Polyethylene, and chlorinated polyethylene thereof

Technical field of polyethylene and its chlorinated polyethylene

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims 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 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 the same, by achieving a molecular structure with a low content of low molecular weight and a high content of high molecular weight, said polyethylene in the preparation of chlorinated polyethylene compounds , capable of increasing tensile strength while maintaining excellent processability and Mooney viscosity characteristics.

Background technique

[0004] Olefin polymerization catalyst systems can be classified 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 their development in the 1950s. However, since the Ziegler-Natta catalyst is a multi-site catalyst in which a plurality of active sites are mixed, it has a feature 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, a polymer chain having a relatively low molecular weight may deteriorate physical properties due to a broad molecular weight distribution.

[0005] Meanwhile, the metallocene catalyst includes a metallocene compound as the main component of the main catalyst and aluminum as the main component of the organometallic compound catalyst. The tacticity, 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 one carrier. The catalyst is prepared by supporting a high molecular weight titanium (Ti) type Ziegler-Natta catalyst and a low molecular weight zirconium (Zr) type metallocene catalyst on a carrier, and produces double mode molecular weight distribution. The disadvantage of this catalyst is that the loading process is complicated and the polymer morphology is poor due to the cocatalyst.

U.S. Patent No. 5,525, No. 678 discloses a kind of method that catalyst system is used for olefin polymerization, and wherein, metallocene compound and non-metallocene compound are loaded on the carrier simultaneously, to realize the simultaneously of high molecular weight polymer and low molecular weight polymer polymerization. However, there are disadvantages in that metallocene compounds and non-metallocene compounds must be supported separately, and supports must be pretreated with various compounds for loading.

[0008] US Patent No. 5,914,289 discloses a method of controlling the molecular weight and molecular weight distribution of polymers using metallocene catalysts separately supported on supports. However, the preparation of supported catalysts requires a large amount of solvent and a long time, and the process of loading metallocene catalysts on various supports is cumbersome.

[0009] Furthermore, according to the prior art, there is the disadvantage that it is difficult to efficiently prepare polyolefins, especially ethylene (co)polymers satisfying both desired density levels and narrow molecular weight distributions.

[0010] Meanwhile, chlorinated polyethylene (CPE) is a product obtained by replacing a part of hydrogen in polyethylene with chlorine, and is used as an impact modifier or crosslinking of polyvinyl chloride (PVC) to make cable sheathing or rubber hose.

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

To prevent damage to the sheath when the cable is bent, chlorinated polyethylene must have excellent tensile strength in cross-linked compounds.

[0012] In the case of PVC compounded products, the strength of the compound will vary depending on the nature of the chlorinated polyolefin. In the case of the currently well-known general-purpose chlorinated polyethylene, since polyethylene prepared using a Ziegler-Natta catalyst is applied, the uniformity of chlorine distribution in the polyethylene is lowered due to a broad molecular weight distribution. There is also a disadvantage of insufficient impact strength when compounded with PVC.

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

Generally, the higher the Mooney viscosity (MV) of chlorinated polyethylene, the higher the Mooney viscosity of the kneaded product, the higher the tensile strength of the kneaded product, but there is a problem that the processability in the compression process decreases .

[0015] Accordingly, there is a need to prepare high density polyethylene capable of increasing the tensile strength of the compound without reducing processability while having a similar Mooney viscosity, and to develop a catalyst therefor.

Contents of the invention

Technical problem

Therefore, a kind of polyethylene and preparation method thereof are provided, by realizing the molecular structure with the low molecular weight of low content and the high molecular weight of high content, when described polyethylene is preparing chlorinated polyethylene compound, can keep Excellent processability and Mooney viscosity characteristics while increasing tensile strength.

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

Technical scheme

[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 more than polyethylene,

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

The area fraction representing the medium molecular weight content of 4.5<log Mw<5.0 is 35% to 50%, and

The area fraction representing the low molecular weight content of log Mw<4.0 is below 10%,

The above area fractions are relative to the molecular weight distribution plotted using gel permeation chromatography with the logarithmic value of the weight average molecular weight (log Mw) as the x-axis and the molecular weight distribution relative to the logarithmic value (dw/dlog Mw) as the y-axis the total area of the curve, and

The entanglement molecular weight (M) of following formula 1_e) is 27,000 to 52,000g/mo1:

[formula 1]

[0027] M_e= (pRT)/G_no⁰

In formula 1,

ρ=0.8X (according to the density (kg/m of the polyethylene of ASTM D-1505 measurement)³),

R is the gas constant (8.314Pa·m) of polyethylene³/mo1 K),

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

[0032] G_no⁰is the plateau modulus of polyethylene, which is the storage modulus at which the loss modulus has a minimum value in the region where the storage modulus is greater than the loss modulus, where the storage and loss moduli are measured using a rotational rheometer Measured under conditions of 190°C and 0.5% strain varying the angular frequency from 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

Chemicalized polyethylene.

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

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

[0036] Since the present invention can be variously modified and have various forms, specific embodiments of the present invention will be shown by way of example 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 replacements 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 for rubber hose or cable sheathing requires high tensile strength. Although the tensile strength of chlorinated polyethylene can be increased by increasing the Mooney viscosity of the chlorinated polyethylene or the Mooney viscosity of the kneaded product, there is a problem that extrusion processability deteriorates. In order to solve this problem, it is necessary to optimize the molecular structure of polyethylene, especially high-density polyethylene applied to chlorinated polyethylene.

[0039] It is demonstrated in this disclosure that the combined use of two transition metal compounds having specific structures can provide polyethylene with a high content of high molecular weight and a minimal content of low molecular weight. Therefore, when the chlorinated polyethylene compound is produced, 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 accomplished.

In this disclosure, the molecular weight distribution curve uses gel permeation chromatography (GPC) with the logarithmic value of the weight average molecular weight (log Mw) as the x-axis and the molecular weight distribution relative to the logarithmic value (dw/dlog Mw) as The y-axis is plotted. 10g Mw>6.0, 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/mo1, defined as "low molecular weight"; 4.0Wlog MwW6.0, that is, 10⁴,⁰More than g/mol and 10⁶,⁰The weight average molecular weight (Mw) below g/mol is defined as "medium molecular weight".

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

[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 may be 160° C., and 1,2,4-trichlorobenzene may be used for the solvent at a flow rate of 1 mL/min. Each polyethylene sample can be pretreated by dissolving each polyethylene sample in 1,2,4-trichlorobenzene containing 0.0125% BHT (butylated hydroxytoluene) for 10 hours using a GPC analyzer (PLGP220), and can be analyzed by 200 UL Provide a sample with a concentration of 10mg/10mL. Mw and Mn can be obtained using calibration curves 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, the polyethylenes of the present disclosure have 0.945 g/cm when measured according to ASTM D-1505³above the density,

Wherein, the area fraction representing the high molecular weight content of 10g Mw>6.0 is 4% to 12%, represents 4.5<log Mw

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

[0046] The high and low molecular weight content of the polyethylene molecule affects the physical properties of the 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 produced, the Mooney viscosity increases, resulting in decreased processability. On the other hand, when the low-molecular-weight content in polyethylene is too high, the low-molecular-weight components melt and become high in fluidity, so that the pores of polyethylene particles may be clogged, resulting in low chlorination productivity.

In polyethylene according to an embodiment of the present disclosure, less than Mw 10⁴·⁰The fraction of low molecular weight content in g/mol, ie the area fraction in the molecular weight distribution curve representing low molecular weight content of log Mw&lt;4.0, 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 10³·⁵The fraction of ultra-low molecular weight content in g/mol, that is, the area fraction representing ultra-low molecular weight content of log Mw&lt;3.5 in the molecular weight distribution curve is less than 2%, less than 1.5% or less than 1%, and Mw 10³·⁵More than g/mo1 and less than Mw 10⁴·⁰The 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 increases, and reduction in chlorination productivity caused by melting of low molecular weight components can be prevented.

In addition, in polyethylene, greater than Mw 10⁶·⁰The fraction of high molecular weight content in g/mol, ie the area fraction representing high molecular weight content of log Mw > 6.0 in the molecular weight distribution curve, is from 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 decreases, and when it exceeds 12%, there is an increase in the Mooney viscosity of chlorinated polyethylene due to an excessively high content of the high molecular weight content, so There is concern that processability may deteriorate. 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] Furthermore, 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 having a higher ultra-high molecular weight content than conventional ones, it can exhibit more improved cross-linking degree and entanglement properties.

[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 thus processability decreases during the production of chlorinated polyethylene compounds. 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 specifically 35% or more and 50% or less or 45%, the excellent performance of chlorinated polyethylene can be maintained. processability and Mooney viscosity properties.

In addition, polyethylene has 0.945g/cm³Above, or 0.945 to 0.955g/cm³high 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 polyethylene has an entanglement molecular weight (Me) of 27,000 g/mol to 52,000 g/mol. Entanglement molecular weight refers to the average molecular weight of the entanglement points between ethylene polymer chains. When the entanglement molecular weight is small, the degree of entanglement of ethylene polymer chains increases, which means excellent resistance to deformation by external force and excellent crack resistance. Generally, processability and long-term durability are opposite properties, so if the melt index or melt flow rate ratio is increased to improve processability, long-term durability decreases.

When according to the following formula 1 by using the storage modulus of polyethylene measured at an angular frequency of 0.05rad/s to 500rad/s at a temperature of 150 to 230°C, particularly 190°C, at 0.5% strain and the plateau modulus obtained from the loss modulus (G_N⁰) calculated, the polyethylene of the present disclosure has an entanglement molecular weight within the above range, thereby having excellent long-term durability without reducing processability. More specifically, the polyethylene has an entanglement molecular weight of 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.

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

[Formula 1]

[0056] M_e= (pRT)/G_no⁰

In formula 1,

ρ=0.8X (according to the density (kg/m of the polyethylene of ASTM D-1505 measurement)³),

R is the gas constant (8.314Pa·m) of polyethylene³/mol K),

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

[0061] G_N⁰is the plateau modulus of polyethylene, which is the storage modulus at which the loss modulus has a minimum value in the region where the storage modulus is greater than the loss modulus, where the storage and loss moduli are measured using a rotational rheometer Measured under conditions of 190°C and 0.5% strain varying the angular frequency from 0.05 to 500 rad/s.

In addition, when polyethylene is used for the preparation of Mooney viscosity (MV) is chlorinated polyethylene more than 70 to prevent the physical properties of CPE kneaded material from reducing, melt index (MI₅; measured according to ASTM D 1238 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 in order to prevent a decrease in the processability of the CPE kneaded product, 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.

The melt flow rate ratio (MFRR) of described polyethylene₂₁._6/5) can be from 10 to 20, the melt flow rate ratio (MFRR₂₁._6/5) by taking the MFR measured at 190°C under a load of 21.6 kg according to ASTM D 1238₂₁.₆Divided by the MFR measured at 190°C under a load of 5 kg according to ASTM D 1238₅get. When the melt flow index is within the above range, the MV can be properly controlled without degrading 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 deteriorate, and if it is less than 10, the processability of the CPE compound may decrease. 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 polyethylene has a weight average molecular weight (Mw) of 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 polyethylene has a PDI of 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 molecular weight difference among polyethylenes is large, so it is difficult to uniformly distribute chlorine in the chlorinated polyethylene after the chlorination reaction. When Mw and PDI are within the above ranges, the effects of improving processability and having excellent mechanical properties can be obtained in good balance. In particular, there is little difference in molecular weight among polyethylenes after chlorination, so chlorine can be substituted uniformly.

[0065] In the present disclosure, weight average molecular weight and molecular weight distribution (PDI, polydispersity index) can be measured using gel permeation chromatography. The molecular weight distribution can be determined by measuring 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 examples described later.

In addition, the MDR torque of polyethylene (M_h - M_L) can be above 7Nm, above 10Nm, or above 11Nm, and above 12Nm

Under, 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 of polyethylene (eg - this) refers to the degree of crosslinking. The higher the degree of cross-linking, the higher the consistency. When using the same crosslinking agent, a high MDR torque means excellent crosslinking efficiency. The MDR torque of polyethylene can be measured e.g. The MDR torque was measured by subtracting the gross value from this value to calculate the MDR. Here, as is the maximum vulcanization torque measured at full cure, but also the minimum vulcanization torque stored. The specific method is as described in the experimental examples described later.

[0068] Also, the polyethylene of the present disclosure may be an ethylene homopolymer containing no comonomer.

The optimum molecular structure and physical property of polyethylene can be realized by the preparation method that comprises the following steps: when introducing hydrogen, in the first transition metal compound that comprises following chemical formula 1, the second transition metal compound of following chemical formula 2 Polymerizing ethylene monomer in the presence of a hybrid supported catalyst supporting a first and second transition metal compound, wherein the first transition metal compound and the second transition metal compound are used in a molar ratio of 1:3 to 3 :1. Therefore, another embodiment of the present disclosure provides a method for preparing polyethylene.

[chemical formula 1]

(CplR ") m (Cp2₁y called

In chemical formula 1,

Ming is a transition metal of Group 4;

CP1 and Cp2 are identical or different from each other, and each independently is any one selected from the group consisting of cyclopentadienyl, cyanidyl, 4,5,6,7 tetrahydro 7-xenyl and sulphuryl kind. Here, they can replace Gw Huang.

R and each other are the same or different, each independently hydrogen, such as a 20 alkyl, such as a 20 alkoxyl group, C2-20 alkoxyalkyl, 06-20 aryl, 06-20 aryloxy, alkenyl Base, 07-40 alkyl aryl, 07-40 aryl alkyl, 08 (aryl alkenyl, C2-20 carboxyl, or one or more selected from the group consisting of N, O and S Czroheteroaryl of heteroatoms;

Z is halogen, C alkyl, C alkenyl, C7-40 alkylaryl, C7-40 aralkyl, C6-20 aryl, substituted or unsubstituted J T0 alkylene, substituted or unsubstituted Substituted amino, 20 alkylalkoxy or C7-arylalkoxy; and

m is 1 or 0;

[chemical formula 2]

[0079]

<img file="CN113166316B_D0001.tif" />

In chemical formula 2,

A is carbon or silicon,

M2 is the transition metal of the 4th group,

Rzi is the C6-20 aryl group that is substituted with C mo alkyl,

hz for Co branched alkyl,

[0085] R₂₃to R₂₅each independently for C1_₂₀alkyl,

Z₂₁and Z₂₂each independently halogen or C₁T_oalkyl, and

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

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

[0089] CL₂₀Alkyl 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 straight chain or branched alkylene group, specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, or hexylene group, etc., but not limited thereto.

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

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

[0093] C_6-20The aryl group may include monocyclic or condensed ring aryl groups, specifically, phenyl, biphenyl, naphthyl, phenanthrenyl, or phenanthrenyl, but not limited thereto.

[0094] C₁r_oThe alkoxy group may include methoxy, ethoxy, phenoxy or cyclohexyloxy, etc., but is not limited thereto.

[0095] C_2-20Alkoxyalkyl can be the functional group wherein one or more hydrogens of the above-mentioned alkyl are substituted by alkoxy, specifically, can include: alkoxyalkyl, such as methoxymethyl, methoxyethyl , ethoxymethyl, isopropoxymethyl, isopropoxyethyl, isopropoxyhexyl, tert-butoxymethyl, tert-butoxyethyl or tert-butoxyhexyl, etc.; or aromatic Oxyalkyl, such as phenoxyhexyl, etc., but not limited thereto.

[0096] C₁r_oAlkylsilyl or C₁r_oAlkoxysilyl can be where - $ up to₃A functional group in which 1 to 3 hydrogens are substituted by 1 to 3 alkyl or alkoxy groups as described above, specifically, may include: an alkylsilyl group, such as a methylsilyl group, a dimethylsilyl group base, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl or dimethylpropylsilyl, etc.; alkoxysilyl, such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group or dimethoxyethoxysilyl group, etc.; alkoxyalkylsilyl group, such as methoxydimethylsilyl group, two Ethoxymethylsilyl or dimethoxypropylsilyl, etc., but not limited thereto.

[0097] C_1-20A silylalkyl group is a functional group in which one or more hydrogens of the above-mentioned alkyl groups are replaced by a silyl group, specifically, may include -CH₂-SiH₃, methylsilylmethyl or dimethylethoxysilylpropyl, etc., but not limited thereto.

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

[0099] Sulfonate group has -O-SO₂- the structure of R', where R' can be C₁r_oalkyl. Specifically, C₁r_oThe sulfonate group may include mesylate group, benzenesulfonate group, etc., but is not limited thereto.

Heteroaryl is C comprising one or more of N, O and S as heteroatoms_2-20Heteroaryl, specific examples of which may include xanthene, thioxanthen, thiophene, bifuryl, fenazole, imidazole, thiazole, oxazole, xanthene, triazole, pyridyl, bicyclyl , pyridyl, triazine, acridinyl, pyridazine, pyrazinyl, quinolinyl, quinazoline, quinoxalinyl, phthaloyl, this pyridinyl, pyridopyrazinyl , pyrazinoxazinyl, isoquinoline, indole, carbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiaphne, benzoenyl, phenanthrole phenanthroline, isoxazolyl, thiadiazolyl, phenothiazinyl or dibenzopyranyl, etc., but not limited thereto.

[0101] Within the scope of having the same or similar effects as the desired effect, the above-mentioned substituents can optionally be substituted with one

or more substituents selected from the group consisting of: hydroxyl; halogen; alkyl, alkenyl, aryl or alkoxy; one or more heteroatoms comprising Groups 14 to 16 Alkyl, alkenyl, aryl or alkoxy; silyl; alkylsilyl or alkoxysilyl; instantaneous; phosphides; sulfonates and sulfones.

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

[0103] Among the hybrid supported catalysts, the first transition metal compound exhibits high polymerization activity and easy preparation of low molecular weight polymers. Also, it is easier to prepare high molecular weight polymers with the second transition metal compound than with 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 obtained 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 so produced may have an increased degree of crosslinking and entanglement.

Specifically, the first transition metal compound represented by chemical formula 1 contains Cp¹and Cp²The uncrosslinked compound of the ligand, where Cp¹and Cp²The ligands may be the same as 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 indenyl. These ligands can be substituted with one or more or 1 to 3 C"₂₀Hydrocarbons, more especially C₁T_oalkyl. Due to Cp¹and Cp²The ligand has a pair of non-covalent electrons that can act as a Lewis base, thus enabling high polymerization activity. In particular, when Cp¹and Cp²When the ligands are cyclopentadienyl groups with relatively small steric hindrance, they show high polymerization activity and low hydrogen reactivity, so low molecular weight olefin polymers can be polymerized with high activity.

In addition, Cp¹and Cp²Ligands can easily control properties of olefin polymers to be prepared, such as chemical structure, molecular weight, molecular weight distribution, mechanical properties and transparency, by adjusting the degree of steric hindrance effect depending on the type of substituted functional group. Specifically, Cp¹and Cp²Ligands are substituted with Rn and R, respectively₁₂, among them, Rn and R₁₂The same or different from each other, and each can be independently hydrogen, C₁r_oAlkyl, C₂.₂₀Alkoxyalkyl, C₇(4) Arylalkyl or C containing at least one heteroatom selected from the group consisting of N, O and S₂ T₂Heteroaryl, more specifically C₁T_oAlkyl, C₂ T_oAlkoxyalkyl, *one₂₀Aralkyl or C containing at least one heteroatom selected from the group consisting of N, O and S₄.₁₂heteroaryl. In order to have excellent catalytic activity, when R and R₁₂When each is a substituent defined above, R and R₁₂At least one of the can be C₂ r_oAlkoxyalkyl or C₂T_oAlkoxyalkyl.

Outside only dagger, in Cp¹and Cp²There are Minghua]) products between ligands, and MjZ)r. can affect the storage stability of metal complexes. In order to ensure the effect more effectively, Z1 can be independently halogen or C₁r_oAlkyl, more specifically, is 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.

More specifically, in the first transition metal compound M] is Ti, Zr or Hf; Cpi and Cp²are the same or different from each other, and are independently selected from the group that can be selected by C₁T_oAny one of the group consisting of alkyl substituted or unsubstituted cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and phenanthyl; R and R₁₂Each independently hydrogen, Cb_2oAlkyl, C₂ r_oAlkoxyalkyl, C₆._2oAryl, C₇._2oArylalkyl, pyranyl or thienyl, where Rn and R₁₂at least one of the C₂._2oAlkoxyalkyl; Z1 is halogen.

The first transition metal compound represented by chemical formula 1 can be, for example, a compound represented by any one of the following structural formulas, but is not limited thereto:

CN 113166316 Β

<img file="CN113166316B_D0002.tif" />

In addition, the first transition metal compound can be the following compound, wherein u is Zr; CPI and Cpz are each independently unsubstituted cyclopentadienyl or substituted with at least one added alkyl such as methyl etc. Cyclopentadienyl; Rn and Jiang are each independently hydrogen, C1.20 alkyl, C2-20 alkoxyalkyl, C7-20 aryl or C7-20 arylalkyl, wherein, Ru and in At least one or two are C2-20 alkoxyalkyl, more particularly C2-10 alkoxyalkyl, even more particularly tert-butoxyhexyl; Z1 is a halogen group; m is 1 in Chemical Formula 1.

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

Simultaneously, in the hybrid supported catalyst, the second transition metal compound represented by chemical formula 2 forms the ligand structure in which the elastic derivative and the amine derivative are crosslinked by the bridge compound, and has a pair of in the non-covalent electrons as a Lewis base, thus exhibiting high polymerization activity. In particular, the catalyst can exhibit high catalytic activity by having a structurally stable and electron-rich Xenon structure, and can exhibit excellent loading stability to the support by including a tethering group in the bridging group.

In addition, the second transition metal compound is replaced with the functional group (R₂₂), and the hydrogen in the polymer chain in which the nitrogen atom of the amine derivative grows is stabilized by hydrogen bonding, thereby preparing medium and high molecular weight polymers. In addition, the polymers to be prepared have a narrow molecular weight distribution, thereby exhibiting excellent mechanical properties. Specifically, R22 can be Gr or G-6 branched alkyl, such as isopropyl, isobutyl, tert-butyl, and isopentyl, etc., and can be isopropyl, which is more effective in terms of steric effects. advantageous.

[0114] In addition, the bomb structure has an inductive effect capable of providing sufficient electrons by bonding H21 at the 4-position, especially a C6.20 aryl group substituted with one or more (or one or two) C120 alkyl groups , resulting in higher catalytic activity. More specifically, in Chemical Formula 2, R21 can be substituted with one or two Cr6 branched alkyl groups (such as 4-tert-butylphenyl and 3,5-di

tert-butylphenyl) phenyl.

In addition, in chemical formula 2, the R bonded to N₂₃Can be Cb₂₀Straight chain or branched alkyl, more specifically C₃_C₁₂or C₃_C₆Branched alkyl groups such as tert-butyl. When R₂₃With a branched structure, the transition metal compound is sterically stabilized, and the catalyst is stabilized by the electron-donating effect, thereby exhibiting higher catalytic activity.

More specifically, in chemical formula 2, R₂₁to replace with one or two C₃.₆branched alkyl phenyl, and R₂₂and R₂₃can each independently be C₃.₆branched alkyl. Even more specifically, R₂₂Can be isopropyl.

In addition, in chemical formula 2, bridging group comprises can be with R₂₄The functional groups are tied together to the carrier's -(CH₂)nOR₂₅the tethering group. Therefore, excellent loading stability can be exhibited, and excellent catalytic activity can be maintained to prepare polymers with high molecular weight.

Specifically, R₂₄can be C₁T₂or CL₆Straight chain or branched alkyl. More specifically, it can be C₁T straight chain alkyl or methyl to increase solubility and thus improve loading efficiency.

In addition, the R in the tethering group₂₅can be C₁T₂or CL₆Straight chain or branched alkyl, more specifically, can be C₃.₆Branched alkyl, or tert-butyl. When the tethering group has a branched structure such as tert-butyl, it can be easily separated and bound to the support, thus exhibiting excellent loading stability.

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

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

More specifically, in chemical formula 2, A is silicon, (₅is 4 one₆branched alkyl, and n can 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), aluminum (Zr), and hafnium (Hf), as the center metal (M2). When the transition metal compound contains Ti as the central metal, the catalyst shows superior polymerization activity by increasing structural openness than the case containing other transition metals of Group 4 such as Zr and Hf, and is stabilized by the electron-donating effect , resulting in polymers with high molecular weight.

In chemical formula 2, Z₂₁and Z₂₂Can each independently be a halogen such as chlorine; or Ck such as methyl₄alkyl. 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.

More specifically, in chemical formula 2, M₂for titanium, and Z₂₁and Z₂₂can each independently be C₁T alkyl.

More specifically, the compound of chemical formula 2 can be following compound, and wherein, A is silicon; M₂is titanium; R₂₁is substituted with one or two C such as tert-butyl etc.₃To branched alkyl phenyl; % is %₆Branched alkyl, such as isopropyl;(₃for 5₆Branched alkyl groups such as tert-butyl; r₂₄for cb₄Straight chain alkyl, such as methyl;₂₅for 4 a₆branched alkyl, such as tert-butyl; z₂₁and z₂₂each independently for C₁T alkyl, such as methyl; n is an integer of 4 to 6.

The second transition metal compound represented by chemical formula 2 may be a compound represented by one of the following structural formulas, but is not limited thereto:

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The second transition metal compound described above can be prepared by lithiation of a ligand compound of formula 3 and subsequent reaction with a halide containing a Group 4 transition metal:

[chemical formula 3]

R21^[0131] R₂₅-O-(CH₂)₍₁ / ^xNH

R23

[0132] In Chemical Formula 3, Agi 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 for illustrating the present invention, but the present invention is not limited thereto:

[0134]

[0135]

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In Reaction Scheme 1, a, T, R to R26, Z21, Z22 and n are the same as defined above, and Xi and X2 are each independently

[0136] is a halogen.

As described in Reaction Scheme 1, lithiation can be carried out by reacting the ligand compound (B) of chemical formula 3 with alkyllithium such as n-butyllithium (NBL), followed by halogenation with a transition metal containing Group 4 Compound (such as TiCl/ reaction to prepare compound of chemical formula 2. In addition, when Z21 and Z22 in compound of chemical formula 2 are each an organoalkyl group, an alkyl group for metal m can be additionally added after lithiation Alkylating reagents such as NMB (methylmagnesium bromide).

[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 Reaction Scheme 2 as follows. Reaction Scheme 2 is just an example for explaining the present invention, and the present invention is not limited thereto.

[Reaction scheme 2]

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<img file="CN113166316B_D0007.tif" />

[0141] In Reaction Scheme 2, A, R to R and n are the same as defined above, and R and R are each independently halogen.

With reference to reaction scheme 2, ligand compound (3) can be prepared, comprising the steps of: making the bomb compound (5) as a Cp unit react with alkyllithiums such as n-butyl lithium (NBL) to carry out lithiation; making the obtained The reactant is reacted with a raw material (6) for providing a tethering group to prepare a compound (7) in which the tethering group is bonded to the xenon structure; compound (7) is reacted with a tertiary amine (8) having a % substituent (such as LBuN% )reaction.

The reaction in each step can be carried out by applying known reaction, and more detailed synthetic method can refer to the preparation example mentioned later.

[0144] As mentioned above, hybrid supported catalysts comprising a first transition metal compound and a second transition metal compound can effectively provide polyalkenes, especially in the preparation of chlorinated polyalkenes and chlorinated compounds due to the High-density polyethylene with increased cross-linking can increase tensile strength because polyalkenes have minimized low-molecular-weight content and broad molecular weight distribution by forming high-molecular-weight tails in the molecular weight distribution curve. In addition, the above effects can be further enhanced by controlling the mixing ratio of the first transition metal compound and the second transition metal compound in the hybrid supported catalyst. 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 first transition metal compound and the second transition metal compound are contained in the form of a supported catalyst supported on a carrier. 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. Supports can be surface modified by sintering, 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, Sulfates or nitrates, such as Na20, K2cO, small BaSO, and her (N0₃) ₂wait.

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

[0148] The amount of hydroxyl groups can be controlled by the preparation method of the carrier, preparation conditions or drying conditions, such as temperature, time, vacuum or spray drying. When the amount of hydroxyl groups is too low, there may be insufficient reactive sites with co-catalysts. When the amount of hydroxyl groups is too high, it may be caused by moisture in addition to the hydroxyl groups present on the surface of the carrier particles, which is not desirable. For example, the amount of hydroxyl groups on the surface may be 0.1 to 10 mmol/g, or 0.5 to 5 mmol/g.

Polymerization of propylene by sintering silica, especially silica gel, in the above carrier

There is little catalyst release from the support surface during the process because the transition metal compound is chemically bonded and supported on the silica support. As a result, when polyethylene is produced by slurry polymerization or gas phase polymerization, fouling phenomenon adhering to the reactor wall surface or to each other can be minimized.

When the transition metal compound is used in the form of a supported catalyst, based on the weight of the carrier, such as 1g of silica, the content of the first transition metal compound and the second transition metal compound can be more than 10umol, more than 30umol or 60umol 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 produce polyethylene with a structure optimized to improve the tensile strength of chlorinated polyethylene or chlorinated compound.

The hybrid supported catalyst can be directly introduced into the polymerization system, or can be dissolved or diluted in a C5 to C12 aliphatic hydrocarbon solvent (such as pentane, hexane, heptane, nonane, decane and its isomers) Medium, aromatic hydrocarbon solvents (such as toluene and benzene) or chlorine-substituted hydrocarbon solvents (such as methylene chloride 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 treating with a small amount of alkylaluminum.

[0153] In addition, in terms of improving activity and stability, the above-mentioned catalyst composition may further include a cocatalyst. 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]

-[Al(R_a)-O]_mIn chemical formula 9;

[0157] R_a' can be the same or different from each other, and are independently halogen, C"₂₀Hydrocarbon, or halogen substituted C"₂₀hydrocarbon;

and

m is an integer of 2 or more;

[chemical formula 10]

J (R_b）₃

In chemical formula 10,

[0162] R_b' can be the same or different from each other, and are independently halogen, C"₂₀Hydrocarbon, or halogen substituted C"₂₀hydrocarbon;

and

J is aluminum or boron;

[chemical formula 11]

[0165] [EH] + [ZQ₄"or [E] + [ZQ₄「

In chemical formula 11,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is an element of Group 13; and

Q can be identical or different from each other, and each independently is wherein one or more hydrogen atoms are unsubstituted or by halogen, C₁r_oHydrocarbon, alkoxy or phenoxy substituted C₆.₂₀Aryl or Cb₂₀alkyl.

The example of the compound represented by chemical formula 9 may include C₁r_oAlkylalumoxane compounds, such as methylalumoxane, ethylalumoxane, isobutylalumoxane or butylalumoxane, etc., among them, any one or a mixture of two or more can be used.

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

Tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, Octyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-cresyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron , triisobutylboron, tripropylboron or tributylboron, etc., more specifically, it may be selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

In addition, the example of the compound represented by Chemical Formula 11 may include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, Trimethylammonium tetrakis(p-tolyl)boron, trimethylammonium tetrakis(o,p-dimethylphenyl)boron, tributylammonium tetrakis(p-trifluoromethylphenyl)boron, trimethyliron Tetrakis(p-trifluoromethylphenyl)boron, tributyliron tetrakis(pentafluorophenyl)boron, N,N-diethylaniline tetraphenylboron, N,N-diethylanilinium tetrakis(pentafluorophenyl)boron Fluorophenyl) boron, diethyl nuclear tetrakis (pentafluorophenyl) boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyliron tetraphenyl aluminum, tributylammonium Tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl iron tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (p-tolyl) aluminum Ammonium tetrakis(o,p-dimethylphenyl)aluminum, tributylammonium tetrakis(p-trifluoromethylphenyl)aluminum, trimethyliron tetrakis(p-trifluoromethylphenyl)aluminum, tributyl Iron tetrakis(pentafluorophenyl)aluminum, N,N-diethylanilinium tetraphenylaluminum, N,N diethylanilinium tetrakis(pentafluorophenyl)aluminum, diethylammonium tetrakis(pentafluorophenyl)aluminum base) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetrakis (p-tolyl) boron, triethylammonium tetrakis (o, p-dimethylphenyl) Boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, triphenylcarbenium tetrakis (p-trifluoromethylphenyl) boron or triphenylcarbon tetrakis (pentafluorophenyl) boron, etc., in, Any one or a mixture of two or more thereof may be used.

In above-mentioned cocatalyst, considering that cocatalyst can show more excellent catalytic activity when being used together with transition metal compound, described cocatalyst can be the compound represented by chemical formula 9, more specifically, CLC₂₀Alkyl aluminoxane compounds, such as methyl aluminoxane, etc. Alkyl aluminoxane compounds are used as scavengers of hydroxyl groups present on the surface of the support to improve catalytic activity, and convert halogen groups of catalyst precursors into methyl groups, thereby promoting chain growth during polyethylene polymerization.

Based on carrier weight, such as 1 gram of silicon dioxide, the loading capacity of promoter can be more than 0.1mmol, or more than 5mmol, or more than 8mmol, or more than 10mmol, and less than 25mmol, or less than 20mmol. When the content of the co-catalyst is within the above-mentioned content range, the effect of enhancing the catalytic activity due to the use of the co-catalyst and the effect of reducing the generation of fine powder can be sufficiently obtained.

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

[chemical formula 12]

[0178] RN-(CH2CH2OH)2

In chemical formula 12, R can be C_8-30An alkyl group, and when R includes an alkyl group having a carbon number within the above range, it can exhibit an effect of reducing fine powder through excellent antistatic effect without causing an unpleasant smell.

[0180] More specifically, the ethoxylated alkylamine may be a compound of formula 12, wherein R is C_8-22straight chain alkyl or C₁₀T₈straight chain alkyl or C₁₃T₅straight-chain alkyl groups, and these compounds may be used alone or in admixture of two or more. Specific examples thereof may include N,N-bis(2-hydroxyethyl)tridecylamine or N,N-bis(2-hydroxyethyl)pentadecylamine, etc., and commercially available Atmer 163^tm (Available from CRODA).

When further comprising an antistatic agent, based on 100 parts by weight of the carrier, such as silicon dioxide, its content can be more than 0.5 parts by weight, more than 1 part by weight or more than 2 parts by weight, and less than 20 parts by weight, 10 parts by weight Parts or less or 7 parts by weight or less.

[0182] The above-mentioned cocatalyst and antistatic agent may be used in combination with the above-mentioned 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 supported on a carrier in a hybrid supported catalyst, the catalyst composition can be prepared by a production method comprising the steps of: supporting a cocatalyst compound on a carrier, and supporting a transition metal compound on a carrier Above; the antistatic agent in the slurry state is introduced into the carrier loaded with the co-catalyst and the transition metal compound, and then heat-treated. In this regard, the loading of the transition metal compound may be carried out by loading the first transition metal compound and then the second transition metal compound, or vice versa. The supported catalyst with a structure determined according to this loading order can exhibit higher catalytic activity and excellent process stability during polyethylene production.

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

When the catalyst composition is used as a slurry or as a dilution in a solvent, the solvent is an aliphatic hydrocarbon solvent with 5 to 12 carbon atoms suitable for the polymerization process of propylene monomer, such as pentane, hexane , heptane, nonane, decane and its isomers, and aromatic hydrocarbon solvents such as toluene and benzene, or chlorine atom-substituted hydrocarbon solvents 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 contain 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 alkylaluminum before use.

[0185] On the other hand, the polymerization reaction for producing 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 control molecular weight distribution more effectively, slurry polymerization or gas phase polymerization is more suitable.

[0186] In particular, the polymerization reaction may 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 an aliphatic hydrocarbon solvent, 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 one embodiment of the present invention can be carried out in a single CSTR reactor.

[0188] In the polymerization reactor, the polymerization can be carried out, 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 beginning of the polymerization reaction.

[0189] In addition, the polymerization reaction was carried out while introducing hydrogen gas.

[0190] The hydrogen introduced during the polymerization reaction activates the inert sites of the metallocene catalyst and causes chain transfer reactions, thereby controlling 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 part by weight or more, or 0.005 part 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 Hydrogen gas was introduced in the following amount. When hydrogen gas 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 may 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, fouling in the reactor may be caused.

In addition, polymerization pressure can be 6.8 to 8.7kg/cm², 7.0 to 8.5kg/cm²or 7.0 to 7.5kg/cm², to ensure optimum productivity. Polymerization pressure can be about 6.8kg/cm²above to prevent the excessive production of high molecular weight

CN 113166316 B Adhesion from and optimization of productivity and can be about 8.7kg/cm²The following is to prevent unit degradation of the ethylene source under high pressure polymerization conditions.

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

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

[0195] When moisture or impurities are present in the polymerization reactor, a portion of the catalyst decomposes. The trialkylaluminum is used as a scavenger to pre-trap moisture or impurities in the reactor or moisture contained in the monomer. Therefore, the activity of the catalyst used in the production can be maximized, and as a result, a homopolyethylene having excellent physical properties, particularly a narrow molecular weight distribution, can be produced more efficiently. In particular, in trialkylaluminum, the alkyl group is as defined above, specifically c"₂₀Alkyl, and more specifically c"₆Straight chain or branched alkyl, such as methyl, ethyl or isobutyl, etc.

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

[0197] A polyethylene having an optimized molecular structure, in particular a molecular structure with a minimized low molecular weight content and a relatively high high molecular weight content, is prepared by the above-mentioned 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 containing no additional copolymers. For example, when the polyethylene is an ethylene homopolymer, preferably high-density polyethylene (HDPE), the above physical properties can be more suitably satisfied. HDPE has excellent softening point, hardness, strength and electrical insulation, so it can be used in various containers, packaging films, fibers and tubes, etc.

Preparation of Chlorinated Polyethylene

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

Specifically, the preparation method of chlorinated polyethylene comprises the steps of: preparing polyethylene by polymerizing vinylic monomers in the presence of a catalyst composition comprising a hybrid supported catalyst while introducing hydrogen, 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 support; and polyethylene is chlorinated by treating it with chlorine.

As mentioned above, specific examples of the reaction conditions in the step of polymerizing vinylic monomers to produce polyethylene, first and second transition metal compounds, supports, cocatalysts, and hybrid supported catalysts including them are as above mentioned.

[0203] In addition, the chlorination of polyethylene can be carried out 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 an emulsifier and dispersant and water, and the acid phase method is a method of chlorinating an acidic aqueous solution such as hydrochloric acid (HCl) solution using an emulsifier and a dispersant. More specifically, in the preparation method of chlorinated polyethylene according to the present disclosure, chlorine can be carried out by dispersing the prepared polyethylene with water, emulsifier and dispersant, and then adding catalyst and chlorine to react reaction.

[0205] As emulsifiers, polyethers or polyoxyalkylenes can be used. The dispersant may be a polymer salt or an organic acid polymer salt. The organic acid can 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 may be used alone or may be mixed with an inert gas and then used.

[0207] The chlorination reaction may be carried out 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 carried out for about 10 minutes to 10 hours, 1 hour to 6 hours, or 2 hours to 4 hours.

For example, the chlorination reaction can be dispersed in water by 100 parts by weight of polyethylene, 0.01 to 1.0 parts by weight or 0.05 to 0.5 parts by weight of emulsifier and 0.1 to 10 parts by weight or dispersant of 0.5 to 5.0 parts by weight , and then add 0.01 to 1.0 parts by weight or 0.05 to 0.5 parts by weight of catalyst and 80 to 200 parts by weight or 100 to 150 parts by weight of chlorine for reaction.

[0210] The chlorinated polyethylene prepared by the above-mentioned reaction or chlorination process can be further subjected to a neutralization process, a washing process, and a drying process, whereby it can be obtained in a powder form.

[0211] The neutralization process may be, for example, a process of neutralizing the reactants that have undergone the chlorination treatment 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 production 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 the chlorinated polyethylene measured at a temperature of 121° C. is 70 to 80, more specifically 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. A more specific method thereof will be described in detail in Experimental Examples 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 effect, and thus can be used for electric wires or cables.

Mixture

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

[0219] The kneaded product may specifically be a CPE kneaded product comprising cross-linked chlorinated polyethylene obtained by cross-linking the chlorinated polyethylene in the presence of a peroxide-based cross-linking agent while preparing.

[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, antioxidants may optionally be further added during the crosslinking reaction.

For example, based on 100 parts by weight of chlorinated polyethylene, the chlorinated polyethylene (CPE) compound can contain 100 parts by weight to 280 parts by weight of inorganic additives (such as talc and carbon black), 20 parts by weight to 50 parts by weight A plasticizer in parts by weight and a crosslinking agent in parts by weight of 1 to 20 parts by weight.

[0222] The compound comprising chlorinated polyethylene can exhibit excellent tensile strength, specifically, a tensile strength of 12 or more, or 12 to 14, measured at 500 mm/min according to ASTM D412.

[0223] In addition, conventional methods in the art can be applied to the method of preparing shaped articles from the chlorinated polyethylene according to the present disclosure. For example, chlorinated polyethylene can be pad compounded and extruded to make shaped products.

Beneficial effect

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, so it is possible to produce chlorinated polyethylene compounds while maintaining excellent processability and Mooney viscosity characteristics. Improve tensile strength.

Detailed ways

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

<Preparation of the first transition metal compound>

Synthetic Example 1: [tert-butyl-O-(CH₂)₆-C₅h₄]₂ZrCl₂preparation of

[0229] tert-butyl-. -(CH₂)₆-Cl is prepared by the method shown in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol and reacted with NaCp to give tert-butyl-O- (CH₂)₆-C₅h₅(Yield 60%, boiling point 80°C/0.1mmHg).

[0230] In addition, the tert-butyl-O-(CH₂)₆-C₅h₅It was dissolved in THF, and n-butyllithium (n-BuLi) was slowly added thereto. After that, it was heated to room temperature and reacted for 8 hours. At -78 °C, the lithium salt solution synthesized as described above was slowly added to the ZrCl₄ (THF)₂ (1.70g, 4.50mmol)/THF (30mL), and further reacted at room temperature for about 6 hours.

[0231] All volatiles were dried in vacuo and the resulting oily liquid material was filtered by addition of hexane solvent. The filtered solution was dried in vacuo 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,

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

[0233] ¹³CNMR (CDCl₃) :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>

Synthetic example 2

Step 1: Preparation of Ligand Compound

4-(3,5-di-tert-butylphenyl)-2-isopropyl-1H-indene (1.39 g, 4 mmol) was added as a Cp unit to a 50 ml Schlenk flask, and THF ( 13ml), and then cooled to below -20°C. After the cooled mixed solution was stirred for 5 minutes, NBL (1.7ml, 2.5M 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 for reaction. 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 to react, and the resulting precipitate was filtered using hexane to obtain 1-(6-(tert-butoxy)hexyl)K-(tert-butyl)-1-(4-( 3,5-di-tert-butylphenyl)-2-isopropyl-11 inden-1-yl)-1-methylsilylamine ligand compound (yellow oil, 2.41g, yield 97% (with Molar meter)).

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) [0240] Step 2: Preparation of transition metal compound

1-(6-(tert-butyloxy)hexyl)-N-(tert-butyl)-1-(4-(3,5-di-tert-butylphenyl)- The ligand compound (2.4g, 3.9mmol) of 2-isopropyl-1H-inden-1-yl)-1-methylsilylamine is added in the Schlenk flask of 100ml, and toluene (13ml) is added wherein, then Cool to below -20°C. After sufficiently cooling by stirring for 5 minutes, NBL (5.1 ml, 2.5M hexane solution) was added to the resulting mixed solution for lithiation. It was confirmed that the color of the mixed solution changed to brown after lithiation. When the lithiation was complete, the resulting reaction solution was cooled to 0 °C. After NMB (13ml, 3M ether solution) was added thereto, the temperature was immediately lowered to -20°C, and TiCl was added₄(3.9ml, 1M toluene). Smoke is generated when adding, the reaction dissolves

The liquid turned brown immediately. After adding, carry out o/n stirring, then remove salt by filter, obtain transition metal compound (2a) (brown oil, 2.16g, yield 80% (by mole)).

[0242]

<img file="CN113166316B_D0008.tif" />

NMR (400MHz, C6D6), 7.79-7.76 (m, 2H), 7.64-7.47 (m, 5H), 3.35-3.21 (m, 2H),

2.76- 2.49 (s,2H) ,1.99-1.91 (m,4H),1.70-1.60 (m,4H),1.53(s,9H) ,1.51-1.44 (m,4H), 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] <Preparation of hybrid supported catalyst> [0245] Synthesis Example 3

(1) preparation of carrier

[0199] Silica (SYLOPOL 948TM, manufactured by Grace Davison) was dehydrated and dried under vacuum at a temperature of 600° C. for 12 hours.

(2) preparation of hybrid supported catalyst

[0249] 10 g of silica dried in step (1) was introduced into a glass reactor, and 100 mL of toluene was additionally 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 raised to 80° C., and the mixture was reacted slowly 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 together and reacted for 1 hour. After the reaction was finished, 0.0% of the second transition metal compound prepared in Synthesis Example 2 dissolved in toluene was added, and further reacted for 2 hours under stirring. After the reaction was complete, 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 the hybrid supported catalyst.

Synthetic example 4

In addition to changing the amount of the second transition metal compound to 0.06mmol (the first transition metal compound: the molar ratio of the second transition metal compound=4:1), prepare a hybrid load-type in the same manner as in Synthesis Example 3 catalyst.

<Preparation of polyethylene>

Embodiment 1

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

First, 30 kg/hr of hexane, 10 kg/hr of ethylene, 1 g/hr of hydrogen and 130 cc/hr of triethylaluminum (TEAL) were introduced into the ORii® single CSTR reactor, and then Synthetic Example 3 The hybrid supported catalyst prepared in was injected therein 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/cm2 to 7.5 kg/cm2, and polymerization was carried out for about 4 hours. Afterwards, the polymerized product is made into final polyethylene through solvent removal equipment and dryers.

Embodiment 2

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

Embodiment 3

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

Comparative Example 1

Use the high density polyethylene (CE2080 that utilizes Ziegler-Natta catalyst to prepare^tm, manufactured by LG Chem).

Comparative example 2

Use the high density polyethylene (SC200 that utilizes metallocene catalyst to prepare^tm, manufactured by LG Chem).

Comparative example 3

Use the high density polyethylene (SC100E that utilizes metallocene catalyst to prepare^tm, manufactured by LG Chem).

Comparative example 4

Use the high density polyethylene (CE6040X that utilizes Ziegler-Natta catalyst to prepare^tm, manufactured by LG Chem).

Comparative Example 5

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

Comparative example 6

[0271] Except using the hybrid supported catalyst prepared in Synthesis Example 4, polyethylene was prepared in the same manner as in Example 1.

Comparative example 7

Use commercially available polyethylene (5000Cp^tm, manufactured by Lotte Chemical).

Experimental example 1

[0275] The polyethylene prepared in Examples and Comparative Examples is analyzed by GPC in the following manner, and the content of each molecular weight distribution, i.e. fraction, is calculated. The results are shown in Table 1 below.

[0276] Fraction (%): GPC analysis was performed, and the fraction was calculated as the area (%) occupied by the log Mw fraction 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.

GPC analysis is specifically carried out 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 300mm long column was used. The evaluation temperature was 160°C, and 1,2,4-trichlorobenzene was used as a solvent at a flow rate of 1E1/g3. Using a GPC analyzer (PL-GP220), each polyethylene sample was dissolved in 1,2,4-trichlorobenzene containing 0.0125% BHT for 10 hours for pretreatment, and a concentration of 10 mg/10 mL was provided in 200 UL sample. Mw and Mn were obtained using calibration curves 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.

[Table 1]

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

<td>Log Mw</td><td>Little J¹ 3.5</td><td>More than 3.5 and less than 4.0</td><td>Above 4.0 and below 4.5</td><td>Large "4.5 and small wide 5.0</td><td>5.0 or more and 6.0 or more</td><td>Greater than 6.0 and less than 6.5</td><td>Greater than 6.5 and 7.0 or more</td><td>Greater than 7.0</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>341</td><td>13</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>651</td><td>3.63</td><td>20.24</td><td>41.19</td><td>29 will</td><td>3.53</td><td>L09</td><td>0</td>

<td>Comparative example 1</td><td>2.64</td><td>8.89</td><td>22. S9</td><td>29.03</td><td>31.99</td><td>3.94</td><td>0.62</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>42.85</td><td>2.51</td><td>0.07</td><td>0</td>

<td>Comparative example 4</td><td>0,57</td><td>4.30</td><td>16.22</td><td>34.09</td><td>42.47</td><td>2.35</td><td>0</td><td>0</td>

<td>Comparative Example 5</td><td>028</td><td>2.94</td><td>21.85</td><td>40.81</td><td>2S.42</td><td>3.74</td><td>LS6</td><td>0</td>

<td>Comparative Example 6</td><td>S51</td><td>4.27</td><td>22.49</td><td>41.21</td><td>28_.25</td><td>2.74</td><td>S53</td><td>0</td>

<td>Comparative Example 7</td><td>S73</td><td>5.12</td><td>17.45</td><td>30.62</td><td>43.69</td><td>235</td><td>03</td><td>0</td>

Experimental example 2

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

(1) weight-average molecular weight (Mw, g/mol) and molecular weight distribution (PDI, polydispersity index); Carry out GPC analysis in the same manner as Experimental Example 1, and by measuring 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).

(2) hq. and MFRRzi 6/5: The melt index (called 0) of the polyethylenes prepared in Examples and Comparative Examples was measured according to ASTM D1238 (Condition E, 190° C., 5.0 kg load). Additionally, the melt flow rate ratio (MFR%_fi/J , MFR₉₁ 6 Measured according to ASTM D 1238 at 190°C under a load of 21.6 kg Measured according to ASTM D 1238 at 190°C under a load of 5 kg.

(3) Density (g/cm³): Density measured according to ASTM D-1505 (g/cm³)。

(4) MDR torque (gq): In order to evaluate the degree of crosslinking of polyethylene, the MDR torque of each polyethylene sample was measured with Alpha Technologies Production MDR (Moving Die Rheometer).

Specifically, 100 g of each polyethylene sample prepared in Examples and Comparative Examples, 0.4 g of phenolic antioxidant (A0) and 1.2 g of crosslinking agent (DCP, dicumyl peroxide) were prepared at 80° C. ) after mixing, a sample piece was prepared at 140° C. for 10 minutes. Then, the call value and the total value of the sample piece were measured at 180° C. for 10 minutes with an MDR (Moving Die Rheometer). Calculate the MDR torque (M_h-M_l). This is the maximum vulcanization torque measured at full cure, but also the minimum vulcanization torque stored.

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

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

[Formula 1]

Mθ=(PRT)/G_N°

In formula 1,

p=0.8X (density (kg/n ) of polyethylene measured according to ASTM D-1505,

R is the gas constant (8.314Pa·m) of polyethylene³/mol K),

t is the absolute temperature (r) of the measured temperature, and

Gj is the plateau modulus of polyethylene, which is the loss modulus having the greatest value in the region where the storage modulus is greater than the loss modulus

Storage modulus at small values, where the storage modulus and loss modulus were measured using a rotational rheometer at 190°C and 0.5% strain varying the angular frequency from 0.05 to 500 rad/s.

[table 2]

<td></td><td>Mw (g/mol)</td><td>PDl</td><td>MM (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]</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>11.5</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>1 L8</td><td>34,800</td>

<td>Comparative example 1</td><td>177,000</td><td>9.1</td><td>1.30</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>5.0</td><td>OS</td><td>16.0</td><td>0.955</td><td>7.7</td><td>10,300</td>

<td>Comparative example 3</td><td>]71,000</td><td>4.5</td><td>OS</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>L2</td><td>12.3</td><td>0.952</td><td>9.5</td><td>31 JOO</td>

Experimental example 3

Chlorinated polyethylene was prepared using the polyethylene prepared in one of the above Examples and Comparative Examples, 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

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 acid and benzoyl peroxide as catalyst. Chlorination was then carried out 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.

(2) Mooney Viscosity (MV): Wrap the rotor in the Mooney Viscometer with the CPE sample, then close the mold. Warm up to

121 After 1 min at °C, spin the rotor for 4 min to measure the MV (Mooney viscosity, 121 °C, Blood 1+4).

[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>

Experimental example 4

[0199] A CPE compound was prepared using polyethylene prepared in one of the above Examples and Comparative Examples in Experimental Example 3, and physical properties were evaluated.

(1) Preparation of CPE Mixture

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

(2) MV (Mooney Viscosity) of the CPE kneaded product: the rotor was wrapped in the Mooney viscometer with the CPE kneaded product, and then the mold was closed. After preheating to 100C for 1 minute, the rotor was rotated for 4 minutes to measure MV (Mooney viscosity, 100C, Blood 1+4). The results are shown in Table 4.

(3) Tensile strength (MPa) of CPE compound: After cross-linking the CPE compound sample prepared above at 160° C. for 10 minutes, measure CPE compound under the condition of 500 mm/inin 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>137</td>

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

<td>Comparative example 1</td><td>53</td><td>11.9</td>

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

<td>Comparative example 3</td><td>60</td><td>12.5</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, the CPE compounds prepared using the polyethylenes of Examples 1 to 3 had improved tensile strength compared to the comparative examples while maintaining excellent Mooney viscosity characteristics.