Polyethylene, and chlorinated polyethylene thereof

Polyethylene and its chlorinated polyethylene technical field

[0001] Cross reference to related applications

[0002] This application requires Korean Patent Application Nos. 10-20190120102 and 10-2019-0120103 filed with the Korean Intellectual Property Office on September 27, 2019, and Korean Patent Application No. 10-2020 filed on September 24, 2020 The rights and interests of No. 0123878, the disclosure of which is incorporated herein by reference in its entirety.

[0003] The present disclosure relates to a polyethylene and a chlorinated polyethylene prepared using it. By achieving a molecular structure with a low content of low molecular weight and a high content of high molecular weight, the polyethylene is used in the preparation of chlorinated polyethylene compounds. , It can improve the tensile strength while maintaining excellent processability and Mooney viscosity characteristics.

Background technique

[0004] Olefin polymerization catalyst systems can be divided into Ziegler-Natta catalysts and metallocene catalysts, and these highly active catalyst systems have been developed according to their characteristics. Ziegler-Natta catalysts have been widely used in commercial processes since they were developed in the 1950s. However, since the Ziegler-Natta catalyst is a multi-site catalyst mixed with multiple active sites, it has the characteristic that the resulting polymer has a broad molecular weight distribution. In addition, since the composition distribution of the comonomer is not uniform, there is a problem that it is difficult to obtain desired physical properties. In particular, due to the wide molecular weight distribution, polymer chains having a relatively low molecular weight may deteriorate physical properties.

[0005] At the same time, the metallocene catalyst includes a main catalyst with a metallocene compound as the main component and an organometallic compound co-catalyst with aluminum as the main component. The stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the obtained polymer can be controlled by changing the ligand structure of the catalyst and the polymerization conditions.

[0006] US Patent No. 5,032,562 discloses a method for preparing a polymerization catalyst by supporting two different transition metal catalysts on a carrier. The catalyst is prepared by supporting a high-molecular-weight titanium (Ti)-based Ziegler-Natta catalyst and a low-molecular-weight zirconium (Zr)-based metallocene catalyst to produce a dual-mode molecular weight distribution. The disadvantage of this catalyst is that due to the co-catalyst, the supporting process is complicated and the polymer morphology is poor.

[0007] U.S. Patent No. 5,525,678 discloses a method of using a catalyst system for olefin polymerization, in which a metallocene compound and a non-metallocene compound are simultaneously supported on a carrier to achieve simultaneous high molecular weight polymer and low molecular weight polymer. polymerization. However, there are disadvantages in that the metallocene compound and the non-metallocene compound must be loaded separately, and the support must be pretreated with various compounds for loading.

[0008] US Patent No. 5,914,289 discloses a method for controlling the molecular weight and molecular weight distribution of a polymer using metallocene catalysts respectively supported on a carrier. However, the preparation of the supported catalyst requires a large amount of solvent and a long time, and the process of supporting the metallocene catalyst on various supports is troublesome.

[0009] Furthermore, according to the prior art, there is a disadvantage that it is difficult to efficiently prepare polyolefins, particularly ethylene (copolymer) polymers that simultaneously satisfy a desired density level and narrow molecular weight distribution.

[0010] At the same time, chlorinated polyethylene (CPE) is a product obtained by substituting a part of the hydrogen in polyethylene with chlorine, and is used as an impact modifier or crosslinking of polyvinyl chloride (PVC) to manufacture cable sheaths Or rubber hose.

[0011] Chlorinated polyethylene is used as a material for the cable sheath in a structure that is thermally crosslinked by a peroxide-based crosslinking agent. In order to prevent

To prevent damage to the sheath when the cable is bent, the chlorinated polyethylene must have excellent tensile strength in the crosslinked compound.

[0012] In the case of PVC compound products, the strength of the compound will vary according to the properties of the chlorinated polyolefin. In the case of the currently widely known general-purpose chlorinated polyethylene, since polyethylene prepared using Ziegler-Natta catalyst is used, the uniformity of the chlorine distribution in the polyethylene is reduced due to the wide molecular weight distribution. Another disadvantage is insufficient impact strength when compounded with PVC.

[0013] Recently, in order to increase the tensile strength of the chlorinated polyolefin compound for cables, high-density polyethylene (HDPE) prepared using a metallocene catalyst is chlorinated to produce chlorinated polyethylene, and then added thereto Cross-linking agent to prepare a mixture.

[0014] Generally, the higher the Mooney viscosity (MV) of the chlorinated polyethylene, the higher the Mooney viscosity of the compound, and the higher the tensile strength of the compound, but there is a problem that the processability during compression decreases. .

[0015] Therefore, there is a need to prepare high-density polyethylene that can increase the tensile strength of the compound without reducing processability while having a similar Mooney viscosity, and to develop a catalyst for it.

Summary of the invention

[0016] Technical Problem

[0017] Therefore, there is provided a polyethylene and a preparation method thereof. By achieving a molecular structure with a low content of low molecular weight and a high content of high molecular weight, the polyethylene can maintain the Excellent processability and Mooney viscosity characteristics while improving tensile strength.

[0018] Also provided is a chlorinated polyethylene prepared using the above-mentioned polyethylene.

[0019] Technical Solution

[0020] According to an embodiment of the present disclosure, there is provided a density (measured according to ASTM D-1505) of 0.945 g/cm³ Above polyethylene,

[0021] Wherein, the area fraction representing the high molecular weight content of 10g Mw>6.0 is 4% to 12%,

[0022] The area fraction representing a medium molecular weight content of 4.5<1 log Mw<5.0 is 35% to 50%, and

[0023] The area fraction representing the low molecular weight content of log Mw<4.0 is 10% or less,

[0024] The above area fraction is relative to the molecular weight distribution plotted using gel permeation chromatography with the logarithm of the weight average molecular weight (log Mw) as the x-axis and the molecular weight distribution relative to the logarithm (dw/dlog Mw) as the y-axis. The total area of the curve, and

[0025] The entanglement molecular weight (Me) of the following formula 1 is 27,000 to 52,000 g/mol:

[0026] [Equation 1]

[0027] M_e= (pRT) /GN⁰

[0028] In Formula 1,

[0029] ρ=0.8X (density of polyethylene measured in accordance with ASTM D-1505 (kg/m³),

[0030] R is the gas constant of polyethylene (8.314Pa·m³/mo1 · K),

[0031] T is the absolute temperature (K) of the measured temperature, and

[0032] G_N⁰It is the platform modulus of polyethylene, which is the storage modulus when the loss modulus has the minimum value in the region where the storage modulus is greater than the loss modulus, where the storage modulus and loss modulus use a rotational rheometer Measured under the condition of 190°C and 0.5% strain while changing the angular frequency to 0.05 to 500 rad/s.

[0033] According to another embodiment of the present disclosure, there is provided a chlorine prepared by reacting the polyethylene with chlorine

Chemicalpolyethylene.

[0034] In the present disclosure, the terms "first", "second", etc. are used to describe various ingredients, and these terms are only used to distinguish specific ingredients from other ingredients.

[0035] The terms used herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The singular form is intended to also include the plural form, unless the context clearly dictates otherwise. It will be further understood that when used in this context, the terms "comprising", "having" or "containing" designate the existence of stated features, numbers, steps, ingredients or combinations thereof, but do not exclude the presence or addition of one or Multiple other features, numbers, steps, ingredients, or combinations thereof.

[0036] Since the present invention can be variously modified and have various forms, specific embodiments of the present invention will be illustrated by examples and will be described in detail. However, there is no intention to limit the present invention to the specific forms disclosed, and it should be understood that the present invention includes all modifications, equivalents, and alternative forms within the concept and technical scope of the present invention.

[0037] Hereinafter, polyethylene according to specific embodiments of the present disclosure, a preparation method thereof, and chlorinated polyethylene prepared using the polyethylene will be described in more detail.

[0038] Chlorinated polyethylene used for rubber hoses or cable sheaths requires high tensile strength. Although the tensile strength of the chlorinated polyethylene can be improved by increasing the Mooney viscosity of the chlorinated polyethylene or the Mooney viscosity of the kneaded product, there is a problem of deterioration in extrusion processability. In order to solve this problem, it is necessary to optimize the molecular structure of polyethylene, especially high-density polyethylene used in chlorinated polyethylene.

[0039] It is confirmed in the present disclosure that the combined use of two transition metal compounds having a specific structure can provide polyethylene with a high content of high molecular weight and a minimum content of low molecular weight. Therefore, when the chlorinated polyethylene compound is prepared, the polyethylene has an increased degree of crosslinking and maintains excellent processability and Mooney viscosity characteristics while improving tensile strength. On this basis, the present invention has been completed.

[0040] In the present disclosure, the molecular weight distribution curve uses gel permeation chromatography (GPC) with the logarithm of the weight average molecular weight (log Mw) as the x-axis and the molecular weight distribution relative to the logarithm (dw/dlog Mw) as Plot og Mw>6.0 on the y-axis, that is, the weight average molecular weight (Mw) exceeds 10⁶.⁰g/mol, defined as "high molecular weight"; log Mw<4.0, that is, the weight average molecular weight (Mw) is less than 10⁴，⁰g/mol, defined as "low molecular weight"; 4.0Wlog MwW6.0, which is 10⁴，⁰g/mol or more and 10⁶，⁰The weight average molecular weight (Mw) below g/mol is defined as "medium molecular weight".

[0041] In addition, the high molecular weight content and the low molecular weight content can be calculated from the area ratio of log Mw>6.0 area or log Mw<4.0 area relative to the total area of the molecular weight distribution curve, that is, the log Mw obtained by GPC The fraction (%) in the graph on the x-axis and dw/dlogMw on the y-axis.

[0042] In the present disclosure, the molecular weight distribution curve of polyethylene can be specifically measured using Waters PL-GPC220 as a gel permeation chromatography (GPC) instrument and Polymer Laboratories PLgel MIX-B 300mm long column. The evaluation temperature can be 160°C, and 1,2,4-trichlorobenzene can be used for the solvent at a flow rate of 1 mL/min. The GPC analyzer (PLGP220) can be used to dissolve each polyethylene sample in 1,2,4-trichlorobenzene containing 0.0125% BHT (butylated hydroxytoluene) for 10 hours for pretreatment, and it can be pretreated according to 200UL The amount provides a sample with a concentration of 10mg/10mL. Mw and Mn can be obtained using a calibration curve formed using polystyrene standards. Nine polystyrene standards with molecular weights of 2000g/mol, 10000g/mol, 30000g/mol, 70000g/mol, 200000g/mol, 700000g/mol, 2000000g/mol, 4000000g/mol and 10000000g/mol were used.

[0043] Specifically, when measured according to ASTM D-1505, the polyethylene of the present disclosure has 0.945 g/cm³Above density,

[0044] Wherein, the area fraction of the high molecular weight content representing log Mw>6.0 is 4% to 12%, representing 4.5<log Mw

The area fraction of the medium molecular weight content of &lt;5.0 is 35% to 50%, and the area fraction representing the low molecular weight content of 10g Mw&lt;4.0 is 10% or less. The above area fraction is relative to the weight average molecular weight using gel permeation chromatography. The logarithmic value is the total area of the molecular weight distribution curve drawn on the x-axis and the molecular weight distribution relative to the logarithmic value on the y-axis, and [0045] the entangled molecular weight (M_e) Is 27,000 to 52,000 g/mol.

[0046] The high molecular weight content and low molecular weight content in polyethylene molecules affect the physical properties of polyethylene, such as the degree of crosslinking. For example, the lower the low molecular weight content and the higher the high molecular weight content in polyethylene, the higher the degree of crosslinking. However, when the chlorinated polyethylene compound is prepared, the Mooney viscosity increases, resulting in a decrease in processability. On the other hand, when the low molecular weight content in polyethylene is too high, the low molecular weight components melt and the fluidity becomes high, so that the pores of the polyethylene particles may be clogged, resulting in low chlorination productivity.

[0047] In the polyethylene according to the embodiment of the present disclosure, less than Mw 10^4.0The fraction of the low molecular weight content of g/mol, that is, the area fraction of the low molecular weight content representing log Mw&lt;4.0 in the molecular weight distribution curve is 10% or less, more specifically 7% or less, or 5% or less. In addition, in the above-mentioned low molecular weight content, less than Mw 10^3.5The fraction of the ultra-low molecular weight content of g/mol, that is, the area fraction representing the ultra-low molecular weight content of log Mw&lt;3.5 in the molecular weight distribution curve is 2% or less, 1.5% or less, or 1% or less, and Mw 10^3.5g/mo1 or more and less than Mw 10^4.0The low molecular weight content of g/mol, that is, the low molecular weight content of 3.5Wlog Mw&lt;4.0 is 7% or less, 5% or less, or 4% or less. When having a low content of low molecular weight as described above, the degree of crosslinking is increased, and a decrease in chlorination productivity caused by melting of low molecular weight components can be prevented.

[0048] In addition, in polyethylene, greater than Mw 10^6.0The high molecular weight content fraction of g/mol, that is, the area fraction of the high molecular weight content representing log Mw>6.0 in the molecular weight distribution curve is 4 to 12%. When the area fraction representing the high molecular weight content is less than 4%, there is a concern that the degree of crosslinking is reduced, and when it exceeds 12%, the Mooney viscosity of the chlorinated polyethylene is increased due to the excessively high content of the high molecular weight content, so Worries about possible deterioration of workability. More specifically, in the molecular weight distribution curve of polyethylene, the area fraction representing the high molecular weight content of log Mw>6.0 may be 5% or more, 7% or more and 12% or less, or 10% or less.

[0049] In addition, polyethylene has a structure that forms a high molecular weight tail in the molecular weight distribution curve. Therefore, in the above-mentioned high molecular weight content, the area fraction representing the ultra-high molecular weight content of 6.5&lt;log Mw, more particularly 6.5&lt;log MwW7.0 may be 0.1% to 3%, more specifically 0.1% or more, 0.5% Above or above 0.7%, or below 3%, below 2% or below 1.6%. When it has a higher ultra-high molecular weight content than the conventional one, it can exhibit a more improved degree of cross-linking and entanglement characteristics.

[0050] When the low molecular weight content in polyethylene is low and the high molecular weight content is high, there is a problem that the Mooney viscosity increases and therefore the processability is reduced in the process of preparing the chlorinated polyethylene compound. Since the area fraction of polyethylene representing a medium molecular weight content of 4.5&lt;log Mw&lt;5.0 is 35% to 50%, more particularly 35% or more and 50% or less or 45% or less, the superiority of chlorinated polyethylene can be maintained Processability and Mooney viscosity characteristics.

[0051] In addition, polyethylene has 0.945 g/cm³Above, or 0.945 to 0.955g/cm³The high density. This means that the crystal structure content of polyethylene is high and dense, and the crystal structure is difficult to change during the chlorination process. In the present disclosure, the density of polyethylene can be measured according to ASTM D-1505.

[0052] In addition, the entanglement molecular weight (Me) of polyethylene is 27,000 g/mol to 52,000 g/mol. The entanglement molecular weight refers to the average molecular weight of the entanglement points between the ethylene polymer chains. When the entanglement molecular weight is smaller, the degree of entanglement of the ethylene polymer chain increases, which means excellent resistance to external force deformation and excellent crack resistance. Generally, processability and long-term durability are opposite properties, and therefore, if the melt index or melt flow rate ratio is increased to improve the processability, the long-term durability decreases.

[0053] When the storage modulus of polyethylene measured under 0.5% strain at a temperature of 150 to 230° C., particularly 190° C., at an angular frequency of 0.05 rad/s to 500 rad/s, according to the following formula 1 And loss modulus obtained platform modulus (G_N⁰) When calculated, the entangled molecular weight of the polyethylene of the present disclosure is within the above range, thereby having excellent long-term durability without reducing processability. More specifically, the entangled molecular weight of polyethylene is 30,000 g/mol or more, or 33,000 g/mol or more, and 50,000 g/mol or less, or 49,500 g/mol or less.

[0054] In the present disclosure, the entanglement molecular weight (Me) can be calculated according to the following formula 1:

[0055] [Equation 1]

[0056] M_e= (pRT) /GN⁰

[0057] In Equation 1,

[0058] ρ=0.8X (density of polyethylene measured in accordance with ASTM DT505 (kg/m³),

[0059] R is the gas constant of polyethylene (8.314Pa·m³/mol · K),

[0060] T is the absolute temperature (K) of the measured temperature, and

[0061] G_N⁰It is the platform modulus of polyethylene, which is the storage modulus when the loss modulus has the minimum value in the region where the storage modulus is greater than the loss modulus, where the storage modulus and loss modulus use a rotational rheometer Measured under the condition of 190°C and 0.5% strain while changing the angular frequency to 0.05 to 500 rad/s.

[0062] In addition, when polyethylene is used to prepare chlorinated polyethylene with a Mooney viscosity (MV) of 70 or more to prevent the decrease in physical properties of the CPE compound, the melt index (MI₅; According to ASTM D 1238, measured at 190° C. under a load of 5.0 kg) is preferably 3 g/10 min or less. In addition, when polyethylene is used to prepare chlorinated polyethylene having a Mooney viscosity (MV) of 80 or less to prevent the processability of the CPE compound from being reduced, the melt index is preferably 0.5 g/10 min or more. Specifically, the MI of polyethylene₅The melt index may be 0.5 to 3 g/10 min, more specifically 0.5 g/10 min or more, or 1 g/10 min or more and 3 g/10 min or less, or 2.5 g/10 min or less.

[0063] The polyethylene melt flow rate ratio (MFRR₂₁M₅) Can be 10 to 20, the melt flow rate ratio (MFRR₂₁._6/5) By comparing the MFR measured according to ASTM D 1238 at 190°C under a load of 21.6 kg₂₁.₆Divide by the MFR measured according to ASTM D 1238 at 190°C under a load of 5 kg₅get. When the melt flow index is within the above range, the MV can be appropriately controlled without reducing the physical properties of the chlorinated polyethylene, and excellent processability and the effect of improving the tensile strength of the kneaded product can be obtained. If the melt flow rate ratio exceeds 20, there is a concern that the physical properties of the CPE compound may be deteriorated, and if it is less than 10, the processability of the CPE compound may be reduced. More specifically, it may be 10 or more, or 10.3 or more, and 20 or less, 15 or less, 12 or less, or 11 or less.

[0064] In addition, polyethylene has a high weight average molecular weight (Mw) and molecular weight distribution (PDI). Specifically, the weight average molecular weight (Mw) of polyethylene is 150,000 to 300,000 g/mol, more particularly 150,000 g/mol or more, or 185,000 g/mol or more, and 300,000 g/mol or less, or 250,000 g/mol the following. In addition, the PDI of polyethylene is 5 to 15, more specifically 5 or more, or 5.5 or more, and 15 or less, or 10 or less. If the molecular weight distribution exceeds 15, the difference in molecular weight between polyethylenes is large, so it is difficult for the chlorine in the chlorinated polyethylene after the chlorination reaction to be uniformly distributed. When Mw and PDI are within the above range, the effects of improving processability and having excellent mechanical properties can be obtained in a good balance. In particular, there is little difference in molecular weight between polyethylenes after chlorination, so chlorine can be substituted uniformly.

[0065] In the present disclosure, gel permeation chromatography can be used to measure weight average molecular weight and molecular weight distribution (PDI, polydispersity index). The molecular weight distribution can be determined by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn), and then dividing the weight average molecular weight by the number average molecular weight. The specific method is as described in the experimental example described later.

[0066] In addition, the MDR torque of polyethylene (M_H-M_L) Can be 7Nm or more, 10Nm or more, or 11Nm or more, and 12Nm or more

, Or below 11.8Nm. When the MDR torque is within the above range, a high degree of crosslinking and excellent mechanical properties can be achieved.

[0067] In this context, the MDR torque (Mn-M) of polyethylene refers to the degree of crosslinking. The higher the degree of crosslinking, the higher the Mn-Ml. When the same crosslinking agent is used, high MDR torque means excellent crosslinking efficiency. The MDR torque of polyethylene can be measured, for example, by using a dynamic model rheometer (MDR) to calculate the MDR torque by measuring the value and the value at 180° C. for 10 minutes and subtracting the value from the value. Here, Mn is the maximum vulcanization torque measured when fully cured, and generally the minimum vulcanization torque stored. The specific method is as described in the experimental example described later.

[0068] Meanwhile, the polyethylene of the present disclosure may be an ethylene homopolymer that does not include a comonomer.

[0069] The optimal molecular structure and physical properties of polyethylene can be achieved by a preparation method including the following steps: while introducing hydrogen, the first transition metal compound of the following chemical formula 1 and the second transition metal compound of the following chemical formula 2 are included. And polymerizing ethylene monomer in the presence of a hybrid supported catalyst supporting the first and second transition metal compounds, wherein the molar ratio of the first transition metal compound and the second transition metal compound used is 1:3 to 3 :1. Therefore, another embodiment of the present disclosure provides a method for preparing polyethylene.

[0070] [Chemical Formula 1]

[. . 71] (CplRDm(Cp21yMi

[0072] In Chemical Formula 1,

[0073] M1 is a transition metal of group 4;

[0074] Cpi and Cp? are the same or different from each other, and are each independently any selected from the group consisting of cyclopentadienyl, xunyl, 4,5,6,7 tetrahydro7-xunyl and sulfonyl A sort of. Here, they can be replaced with J-20 Huang.

[0075] I and nine are the same or different from each other, and are each independently hydrogen, C-o alkyl, C-o alkoxy, C2.20 alkoxyalkyl, C6.20 aryl, 06.20 aryloxy, Alkenyl, 07.40 alkylaryl, 07.40 arylalkyl, arylalkenyl, C2/0 alkyl, or C2.20 containing one or more heteroatoms selected from the group consisting of N, O and S Heteroaryl

[0076] Z] is halogen, C-0 alkyl, C2-20 alkenyl, C7-40 alkylaryl, C7/0 aralkyl, C6.20 aryl, substituted or unsubstituted 20 alkylene , Substituted or unsubstituted amino, C2.20 alkylalkoxy or C7.40 arylalkoxy; and

[0077] m is 1 or 0;

[0078] [Chemical Formula 2]

[0079]

<img file="CN113166316A_D0001.tif" />

[0080] In Chemical Formula 2,

[0081] A is carbon or silicon,

[0082] M2 is a transition metal of group 4,

[0083] R?i is a C6/0 aryl group substituted with a "3 alkyl group,

[0084] Η?? is a C33 branched alkyl group,

[0085] R₂₃To R₂₅Each independently is C]_₂₀alkyl,

[0086] Z₂₁And Z₂₂Each independently halogen or C₁To alkyl, and

[0087] n is an integer from 1 to 10.

[0088] In the hybrid supported catalyst, the substituents in Chemical Formulas 1 and 2 will be explained in more detail below.

[0089] 4.₂₀Alkyl groups may include linear, branched or cyclic alkyl groups, and are specifically methyl (Me), ethyl (Et), propyl (Pr), isopropyl, n-butyl (n-Bu), Tert-butyl (t-Bu), pentyl (Pt), hexyl (Hx), heptyl, octyl, cyclobutyl, cyclopentyl or cyclohexyl, etc., but not limited thereto.

[0090] C_1.20The alkylene group may include a linear or branched alkylene group, specifically, methylene, ethylene, propylene, butylene, pentylene, or hexylene, etc., but is not limited thereto.

[0091] C_4.20The cycloalkyl group refers to the cyclic alkyl group in the above-mentioned alkyl group. Specifically, it may include cyclobutyl, cyclopentyl, or cyclohexyl, but is not limited thereto.

[0092] C_2-20The alkenyl group may include a linear or branched alkenyl group, specifically, an allyl group, a vinyl group, a propenyl group, a butenyl group, or a pentenyl group, etc., but is not limited thereto.

[0093] C_6.20The aryl group may include a monocyclic or condensed ring aryl group, specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group or a sulfonyl group, etc., but is not limited thereto.

[0094] C_1.20The alkoxy group may include a methoxy group, an ethoxy group, a phenoxy group, a cyclohexyloxy group, etc., but is not limited thereto.

[0095] C_2.20The alkoxyalkyl group may be a functional group in which one or more hydrogens of the above-mentioned alkyl group are replaced by an alkoxy group, and specifically, may include: alkoxyalkyl groups, such as methoxymethyl, methoxyethyl , Ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl or tert-butoxyhexyl, etc.; or aryl Oxyalkyl, such as phenoxyhexyl, etc., but not limited thereto.

[0096] C_1-20Alkylsilyl or C_1-20The alkoxysilyl group can be where -SiH₃The functional groups in which 1 to 3 hydrogens are substituted by 1 to 3 alkyl groups or alkoxy groups as described above, specifically, may include: alkylsilyl groups, such as methylsilyl groups, dimethylsilyl groups Group, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl, etc.; alkoxysilyl, such as methoxysilyl Group, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl, etc.; alkoxyalkylsilyl, such as methoxydimethylsilyl, two Ethoxymethylsilyl or dimethoxypropylsilyl, etc., but not limited thereto.

[0097] “_-20A silylalkyl group is a functional group in which one or more hydrogens of the above-mentioned alkyl group are replaced by a silyl group, and specifically, may include -CH₂-SiH₃, Methylsilylmethyl or dimethylethoxysilylpropyl, etc., but not limited thereto.

[0098] Halogen can be fluorine (F), chlorine (Cl), bromine (Br) or iodine (1).

[0099] Sulfonate group has -O-SO₂-R' structure, where R'can be C_1-20alkyl. Specifically, ^_.20The sulfonate group may include a mesylate group or a benzenesulfonate group, etc., but is not limited thereto.

[0100] Heteroaryl is C containing one or more of N, O and S as a heteroatom_2.20Heteroaryl groups, specific examples of which may include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, pyridine Group, triazine, acridinyl, pyridazine, pyrazinyl, quinolinyl, quinazoline, quinoxalinyl, phthaloyl, pyridocarbidine, pyridopyrazinyl, pyrazino Pyrazinyl, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, benzofuranyl, phenanthroline, isoam Azolyl, thiadiazolyl, phenothiazinyl, or dibenzofuranyl, etc., but not limited thereto.

[0101] Within a range having the same or similar effects as the desired effects, the above-mentioned substituents may be optionally substituted with one

Or more substituents selected from the group consisting of: hydroxy; halogen; alkyl, alkenyl, aryl, or alkoxy; containing one or more heteroatoms from groups 14 to 16 Atoms of alkyl, alkenyl, aryl or alkoxy; silyl; alkylsilyl or alkoxysilyl; transient; phosphide; sulfonate and sulfone.

[0102] In addition, the transition metal of Group 4 may include titanium (Ti), zirconium (Zr), hafnium (Hf), etc., but the present disclosure is not limited thereto.

[0103] In the hybrid supported catalyst, the first transition metal compound exhibits high polymerization activity, and it is easy to prepare a low molecular weight polymer. Moreover, it is easier to prepare high molecular weight polymers from the second transition metal compound than the first transition metal compound. Therefore, when the mixing ratio of the first transition metal compound and the second transition metal compound in the hybrid supported catalyst is adjusted, the low molecular weight content in the prepared polymer is minimized, and due to the high content of the second transition metal compound Molecular weight characteristics, molecular weight distribution can be improved. In addition, the viscosity can be easily adjusted. The polyethylene thus prepared may have an increased degree of crosslinking and entanglement.

[0104] Specifically, the first transition metal compound represented by Chemical Formula 1 contains Cp¹And Cp²Ligand uncrosslinked compound, where Cp¹And Cp²The ligands may be the same or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5, 6,7-tetrahydro-1-indenyl, and sulfonyl. These ligands can be substituted with one or more or 1 to 3 "-₂₀Hydrocarbons, more particularly C₁T₀alkyl. Due to Cp¹And Cp²The ligand has a pair of non-covalent electrons capable of acting as a Lewis base, and therefore can achieve high polymerization activity. Especially when Cp¹And Cp²When the ligands are cyclopentadienyl groups with relatively small steric hindrance, they exhibit high polymerization activity and low hydrogen reactivity, and therefore can be polymerized with high activity to obtain low molecular weight olefin polymers.

[0105] In addition, Cp¹And Cp²The ligand can easily control the properties of the olefin polymer to be prepared, such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency by adjusting the degree of steric hindrance depending on the type of substituted functional group. Specifically, Cp¹And Cp²Ligand to replace human] and R₁₂, Where, where] and R₁₂The same or different from each other, and each can independently be hydrogen, 4.₂₀Alkyl, C₂.₂₀Alkoxyalkyl, C₇.₄₀Arylalkyl or C containing at least one heteroatom selected from the group consisting of N, O and S₂ T₂Heteroaryl, more specifically C₁To alkyl, C₂ To alkoxyalkyl, points.₂₀Aralkyl or C containing at least one heteroatom selected from the group consisting of N, O and S₄ T₂Heteroaryl. In order to have excellent catalytic activity, when Xi and R₁₂When each is a substituent defined above, mountain and &amp;₂At least one of them can be C₂.₂₀Alkoxyalkyl or C₂ one _1clAlkoxyalkyl.

[0106] In addition, in Cp¹And Cp²The presence of MjZjf between the ligands and the small bright area can affect the storage stability of the metal complex. In order to ensure the effect more effectively, Z1 can each independently be halogen or "-_2cAlkyl groups, more specifically, are each independently F, Cl, Br, or I. In addition, M1 may be Ti, Zr or Hf, more specifically Zr or Hf, and more specifically Zr.

[0107] More specifically, in the first transition metal compound"₁For towel 1 or Hf; CpI and Cp²The same or different from each other, and each independently is free to be selected by C₁To alkyl substituted or unsubstituted cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and any one of the group consisting of; where] and R₁₂Each independently is hydrogen, Cr _2cAlkyl, C₂.₂. Alkoxyalkyl, C₆.₂₀Aryl, C₇.₂₀Arylalkyl, furyl or thienyl, where Ru and R₁₂At least one of them is C₂.₂₀Alkoxyalkyl; Z1 is halogen.

[0108] The first transition metal compound represented by Chemical Formula 1 may be, for example, a compound represented by any one of the following structural formulae, but is not limited thereto:

<img file="CN113166316A_D0002.tif" />

<img file="CN113166316A_D0003.tif" />

Ph

<img file="CN113166316A_D0004.tif" />

[0110] In addition, the first transition metal compound may be a compound in which M1 is Zr; Cpi and Cp2 are each independently an unsubstituted cyclopentadienyl group or substituted with at least one Co alkyl group such as a methyl group. Cyclopentadienyl; E and each independently are hydrogen, C]_20 alkyl, C2.20 alkoxyalkyl, C7/0 aryl or C7-20 arylalkyl, wherein the mountain and the nine in At least one or two is a C2 .20 alkoxyalkyl group, more particularly a C? .10 alkoxyalkyl group, even more particularly a tert-butoxyhexyl group; Z] is a halogen group; in chemical formula 1 m is 1.

[0111] The first transition metal compound represented by Chemical Formula 1 can be synthesized by applying a known reaction. Specifically, a ligand compound is prepared by various synthetic methods, and then metallization is performed by adding a metal precursor compound. However, the present disclosure is not limited to this, and the synthesis method can refer to the embodiment.

[0112] Meanwhile, in the hybrid supported catalyst, the second transition metal compound represented by Chemical Formula 2 forms a ligand structure in which a Xun derivative and an amine derivative are cross-linked by a bridging compound, and has a pair of As a non-covalent electron of a Lewis base, it exhibits high polymerization activity. In particular, the catalyst may exhibit high catalytic activity by having a structurally stable and electron-rich Xun structure, and may exhibit excellent loading stability to the carrier by including a tethering group in the bridging group.

[0113] In addition, the second transition metal compound is substituted with a functional group (H?) having a branched structure at the 2-position of the Xun structure, and 8-hydrogen in the polymer chain in which the nitrogen atom of the amine derivative grows passes through hydrogen. The bond is stabilized, thereby preparing polymers of medium molecular weight and high molecular weight. In addition, the polymer to be prepared has a narrow molecular weight distribution, thus exhibiting excellent mechanical properties. Specifically, R22 can be a C3.12 or C3.6 branched alkyl group, such as isopropyl, isobutyl, tert-butyl, and isopentyl, etc., and can be isopropyl. In terms of steric effect, it Is more advantageous.

[0114] In addition, the Xun structure has a C6-20 aryl group substituted with one or more (or one or two) "3 alkyl groups by bonding R?i at the 4-position to provide sufficient electrons. The inducing effect of, thus showing higher catalytic activity. More specifically, in chemical formula 2, R? i can be substituted with one or two C3.6 branched alkyl groups (such as 4-tert-butyl phenyl And 3,5-two

Tert-butylphenyl) phenyl.

[0115] In addition, R bonded to N in Chemical Formula 2₂₃Can be "-₂₀Straight-chain or branched alkyl, more specifically ^^ or ^. C₆Branched alkyl, such as tert-butyl. When R₂₃When having a branched structure, the transition metal compound is sterically stable, and the catalyst is stabilized by the electron donating effect, thereby exhibiting higher catalytic activity.

[0116] More specifically, in Chemical Formula 2, R₂₁To replace with one or two C₃.₆Phenyl of branched alkyl group, and R₂₂And r₂₃Can each independently be C₃.₆Branched alkyl. Even more specifically, r₂₂It can be isopropyl.

[0117] In addition, in the chemical formula 2, the bridging group includes an R₂₄The functional groups are tied together to the carrier "(CH₂)nOR₂₅The tethering group. Therefore, it is possible to exhibit excellent load stability and maintain excellent catalytic activity to prepare a polymer having a high molecular weight.

[0118] Specifically, R₂₄Can be C₁T₂or"-₆Straight or branched alkyl. More specifically, it may be a C straight-chain alkyl group or a methyl group to increase solubility, thereby improving loading efficiency.

[0119] In addition, R in the tethering group₂₅Can be C₁T₂or"-₆Linear or branched alkyl, more specifically, can be C₃.₆Branched alkyl, or tert-butyl. When the tethering group has a branched structure such as t-butyl, it can be easily separated and bonded to the carrier, thereby exhibiting excellent load stability.

[0120] In addition, n in the tethering group may specifically be 3 to 8 or 4 to 6, and the tethering group within the above range may have an appropriate length, thereby stably exhibiting excellent load stability Sexual catalytic activity.

[0121] In the bridging group, A may be silicon (Si).

[0122] More specifically, in Chemical Formula 2, A is silicon, and R₂₅Is C₃.₆A branched alkyl group, and n may be an integer from 4 to 6.

[0123] In addition, the second transition metal compound of Chemical Formula 2 may include a transition metal of Group 4, such as titanium (Ti), zirconium (Zr), and hafnium (Hf), as the central metal (M2). When the transition metal compound contains Ti as the central metal, the catalyst exhibits a more excellent polymerization activity than the case of containing other group 4 transition metals such as Zr and Hf by increasing the openness of the structure, and is stabilized by the electron donating effect , Resulting in a polymer with a high molecular weight.

[0124] In Chemical Formula 2, Z₂₁And Z₂₂Can each independently be a halogen such as chlorine; or C such as methyl₁T alkyl. More specifically, Z₂₁And Z₂₂Both can be methyl, and in this case, with Z₂₁And Z₂₂Compared with the case of halogen, it can show better catalytic activity.

[0125] More specifically, in Chemical Formula 2, M₂Is titanium, and Z₂₁And Z₂₂Can each independently be C₁T alkyl.

[0126] More specifically, the compound of Chemical Formula 2 may be the following compound, wherein A is silicon; M₂Is titanium; R₂₁Is substituted with one or two C such as tert-butyl etc.₃ To the phenyl of branched alkyl group; R₂₂Is C₃.₆Branched alkyl, such as isopropyl; R₂₃Is C₃.₆Branched alkyl, such as tert-butyl; r₂₄Is C₁T straight-chain alkyl, such as methyl; r₂₅Is C₃.₆Branched alkyl, such as tert-butyl; Z₂₁And Z₂₂Each independently is q-₄Alkyl, such as methyl; n is an integer from 4 to 6.

[0127] The second transition metal compound represented by Chemical Formula 2 may be a compound represented by one of the following structural formulae, but is not limited thereto:

<img file="CN113166316A_D0005.tif" />

<img file="CN113166316A_D0006.tif" />

[0129] The above-mentioned second transition metal compound can be prepared by lithiation of the ligand compound of the following chemical formula 3 and subsequent reaction with a halide containing a group 4 transition metal:

[0130] [Chemical Formula 3] ^Rtwenty one ° ]Ze25-"out)2 7

R2"^xnh ^R23

[0132] In Chemical Formula 3, A#?] to R25 and n are the same as defined above.

[0133] The following Reaction Scheme 1 represents a method for preparing the second transition metal compound of Chemical Formula 2 according to one embodiment of the present invention. The following reaction scheme 1 is only an example to illustrate the present invention, but the present invention is not limited to this:

<img file="CN113166316A_D0007.tif" />

[0136] In Reaction Scheme 1, A, M?, R?i to R25, Z21, Z22, and n are the same as defined above, and X1 and X2 are each independently a halogen.

[0137] As described in Reaction Scheme 1, it is possible to carry out lithiation by reacting the ligand compound (3) of Chemical Formula 3 with an alkyl lithium such as n-butyl lithium (NBL), and then with a transition metal containing group 4 Halide (4) (such as TiCl, reacts to prepare compound (2) of chemical formula 2. In addition, when X] and X2 in compound of chemical formula 2 are each "γ. Alkyl group, they can be added after lithiation Alkylation reagent used for the alkylation of metal M, such as MMB (Methyl Magnesium).

[0138] In addition, the ligand compound (3) used to prepare the compound (2) of Chemical Formula 2 can be prepared by the synthesis method in the following reaction scheme 2. Reaction scheme 2 is only an example for explaining the present invention, and the present invention is not limited to this.

[0139] [Reaction Scheme 2]

^21

<img file="CN113166316A_D0008.tif" />

r2r γ (6)

[0141] In Reaction Scheme 2, A#2I to R24 and n are the same as defined above, and X3 and X are each independently halogen.

[0142] Referring to Reaction Scheme 2, the ligand compound (3) can be prepared, including the following steps: reacting the Xun-type compound (5) as a Cp unit with alkyl lithium such as n-butyl lithium (NBL) for lithiation; The resulting reactant reacts with the raw material for providing the tethering group to prepare compound (7) in which the tethering group is bonded to the Xun structure; the compound is combined with a tertiary amine having R3 substituent (such as t-BuNH?) reaction.

[0143] The reaction in each step can be performed by applying a known reaction, and a more detailed synthesis method can refer to the preparation example described later.

[0144] As described above, the hybrid supported catalyst containing the first transition metal compound and the second transition metal compound can effectively provide polyolefins, especially when preparing chlorinated polyolefins and chlorinated mixtures. The high-density polyethylene whose degree of crosslinking is increased can increase the tensile strength, because by forming a high-molecular-weight tail in the molecular-weight distribution curve, the polyolefin has a minimized low-molecular-weight content and a broad molecular-weight distribution. In addition, by controlling the mixing ratio of the first transition metal compound and the second transition metal compound in the hybrid supported catalyst, the above effect can be further enhanced. Specifically, the mixing molar ratio of the first transition metal compound and the second transition metal compound may be 1:3 to 3:1, or 1:1.5 to 2:1. [0145] In addition, in the hybrid supported catalyst, The form of the supported catalyst supported on the carrier includes a first transition metal compound and a second transition metal compound. When the transition metal compound is used in the form of a supported catalyst, the morphology and physical properties of the prepared polyethylene can be further improved, and it can be applied to slurry polymerization, bulk polymerization, and gas phase polymerization.

[0146] Specifically, the carrier may have a hydroxyl group, a silanol group, or a siloxane group possessing high reactivity on its surface. The support can be surface modified by simmering or can be dried to remove moisture from the surface. For example, the support may be silica prepared by sintering silica gel, silica dried at high temperature, silica-alumina or silica-magnesia, and it may generally contain oxides, carbonates, Sulfate or nitrate, such as Na?. #2c03, BaS()4 and Mg (NOJ₂Wait.

[0147] The carrier is preferably sintered or dried at 200 to 600°C, more preferably 250 to 600°C. When the temperature is lower than 200°C, the carrier contains too much moisture, so that the moisture on the surface may react with the promoter. In addition, due to excess hydroxyl groups, the co-catalyst loading rate may be relatively high, but this requires a large amount of co-catalyst. When the temperature is higher than 600°C, the pores on the surface of the carrier can be combined with each other to reduce the surface area, and many hydroxyl groups or silanol groups can be lost from the surface, leaving only siloxane groups. Therefore, the reactive sites with the co-catalyst may be reduced, which is not preferable.

[0148] The amount of hydroxyl groups can be controlled by the preparation method, preparation conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying. When the amount of the hydroxyl group is too low, the reactive sites with the co-catalyst may be insufficient. When the amount of the hydroxyl group is too high, in addition to the hydroxyl group present on the surface of the carrier particles, it may be caused by moisture, which is undesirable. For example, the amount of hydroxyl groups on the surface may be 0.1 to or 0.5 to 5 mmol/g.

[0149] Among the above-mentioned supports, the polymerization of silica prepared by sintering silica, especially silica gel in propylene

During the process, almost no catalyst is released from the surface of the support because the transition metal compounds are chemically bonded and supported on the silica support. As a result, when polyethylene is prepared by slurry polymerization or gas phase polymerization, the fouling phenomenon adhering to the wall surface of the reactor or to each other can be minimized.

[0150] When the transition metal compound is used in the form of a supported catalyst, the content of the first transition metal compound and the second transition metal compound may be 10 Pmol or more, 30 umol or more, or 60 umol based on the weight of the support, for example, 1 g of silica. Above and below 120umol or below 100umol. When supported within the above content range, the supported catalyst can exhibit appropriate activity, which is advantageous in maintaining catalytic activity.

[0151] The hybrid supported catalyst having the above configuration exhibits excellent polymerization activity, and can prepare polyethylene having a structure optimized to improve the tensile strength of chlorinated polyethylene or chlorinated kneaded compound.

[0152] The hybrid supported catalyst can be directly introduced into the polymerization system, or can be dissolved or diluted in C5 to C12 aliphatic hydrocarbon solvents (such as pentane, hexane, heptane, nonane, decane and its isomers) Medium and aromatic hydrocarbon solvents (such as toluene and benzene) or chlorinated hydrocarbon solvents (such as dichloromethane and chlorobenzene), and then introduced into the polymerization system. The solvent used here is preferably used after removing a small amount of water or air as a catalyst poison by treatment with a small amount of aluminum alkyl.

[0153] In addition, in terms of improving activity and stability, the above-mentioned catalyst composition may further include a co-catalyst. The co-catalyst may include one or more compounds represented by the following Chemical Formula 9, Chemical Formula 10, and Chemical Formula 11:

[Chemical Formula 9]

[0155] -[Al (R_a) -O]_m[0156] In Chemical Formula 9;

[0157] R_a, Can be the same or different from each other, and are each independently halogen, C_1-20Hydrocarbon, or halogen substituted C_1-20Hydrocarbon; and

[0158] m is an integer of 2 or more;

[Chemical Formula 10]

[0160] J (R_b）₃

[0161] In Chemical Formula 10,

[0162] R_b, Can be the same or different from each other, and are each independently halogen, C_1-20Hydrocarbon, or halogen substituted C_1-20Hydrocarbon; and

[0163] J is aluminum or boron;

[Chemical Formula 11]

[0165] [EH] + [ZQ₄]^-Or [E] + [ZQ₄]^-

In Chemical Formula 11,

[0167] E is a neutral or cationic Lewis base;

[0168] H is a hydrogen atom;

[0169] Z is an element of group 13; and

[0170] Q may be the same or different from each other, and each independently is where one or more hydrogen atoms are unsubstituted or halogenated, C_1.20^, alkoxy or phenoxy substituted C_6-20Aryl or C_1-20alkyl.

[0171] Examples of the compound represented by Chemical Formula 9 may include C_1-20Alkyl aluminoxane compounds, such as methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane, etc., of which any one or a mixture of two or more thereof can be used.

[0172] In addition, examples of the compound represented by Chemical Formula 10 may include trimethylaluminum, triethylaluminum, triisobutylaluminum,

Tripropyl aluminum, tributyl aluminum, dimethyl aluminum chloride, triisopropyl aluminum, tri-sec-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, three Octyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron , Triisobutyl boron, tripropyl boron or tributyl boron, etc., more specifically, it can be selected from trimethyl aluminum, triethyl aluminum and triisobutyl aluminum.

[0173] In addition, examples of the compound represented by Chemical Formula 11 may include triethylammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, 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-diethylaniline tetraphenyl boron, N,N-diethylanilinium tetra(five) Fluorophenyl) boron, diethylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium tetraphenylaluminum, tributylammonium Tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl Ammonium tetra(ortho, p-dimethylphenyl) aluminum, tributylammonium tetra(p-trifluoromethylphenyl) aluminum, trimethylammonium tetra(p-trifluoromethylphenyl) aluminum, tributyl Ammonium tetra(pentafluorophenyl) aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N diethylanilinium tetra(pentafluorophenyl) aluminum, diethylammonium tetra(pentafluorobenzene) Base) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o, p-dimethylphenyl) Boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, triphenyl carbon tetrakis (p-trifluoromethyl phenyl) boron or triphenyl carbon tetrakis (pentafluorophenyl) boron, etc., in, Any one or a mixture of two or more of them can be used.

[0174] Among the above-mentioned co-catalysts, considering that the co-catalyst may exhibit more excellent catalytic activity when used with a transition metal compound, the co-catalyst may be a compound represented by Chemical Formula 9, more specifically, "1₂₀Alkyl aluminoxane compounds, such as methyl aluminoxane and the like. Alkyl aluminoxane compounds are used as scavengers for hydroxyl groups present on the surface of the support to improve catalytic activity, and convert the halogen groups of the catalyst precursor to methyl groups, thereby promoting chain growth during the polyethylene polymerization process.

[0175] Based on the weight of the carrier, for example, 1 gram of silica, the supporting amount of the co-catalyst may be 0.1 mmol or more, or 5 mmol or more, or 8 mmol or more, or 10 mmol or more, and 25 mmol or less, or 20 mmol or less . When the content of the co-catalyst is within the above content range, the effect of increasing the catalytic activity and the effect of reducing the generation of fine powder due to the use of the co-catalyst can be sufficiently obtained.

[0176] In addition, the catalyst composition may further include an antistatic agent. As the antistatic agent, an ethoxylated alkylamine can be used, and specifically, a compound represented by the following Chemical Formula 12 can be used. When the catalyst composition contains an antistatic agent, the generation of static electricity is suppressed during the polyethylene polymerization process, thereby further improving the physical properties of the prepared polyethylene.

[Chemical Formula 12]

[0178] RN-(CH₂cH₂0H)₂

[0179] In Chemical Formula 12, R may be C_8-30An alkyl group, and when R includes an alkyl group having a carbon number in the above-mentioned range, it can exhibit an effect of reducing fine powder without causing an unpleasant odor through an excellent antistatic effect.

[0180] More specifically, the ethoxylated alkylamine may be a compound of formula 12, wherein R is C_8.22Straight chain alkyl or C₁₀ T₈Straight chain alkyl or C₁₃ T₅A straight chain alkyl group, and these compounds may be used alone or in a mixture of two or more kinds. Specific examples thereof may include N,N-bis(2-hydroxyethyl)tridecylamine or N,N-bis(2-hydroxyethyl)pentadecylamine, etc., and commercially available Atmer 163 may be used.^TM (Available from CRODA).

[0181] When further comprising an antistatic agent, based on 100 parts by weight of the carrier, such as silica, its content may be 0.5 parts by weight or more, 1 part by weight or more, or 2 parts by weight or more, and 20 parts by weight or less, 10 parts by weight Parts or less or 7 parts by weight or less.

[0182] The aforementioned cocatalyst and antistatic agent may be used in combination with the aforementioned hybrid supported catalyst, respectively, or may be used in a state of being supported on a carrier in the hybrid supported catalyst. When they are used in a state of being supported on a carrier in a hybrid supported catalyst, the catalyst composition can be prepared by a preparation method including the following steps: the cocatalyst compound is supported on the carrier, and the transition metal compound is supported on the carrier Top; The antistatic agent in the slurry state is introduced into the carrier supporting the cocatalyst and the transition metal compound, and then the heat treatment is performed. In this regard, the supporting of the transition metal compound may be performed by supporting the first transition metal compound and then supporting the second transition metal compound, and vice versa. The supported catalyst with a structure determined according to this loading sequence can exhibit higher catalytic activity and excellent process stability during the polyethylene preparation process.

[0183] The catalyst composition may be used in the form of a slurry or a diluent in a solvent according to the polymerization method, or may be used in the form of a slurry catalyst mixed with a mixture of fats and oils.

[0184] When the catalyst composition is used in the form of a slurry or a diluent in a solvent, the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of propylene monomer, such as pentane, hexane , Heptane, nonane, decane and its isomers, as well as aromatic hydrocarbon solvents such as toluene and benzene, or hydrocarbon solvents substituted with chlorine atoms such as methylene chloride and chlorobenzene, etc., any of them can be used Or a mixture of two or more. In this case, the catalyst composition may further include the above-mentioned solvent, and a small amount of water or air that may be a catalyst poison may be removed by treating the solvent with a small amount of aluminum alkyl before use.

[0185] On the other hand, the polymerization reaction for preparing polyethylene can be carried out using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor. However, according to the method of this embodiment, in order to more effectively control the molecular weight distribution, slurry polymerization or gas phase polymerization is more suitable.

[0186] In particular, the polymerization reaction can be carried out by slurry phase polymerization in a hydrocarbon solvent (for example, an aliphatic hydrocarbon solvent such as hexane, butane, or pentane). Since the first transition metal compound and the second transition metal compound of the present disclosure have excellent solubility in aliphatic hydrocarbon solvents, they are stably dissolved and supplied to the reaction system, and thus the polymerization reaction can be efficiently performed.

[0187] In addition, the method for preparing polyethylene according to an embodiment of the present invention may be performed in a single CSTR reactor.

[0188] In the polymerization reactor, the polymerization can be performed, for example, in the presence of an inert gas such as nitrogen. The inert gas can prolong the reactivity of the metallocene compound contained in the catalyst by suppressing the rapid reaction of the metallocene catalyst at the start of the polymerization reaction.

[0189] In addition, the polymerization reaction was performed while introducing hydrogen.

[0190] The hydrogen introduced during the polymerization reaction activates the inert sites of the metallocene catalyst and causes a chain transfer reaction, thereby controlling the molecular weight and molecular weight distribution. In the preparation of polyethylene according to the present disclosure, based on 100 parts by weight of ethylene monomer, it may be 0.001 parts by weight or more or 0.005 parts by weight or more and 15 parts by weight or less, 5 parts by weight or less, 1 part by weight or less, or 0.015 parts by weight. The following amount of hydrogen is introduced. When hydrogen is introduced within the above range in the presence of the hybrid supported catalyst as described above, the optimized molecular structure and physical properties of the polyethylene of the present disclosure can be achieved.

[0191] In addition, the temperature during the polymerization reaction may be 70°C to 100°C, or 80°C to 90°C. When the polymerization temperature is too low, it is not preferable in terms of polymerization rate and productivity. On the contrary, when the polymerization temperature is higher than necessary, it may cause fouling in the reactor.

[0192] In addition, the polymerization pressure may be 6.8 to 8.7 kg/cm², 7.0 to 8.5kg/cm²Or 7.0 to 7.5kg/cm²To ensure the best productivity. The polymerization pressure can be about 6.8kg/cm²Above in order to prevent the excessive production of high molecular weight

To increase adhesion and optimize productivity, and it can be about 8.7kg/cm²The following is to prevent the unit degradation of the ethylene source under high pressure polymerization conditions.

[0193] In addition, an organic solvent may be further used as a reaction medium or diluent in the polymerization reaction. Considering the content of the ethylene monomer, such an organic solvent may be used in an amount sufficient to appropriately perform slurry phase polymerization or the like.

[0194] In addition, a trialkylaluminum, such as triethylaluminum, may optionally be added during the polymerization reaction.

[0195] When moisture or impurities are present in the polymerization reactor, a part of the catalyst is decomposed. The trialkyl aluminum is used as a scavenger to capture the moisture or impurities in the reactor or the moisture contained in the monomer in advance. Therefore, the activity of the catalyst used in the preparation can be maximized, and as a result, a homopolyethylene having excellent physical properties, particularly a narrow molecular weight distribution, can be more efficiently prepared. Specifically, in the trialkyl aluminum, the alkyl group is as defined above, specifically 4.₂₀Alkyl, and more specifically "one₆Straight-chain or branched alkyl, such as methyl, ethyl or isobutyl.

[0196] Based on 1 kg of ethylene monomer, the addition amount of trialkyl aluminum (based on 1 M) may be 10 cc or more and 50 cc or less, or 30 cc or less. When the polymerization reaction is performed in the presence of trialkylaluminum within this content range, it is possible to more easily prepare homopolyethylene having excellent strength characteristics.

[0197] Preparation of polyethylene having an optimized molecular structure, particularly a molecular structure with a minimized low molecular weight content and a relatively high high molecular weight content, is prepared by the above preparation method. Polyethylene can increase the degree of crosslinking in the preparation of chlorinated polyethylene, and as a result, the tensile strength can be greatly improved.

[0198] The polyethylene may be a homopolymer of ethylene that does not contain additional copolymers. For example, when polyethylene is an ethylene homopolymer, preferably high-density polyethylene (HDPE), the above-mentioned physical properties can be more appropriately satisfied. High-density polyethylene has excellent softening point, hardness, strength and electrical insulation, so it can be used in various containers, packaging films, fibers and tubes.

[0199] Preparation of chlorinated polyethylene

[0200] According to another embodiment of the present disclosure, there is provided a chlorinated polyethylene prepared by chlorinating the above-mentioned polyethylene with chlorine and a preparation method thereof.

[0201] Specifically, the preparation method of chlorinated polyethylene includes the following steps: while introducing hydrogen, in the presence of a catalyst composition containing a hybrid supported catalyst, polyethylene is prepared by polymerizing ethylene monomers, In the catalyst, at least one first transition metal compound represented by Chemical Formula 1 and at least one second transition metal compound represented by Chemical Formula 2 are supported on a carrier; and it is chlorinated by treating polyethylene with chlorine.

[0202] As described above, specific examples of the reaction conditions in the step of polymerizing vinyl monomers to prepare polyethylene, the first and second transition metal compounds, supports, cocatalysts, and hybrid supported catalysts including them are as above Said.

[0203] In addition, the chlorination of polyethylene can be performed by an aqueous phase method in which polyethylene and chlorine are reacted in a suspended state, or an acid phase method in which polyethylene is reacted with chlorine in an aqueous HCl solution. For example, the aqueous phase method is a method of chlorination using emulsifiers and dispersants and water, and the acid phase method is a method of chlorinating acidic aqueous solutions such as hydrochloric acid (HCl) solutions using emulsifiers and dispersants.

[0204] More specifically, in the preparation method of chlorinated polyethylene according to the present disclosure, the chlorine can be performed by dispersing the prepared polyethylene with water, emulsifier, and dispersant, and then adding a catalyst and chlorine to react.ChemicalChemical reaction. Chemical reaction.

[0205] As the emulsifier, polyether or polyoxyalkylene can be used. The dispersant may be a polymer salt or an organic acid polymer salt. The organic acid may be methacrylic acid or acrylic acid.

[0206] The catalyst is, for example, a chlorination catalyst, and another example thereof is a peroxide or an organic peroxide. Chlorine can be used alone or can be mixed with an inert gas and then used.

[0207] The chlorination reaction can be performed at a temperature of 60°C to 150°C, 90 to 140°C, or 120 to 140°C.

[0208] In addition, the chlorination reaction may be performed for about 10 minutes to 10 hours, 1 hour to 6 hours, or 2 hours to 4 hours.

[0209] For example, the chlorination reaction can be achieved by dispersing 100 parts by weight of polyethylene, 0.01 to 1.0 parts by weight or 0.05 to 0.5 parts by weight of an emulsifier and 0.1 to 10 parts by weight or 0.5 to 5.0 parts by weight of a dispersant in water. , And then add 0.01 to 1.0 parts by weight or 0.05 to 0.5 parts by weight of the catalyst and 80 to 200 parts by weight or 100 to 150 parts by weight of chlorine to carry out the reaction.

[0210] The chlorinated polyethylene prepared through the above reaction or chlorination process may be further subjected to a neutralization process, a washing process, and a drying process, and thus may be obtained in a powder form.

[0211] The neutralization process may be, for example, a process of neutralizing the reactant that has been chlorinated with an alkali solution at 70 to 90°C or 75 to 80°C for 4 to 8 hours.

[0212] The chlorinated polyethylene obtained according to the preparation method of this embodiment has a high degree of crosslinking and an appropriate level of Mooney viscosity, and thus can exhibit excellent tensile strength.

[0213] Specifically, the Mooney viscosity (MV) of chlorinated polyethylene measured at a temperature of 121° C. is 70 to 80, more particularly 70 or more and 80 or less, or 76 or less.

[0214] The Mooney viscosity of chlorinated polyethylene can be measured using a Mooney viscometer. Specifically, it can be measured by rotating the rotor for 4 minutes after preheating at 121°C for 1 minute. The more specific method will be explained in detail in the experimental example described later.

[0215] In addition, the chlorinated polyethylene may be, for example, random chlorinated polyethylene.

[0216] The above-mentioned chlorinated polyethylene has excellent chemical resistance, weather resistance, flame retardancy, processability, and impact strength enhancing effects, and thus can be used for electric wires or cables.

[0217] Mixture

[0218] According to another embodiment of the present disclosure, there is provided a compound having excellent tensile strength properties including the chlorinated polyethylene prepared by the above method.

[0219] The kneaded material may specifically be a CPE kneaded material containing cross-linked chlorinated polyethylene. The cross-linked chlorinated polyethylene is cross-linked by the chlorinated polyethylene in the presence of a peroxide-based cross-linking agent. And preparation.

[0220] The crosslinking reaction can be performed at 140 to 230°C, and a peroxide-based crosslinking agent such as dicumyl peroxide can be used as the crosslinking agent. In addition, an antioxidant may optionally be further added during the crosslinking reaction.

[0221] For example, based on 100 parts by weight of chlorinated polyethylene, the chlorinated polyethylene (CPE) blend may include 100 parts by weight to 280 parts by weight of inorganic additives (such as talc and carbon black), and 20 parts by weight to 50 parts by weight. Parts by weight of plasticizer and 1 part by weight to 20 parts by weight of crosslinking agent.

[0222] The compound containing chlorinated polyethylene may exhibit excellent tensile strength, specifically, the tensile strength measured at 500 mm/min according to ASTM D412 is 12 or more, or 12 to 14.

[0223] In addition, conventional methods in the art can be applied to a method of preparing a molded article from the chlorinated polyethylene according to the present disclosure. For example, chlorinated polyethylene can be roll-kneaded and extruded to produce a shaped product.

[0224] Benefits

[0225] The polyethylene of the present disclosure has a molecular structure with a low content of low molecular weight and a high content of high molecular weight. Therefore, it can maintain excellent processability and Mooney viscosity characteristics while maintaining excellent processability and Mooney viscosity characteristics when preparing chlorinated polyethylene blends Improve tensile strength.

Detailed ways

[0226] The present invention will be described in more detail through the following examples. However, these examples are for illustrative purposes only, and the present invention is not intended to be limited by these examples.

[0227] <Preparation of the first transition metal compound>

[0228] Synthesis Example 1: [tert-Butyl-O- (CH₂)₆-C₅H₄]₂ZrCl₂Preparation

[0229] tert-Butyl-O-(CH₂)₆-Cl was prepared by the method shown in Tetrahedron Lett.2951 (1988) using 6-chlorohexanol and reacted with NaCp to obtain tert-butyl-O- (CH₂) 6-C5H5 (60% yield, boiling point 80°C/0.1mmHg).

[0230] In addition, the tert-butyl-O-(CH₂) ₆-C₅H₅Dissolve in THF, and slowly add n-butyllithium (n-BuLi) to it. After that, it was heated to room temperature and reacted for 8 hours. At -78°C, slowly add the lithium salt solution synthesized as described above to ZrCl₄ (THF) ₂(1.70g, 4.50mmol)/THF (30mL) suspension, and further react at room temperature for about 6 hours.

[0231] All volatiles were vacuum dried, and the resulting oily liquid material was filtered by adding a hexane solvent. The filtered solution was dried in a vacuum, and hexane was added to obtain a precipitate at low temperature (-20°C). The obtained precipitate was filtered at low temperature to obtain [tert-butyl-O-(CH₂)₆-C₅H₄]₂ZrCl₂(Yield 92%).

[0232] ¹H NMR(300MHz, CDCl₃): 6.28 (t, J = 2.6Hz, 2H), 6.19 (t, J = 2.6Hz, 2H) ,3.31 (t,

6.6Hz, 2H), 2.62 (t, J = 8Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H).

[0233] ¹³CNMR (CDC13): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14,

29.18,27.58,26.00。

<Preparation of the second transition metal compound>

[0235] Synthesis Example 2

Step 1: Preparation of Ligand Compound

[0237] 4-(3,5-Di-tert-butylphenyl)-2-isopropyl-1H-indene (1.39g, 4mmol) was added as a Cp unit to a 50ml Schlenk flask, and THF ( 13ml), and then cooled to below -20°C. After the cooled mixed solution was stirred for 5 minutes, NBL (1.7 ml, 2.5 M hexane solution) was added, and reacted overnight to prepare lithiated Cp. When NBL was added, the mixed solution turned reddish brown.

[0238] Dichloro(tert-butoxy)hexyl)methylsilane (1.14 g) was added to another 100 mL Schlenk flask, and THF (13 ml) was added thereto. After cooling the Schlenk flask to below -20°C, the lithiated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the resulting reactant was removed by vacuum distillation under reduced pressure, and the resulting salt was filtered off with hexane (Hex). In the t-BuNH₂ (1.7ml) was added to the resulting reactant for reaction, and the resulting precipitate was filtered using hexane to obtain 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(4- (3,5-Di-tert-butylphenyl)-2-isopropyl-1H inden-1-yl)-1-methylsilylamine ligand compound (yellow oil, 2.41g, yield 97% ( In moles)).

[0239] NMR (400MHz, C6D6), 7.70-7.68 (m, 1H), 7.60-7.47 (m, 4H), 7.34-7.19 (m, 2H), 7.07 (s, 0.5H), 6.89 (s, 0.5 H) ,3.36-3.21 (m,4H) ,3.12(s,1H) ,2.52-2.44 (m,0.5H) ,2.00-1.92 (m,0.5H) ,1.72-1.39 (m,8H), 1.39 ( s,9H), 1.31 (s,9H), 1.23 (s,3H) 1.19 (s,3H) ,1.13(s, 9H)0.98(s,9H)0.32(s,1H) ,0.25 (s, 0.5H) ,0.2 0(s,1H) ,0.12 (s,0.5H)

Step 2: Preparation of transition metal compound

[0241] The 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(4-(3,5-di-tert-butylphenyl)- 2-isopropyl-1H-inden-1-yl)-1-methylsilylamine ligand compound (2.4g, 3.9mmol) was added to a 100ml Schlenk flask, and toluene (13ml) was added to it, and then Cool to below -20°C. After being sufficiently cooled by stirring for 5 minutes, NBL (5.1 ml, 2.5 M hexane solution) was added to the resulting mixed solution to perform lithiation. It was confirmed that the color of the mixed solution changed to brown after lithiation. When the lithiation is completed, the resulting reaction solution is cooled to 0°C. After adding NMB (13ml, 3M ether solution) to it, immediately lower the temperature to -20°C and add TiCl₄(3.9ml, 1M toluene). Smoke is generated when added, and the reaction is dissolved

The liquid turned brown immediately. After adding, proceed. /η was stirred, and then the salt was removed through a filter to obtain the transition metal compound (2a) (brown oil, 2.16 g, yield 80% (by mole)).

[0242]

<img file="CN113166316A_D0009.tif" />

[0243] NMR (400MHz, C6D6), 7.79-7.76 (m, 2H), 7.64-7.47, 3.35-3.21,

2.76-2.49 (s,2H) ,1.99-1.91, 1.70-1.60 (m,4H) ,1.53 (s,9H), 1.51 -1.44,

1.36 (s, 9H), 1.30 (s, 9H), 1.20 (s, 6H), 1.13 (s, 9H), 0.59 (s, 3H), 0.12 (s, 3H) [0244] <Hybrid supported catalyst Preparation> [0245] Synthesis Example 3

[0246] Preparation of the carrier

[0247] Silica (SYLOPOL 948TM, manufactured by Grace Davison) was dehydrated and dried under vacuum at a temperature of 600°C for 12 hours.

[0248] Preparation of hybrid supported catalyst

[0249] 10 g of silica dried in step (1) was introduced into a glass reactor, and another 100 mL of toluene was added and stirred. After the silica was sufficiently dispersed, 60.6 mL of a 10% by weight methylaluminoxane (MA0)/toluene solution was added thereto. Thereafter, the temperature was increased to 80°C, and the mixture was slowly reacted for 16 hours while stirring at 200 rpm. After lowering the temperature to 40°C again, the reaction solution was washed with a sufficient amount of toluene to remove unreacted aluminum-based compounds, and the remaining toluene was removed under reduced pressure. 100 mL of toluene was added thereto again, and 0.24 mmol of the first transition metal compound prepared in Synthesis Example 1 dissolved in toluene was added thereto and reacted for 1 hour. After the completion of the reaction, 0.12 mmol of the second transition metal compound prepared in Synthesis Example 2 dissolved in toluene was added, and the reaction was further carried out for 2 hours under stirring. After the reaction was completed, the stirring was stopped, and the toluene layer was separated and removed. Then, the remaining toluene was removed under reduced pressure at 40°C to prepare a hybrid supported catalyst.

Synthesis Example 4

[0251] Except that the amount of the second transition metal compound was changed to 0.06 mmol (the molar ratio of the first transition metal compound: the second transition metal compound = 4:1), the hybrid supported type was prepared in the same manner as in Synthesis Example 3. catalyst.

[0252] <Preparation of Polyethylene>

Example 1

[0254] Using the hybrid supported catalyst prepared in Synthesis Example 3, the ethylene homopolymerization reaction was carried out under the following conditions.

[0255] First, 30kg/hr of hexane, 10kg/hr of ethylene, 1g/hr of hydrogen and 130cc/hr of triethylaluminum (TEAL) were introduced into 0.2mL³In a single CSTR reactor, then the hybrid supported catalyst prepared in Synthesis Example 3 was injected into it at 0.2 kg/hr. At this time, the reactor was maintained at a temperature of 82° C. and a pressure of 7.0 kg/cm? to 7. Skg/cm?, and polymerization was performed for about 4 hours. After that, the polymerization product is made into the final polyethylene through a solvent removal device and a dryer.

Example 2

[0257] Polyethylene was prepared in the same manner as in Example 1, except that hydrogen was introduced at 1.5 g/hr.

Example 3

[0259] Polyethylene was prepared in the same manner as in Example 1, except that hydrogen was introduced at 0.5 g/hr.

[0260] Comparative Example 1

[0261] The use of high-density polyethylene prepared using Ziegler-Natta catalyst (CE2080^TM, Manufactured by LG Chem).

[0262] Comparative Example 2

[0263] The use of high-density polyethylene prepared using a metallocene catalyst (SC200^TM, Manufactured by LG Chem).

[0264] Comparative Example 3

[0265] The use of high-density polyethylene prepared using a metallocene catalyst (SC100E^TM, Manufactured by LG Chem).

[0266] Comparative Example 4

[0267] The use of high-density polyethylene prepared using Ziegler-Natta catalyst (CE6040X^TM, Manufactured by LG Chem).

[0268] Comparative Example 5

[0269] Polyethylene was prepared in the same manner as in Example 1, except that hydrogen was not introduced during the polymerization.

[0270] Comparative Example 6

[0271] Polyethylene was prepared in the same manner as in Example 1, except that the hybrid supported catalyst prepared in Synthesis Example 4 was used.

[0272] Comparative Example 7

[0273] Commercially available polyethylene (5000Cp^TM, Manufactured by Lotte Chemical).

[0274] Experimental Example 1

[0275] GPC analysis was performed on the polyethylene prepared in the Examples and Comparative Examples in the following manner, and the content of each molecular weight distribution, that is, the fraction, was calculated. The results are shown in Table 1 below.

[0276] Fraction (%): GPC analysis is performed, and the fraction is calculated as the area (%) occupied by the log Mw portion relative to the total area in the obtained molecular weight distribution curve. The sum of the scores is 100±1, which may not be exactly 100.

[0277] The GPC analysis was specifically performed under the following conditions.

[0278] A Waters PL-GPC220 was used as a gel permeation chromatography (GPC) instrument, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. The evaluation temperature was 160°C, and 1,2,4-trichlorobenzene was used for the solvent at a flow rate of 1 μm/μm. Use a GPC analyzer (PL-GP220) to dissolve each polyethylene sample in 1,2,4-trichlorobenzene containing 0.0125% BHT for 10 hours for pretreatment, and provide a concentration of 10mg/10mL in the amount of 200UL sample. A calibration curve formed using polystyrene standards was used to obtain Mw and Mn. Nine polystyrene standards with molecular weights of 2000g/mol, 10000g/mol>30000g/mol>70000g/mol>200000g/mol>700000g/mol>2000000g/mol>4000000g/mol and 10000000g/mol were used.

[0279] [Table 1]

<td></td><td colspan="8">Fraction(%)</td>

<td>Log Mw</td><td>Less than 3.5</td><td>3.5 or more and less than 4.0</td><td>Above 4.0 and 4.5 to BU.</td><td>Greater than 45 and less than 5.0</td><td>5.0 and above 6.0 to BU.</td><td>Greater than 6.0 and less than 6.5</td><td>Greater than 6,5 and 7.0 to Bu.</td><td>Greater than 7. (1</td>

<td>Example 1</td><td>0.54</td><td>3.78</td><td>19.85</td><td>41.58</td><td>29.79</td><td>3.41</td><td>LU5</td><td>0</td>

<td>Example 2</td><td>0.80</td><td>3.93</td><td>18.74</td><td>42.72</td><td>29.63</td><td>3.20</td><td>0,98</td><td>0</td>

<td>Example 3</td><td>0.51</td><td>3.63</td><td>20.24</td><td>41.19</td><td>29.81</td><td>3.53</td><td>L09</td><td>0</td>

<td>Comparative example 1</td><td>N64</td><td>8.89</td><td>22.89</td><td>29.03</td><td>3L99</td><td>3.94</td><td>662</td><td>0</td>

<td>Comparative example 2</td><td>2.22</td><td>8.53</td><td>24.15</td><td>28.17</td><td>34.64</td><td>2.27</td><td>0_.02</td><td>0</td>

<td>Comparative example 3</td><td>0_.00</td><td>2.12</td><td>14.47</td><td>37.98</td><td>42 imaginary 5</td><td>2.51</td><td>(UJ7</td><td>0</td>

<td>Comparative example 4</td><td>657</td><td>430</td><td>16.22</td><td>34.09</td><td>42.47</td><td>235</td><td>0</td><td>0</td>

<td>Comparative example 5</td><td>0.38</td><td>2.94</td><td>21.85</td><td>40.81</td><td>2S.42</td><td>3.74</td><td>1.86</td><td>0</td>

<td>Comparative example 6</td><td>651</td><td>4.27</td><td>22.49</td><td>41.21</td><td>2825</td><td>2.74</td><td>0.53</td><td>0</td>

<td>Comparative example 7</td><td>0.73</td><td>5.12</td><td>17.45</td><td>30.62</td><td>43.69</td><td>2.35</td><td>0.04</td><td>0</td>

[0281] Experimental Example 2

[0282] The physical properties of the polyethylene prepared in the Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2.

[0283] Weight average molecular weight (Mw, g/mol) and molecular weight distribution (PDI, polydispersity index): GPC analysis was performed in the same manner as in Experimental Example 1, and by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn), and then obtain the ratio of Mw/Mn to calculate the molecular weight distribution (PDI).

[0284] Μ*.. And MFRIj 6/5: The melt index (M*0) of the polyethylene prepared in the examples and comparative examples was measured according to ASTM D1238 (condition E, 190°C, 5.0 kg load). In addition, the melt flow rate ratio (MFRR21 6/D, Cai 16 is measured at 190°C under a load of 21.6 kg according to ASTM D 1238, and MF (according to ASTM D ijl.O) is calculated by dividing MFIj 6 by then ?5. /O ώΐ.0 Ο

1238 is measured at 190°C under a load of 5 kg.

(3) Density (g/cm³): The density (g/cn?) is measured according to ASTM D-1505.

[0286] (4) MDR torque (Mr-M1): In order to evaluate the degree of crosslinking of polyethylene, the MDR torque of each polyethylene sample was measured with Alpha Technologies Production MDR (Dynamic Mold Rheometer).

[0287] Specifically, 100 g of each polyethylene sample prepared in Examples and Comparative Examples, 0.4 g of phenolic antioxidant (A0) and L 2 g of crosslinking agent (DCP, dicumyl peroxide) were prepared at 80°C. ) After mixing, prepare sample pieces at 140°C for 10 minutes. Then, use MDR (Moving Mode Rheometer) to measure the actual and visible values of the sample pieces at 180°C for 10 minutes. Calculate the MDR torque (M_h-M_l). Here, Mn is the maximum vulcanization torque measured when fully cured, but should be the minimum stored vulcanization torque.

(5) Entanglement molecular weight (Me): The entanglement molecular weight (Me) is calculated from the storage modulus and loss modulus measured by a rotational rheometer.

[0289] Specifically, the storage modulus and loss modulus of each polyethylene sample of the Examples and Comparative Examples were measured with a rotational rheometer. Then, the platform modulus (G's) is obtained from them, and the entanglement molecular weight is calculated according to the following formula 1.

[Equation 1]

[0291] M_e= (pRT) /G_n°

[0292] In Formula 1,

[0293] p=0.8X (density of polyethylene measured in accordance with ASTM DT505 (kg/πί³),

[0294] R is the gas constant of polyethylene (8.314 Pa·m³/mol · K),

[0295] T is the absolute temperature (Κ) of the measured temperature, and

[0296] G/ is the platform modulus of polyethylene, which is the highest loss modulus in the region where the storage modulus is greater than the loss modulus.

The storage modulus at a small value, where the storage modulus and loss modulus are measured using a rotational rheometer at 190°C and 0.5% strain and changing the angular frequency to 0.05 to 500 rad/s.

[0297] [Table 2]

<td></td><td>Mw (g/mol)</td><td>PD(</td><td>M1₅.o (g/lOmin)</td><td>MFRR₂1.6/5</td><td>Density (g/cm³)</td><td>MDR torque (Nm)</td><td>Me (g/mol)</td>

<td>Example 1</td><td>216,000</td><td>5.7</td><td>1.25</td><td>10.6</td><td>0.948</td><td>11.7</td><td>41,300</td>

<td>Example 2</td><td>196,000</td><td>6.1</td><td>2.41</td><td>10.3</td><td>0.950</td><td>H.5</td><td>49,500</td>

<td>Example 3</td><td>233,000</td><td>5.6</td><td>1.0</td><td>10.9</td><td>0.947</td><td>11.8</td><td>34,800</td>

<td>Comparative example 1</td><td>177,000</td><td>9.1</td><td>1.3。</td><td>15.2</td><td>0.958</td><td>5.6</td><td>13,800</td>

<td>Comparative example 2</td><td>168,000</td><td>5.。</td><td>OS</td><td>160</td><td>0.955</td><td>7.7</td><td>10,300</td>

<td>Comparative example 3</td><td>171,000</td><td>4.5</td><td>0.8</td><td>11.0</td><td>0.950</td><td>9.0</td><td>21,500</td>

<td>Comparative example 4</td><td>174,000</td><td>4.8</td><td>1.0</td><td>11.2</td><td>0.952</td><td>6.3</td><td>15,400</td>

<td>Comparative example 5</td><td>264,000</td><td>5.1</td><td>0.49</td><td>11.2</td><td>0.945</td><td>12.1</td><td>25,100</td>

<td>Comparative example 6</td><td>182,000</td><td>6.0</td><td>3.0</td><td>14.2</td><td>0.953</td><td>10.7</td><td>52,600</td>

<td>Comparative example 7</td><td>175,000</td><td>5,2</td><td>1.2</td><td>12.3</td><td>0.952</td><td>9.5</td><td>31,700</td>

[0299] Experimental Example 3

[0300] The polyethylene prepared in one of the above Examples and Comparative Examples was used to prepare chlorinated polyethylene, and the physical properties of the prepared chlorinated polyethylene were evaluated by the following methods. The results are shown in Figure 3.

(1) Preparation of chlorinated polyethylene

[0302] 5,000 L of water and 550 kg of polyethylene prepared in one of the Examples and Comparative Examples were added to the reactor, followed by sodium polymethacrylate as a dispersant, propylene oxide and ethylene oxide as an emulsifier Copolymerization of aldehydes and benzoyl peroxide as a catalyst. Then, chlorination was performed for 3 hours by injecting gaseous chlorine at a final temperature of 132°C. The chlorinated reactant was neutralized with NaOH or Na2cO3 for 4 hours, washed with running water for 4 hours, and finally dried at 120°C to obtain chlorinated polyethylene in powder form.

[0303] Mooney viscosity (MV): Wrap the rotor in the Mooney viscometer with a CPE sample, and then close the mold. Preheat to

121 After 1 minute at °C, the rotor was rotated for 4 minutes to measure MV (Mooney viscosity, 121 °C, MLl+4).

[0304] [Table 3]

<td></td><td>MV</td>

<td>Example 1</td><td>73</td>

<td>Example 2</td><td>71</td>

<td>Example 3</td><td>76</td>

<td>Comparative example 1</td><td>72</td>

<td>Comparative example 2</td><td>72</td>

<td>Comparative example 3</td><td>85</td>

<td>Comparative example 4</td><td>87</td>

<td>Comparative example 5</td><td>86</td>

<td>Comparative example 6</td><td>64</td>

<td>Comparative example 7</td><td>83</td>

[0306] Experimental Example 4

[0307] The polyethylene prepared in one of the above examples and comparative examples in Experimental Example 3 was used to prepare a CPE compound, and physical properties were evaluated.

[0308] Preparation of CPE compound

40% by weight of chlorinated polyethylene, 15% by weight of plasticizer, 2% by weight of crosslinking agent, and the balance of talc prepared using polyethylene prepared in one of the examples and comparative examples in Experimental Example 3 It is mixed with carbon black inorganic additives and processed to prepare CPE mixed samples.

[0310] MV (Mooney Viscosity) of the CPE compound: Wrap the rotor in the Mooney viscometer with the CPE compound, and then close the mold. After preheating to 100°C for 1 minute, rotate the rotor for 4 minutes to measure MV (Mooney viscosity, 100°C, ML1+4). The results are shown in Table 4.

[0311] Tensile strength (MPa) of the CPE compound: After cross-linking the CPE compound sample prepared above at 160° C. for 10 minutes, the CPE compound was measured under the condition of 500 mm/min according to ASTM D-412 The tensile strength of the material (MPa). The results are shown in Table 4 below.

[03Table 4

<td></td><td>MV</td><td>Tensile strength (MPa)</td>

<td>Example 1</td><td>54</td><td>13.9</td>

<td>Example 2</td><td>53</td><td>13.7</td>

<td>Example 3</td><td>55</td><td>14.0</td>

<td>Comparative example 1</td><td>53</td><td>1L9</td>

<td>Comparative example 2</td><td>53</td><td>12.5</td>

<td>Comparative example 3</td><td>60</td><td>】2.5</td>

<td>Comparative example 4</td><td>60</td><td>12.6</td>

<td>Comparative example 5</td><td>61</td><td>14.2</td>

<td>Comparative example 6</td><td>42</td><td>9.8</td>

<td>Comparative example 7</td><td>59</td><td>13.1</td>

[0314] Referring to the experimental results, compared with the comparative example, the CPE compound prepared using the polyethylene of Examples 1 to 3 has improved tensile strength while maintaining excellent Mooney viscosity characteristics.