is 95% or more of the area before leaving, it is marked as 'good', and if it is 90% or more, If it was less than 95%, it was marked as ‘average’, and if it was less than 90%, it was marked as ‘poor.’

When evaluating dimensional stability, photographs of film specimens before and after leaving are shown in Figure 4, and the dimensional stability of the organic-inorganic hybrid polyethylene composites prepared in Examples 1 to 3 was compared to that of Comparative Examples 1 and 2. It can be seen that the dimensional stability is significantly superior to that of an organic-inorganic hybrid polyethylene composite.

4) Thermal runaway prevention (Shutdown function)

In order to check the thermal runaway function (shutdown function), a film specimen prepared in the same manner as in the previous wettability test was placed on a piece of filter paper and left at 150 ^o C for 1 hour. The film melted and retained its original shape to some extent. It was confirmed whether it could be maintained.

Here, as described above, when the film melts when left at 150 ^o C for 1 hour, if the shape of the film specimen maintains its initial shape before leaving even after leaving under high temperature conditions, it is marked as 'good'; If only the outline of the initial shape before abandonment was maintained, it was marked as 'normal', and if it was difficult to properly check the outline of the initial shape before abandonment, it was marked as 'poor'.

When evaluating the thermal runaway function (shutdown function), photographs of film specimens before and after being left are shown in Figure 5, and it can be seen that Comparative Example 1 and Comparative Example 2 melted into the filter paper with almost no film remaining. On the other hand, it can be confirmed that Examples 1 to 3 were properly dissolved in filter paper while maintaining the initial form of the film.

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

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers obtained in Examples and Comparative Examples were measured using gel permeation chromatography (GPC, manufactured by Water), and the weight average molecular weight was calculated as the number average. Molecular weight distribution (PDI, Mw/Mn) was calculated by dividing by molecular weight.

Specifically, a Waters PL-GPC220 instrument was used as a gel permeation chromatography (GPC) device, and a 300 mm long column from Polymer Laboratories PLgel MIX-B was used. At this time, the measurement temperature was 160 ^o C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. The polyethylene samples according to the examples and comparative examples each contained 0.0125% of dibutylhydroxytoluene (BHT, 2,6-bis(1,1-dimethylethyl)-4-methylphenol) using a GPC analysis device (PL-GP220). It was pretreated by dissolving it in 1,2,4-Trichlorobenzene at 160 ^o C for 10 hours, prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of polystyrene standard specimens is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g. Nine types of /mol were used.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Is silica porous? Non-porous Non-porous Non-porous Porous Non-porous Silica specific surface area (m ² /g) 15 15 15 300 15 Silica content (wt%) 0.5 2.2 8.0 less than 0.01 0.3 Young's modulus (MPa) 310 500 305 200 210 Yield Strength (MPa) 23.5 26.5 22 17 22 Wettability (Contact Angle, º) 40 35 30 70 50 dimensional stability good good good bad commonly Shutdown function good good good bad commonly Mn (g/mol) 93,577 87,974 88,708 66,571 94,194 Mw (g/mol) 302,080 301,370 301,727 314,319 298,717 PDI (Mw/Mn) 3.23 3.43 3.40 4.72 3.17

As shown in Table 1, the organic-inorganic hybrid polyethylene composite of Examples 1 to 3 according to the present invention is obtained by bonding a metallocene compound to non-porous silica, performing an ethylene polymerization process, and specifying the content of the inorganic material. , mixing and dispersion of inorganic materials and olefin polymer is achieved effectively, and has excellent mechanical properties, wettability, dimensional stability, thermal runaway shutdown, and low thermal shrinkage. Not only can this be secured, but the problem of deterioration of physical properties over time can be solved through migration of olefin polymer.

Claims (15)

Comprising polyolefin and a non-porous inorganic material combined with at least a portion of the polyolefin,
The non-porous inorganic material has a specific surface area measured according to the International Organization for Standardization ISO 9277 method of 100 m ² /g or less,
The non-porous inorganic material is contained in an amount of 0.4% by weight or more and 12% by weight or less based on the total weight of the organic-inorganic hybrid polyolefin composite.
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The non-porous inorganic material is contained in an amount of 0.45% by weight or more and 10% by weight or less based on the total weight of the organic-inorganic hybrid polyolefin composite.
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The polyolefin is 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-eicocene, which are homopolymers or copolymers of olefin monomers selected from the group consisting of,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The non-porous inorganic material has a specific surface area measured according to the International Organization for Standardization ISO 9277 method of 80 m ² /g or less,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The non-porous inorganic material is one or more selected from the group consisting of alumina, magnesia, zirconia, zeolite, and silica,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The non-porous inorganic material is chemically bonded to at least some of the polyolefin,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
Having a weight average molecular weight of 300,000 g/mol or more,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
having a molecular weight distribution (Mw/Mn) of 2.5 to 4.5,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The elastic modulus (Young's modulus) measured according to the American Society for Testing and Materials standard ASTM D 638 is 250 MPa or more,
Organic-inorganic hybrid polyolefin composite.
According to paragraph 1,
The contact angle with water is less than 45 ^o , as measured according to the American Society for Testing and Materials standard ASTM D 5946 method.
Organic-inorganic hybrid polyolefin composite.
At least one first metallocene compound represented by the following formula (1); And polymerizing olefin monomers in the presence of a catalyst composition in which a catalytically active component containing at least one second metallocene compound selected from the compounds represented by the following formula (2) is bonded to a non-porous inorganic material,
The non-porous inorganic material has a specific surface area measured according to the International Organization for Standardization ISO 9277 method of 100 m ² /g or less,
The content of the non-porous inorganic material is 0.4% by weight or more and 12% by weight or less based on the total weight of the organic-inorganic hybrid polyolefin composite.
Method for producing the organic-inorganic hybrid polyolefin composite according to claim 1:
[Formula 1]
(Cp ¹ R ^a ) _n (Cp ² R ^b )M ¹ Q ¹ _3-n
In Formula 1,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different from each other, and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical. one, and they are substituted or unsubstituted with C _1-20 hydrocarbons;
R ^a and R ^b are the same or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl, provided that R at least one of ^a and R ^b is not hydrogen;
Q ¹ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkylidene, substituted or unsubstituted amino group, C _2-20 alkoxyalkyl, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;
n is 1 or 0;
[Formula 2]

In Formula 2,
R ¹ to R ¹⁷ are the same as or different from each other, and are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 is arylalkyl;
L is C _1-10 straight or branched chain alkylene;
D is -O-, -S-, -N(R)- or -Si(R)(R')-, where R and R' are the same or different from each other and are each independently hydrogen, halogen, C _{1 -20} alkyl, C _2-20 alkenyl, or C _6-20 aryl;
A is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxy alkyl, C _2-20 heterocycloalkyl, or C _5-20 heteroaryl;
Q is carbon, silicon or germanium;
M ² is a Group 4 transition metal;
_X ^{1 and} _{​ ​ ​ 1-20} alkoxy, or C _1-20 sulfonate group.
According to clause 11,
The content of the non-porous inorganic material is 0.45% by weight or more and 10% by weight or less based on the total weight of the organic-inorganic hybrid polyolefin composite.
Method for producing organic-inorganic hybrid polyethylene composite.
According to clause 11,
The olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene. At least one selected from the group consisting of decene, 1-octadecene, and 1-eicocene,
Method for producing organic-inorganic hybrid polyethylene composite.
According to clause 11,
The molar ratio of the first metallocene compound and the second metallocene compound is 1:9 to 9:1,
Method for producing an organic-inorganic hybrid polyolefin composite.
A material for a separator manufactured from the organic-inorganic hybrid polyolefin composite according to any one of claims 1 to 10.