WO2021060907A1 - Polyéthylène et polyéthylène chloré associé - Google Patents

Polyéthylène et polyéthylène chloré associé Download PDF

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WO2021060907A1
WO2021060907A1 PCT/KR2020/013051 KR2020013051W WO2021060907A1 WO 2021060907 A1 WO2021060907 A1 WO 2021060907A1 KR 2020013051 W KR2020013051 W KR 2020013051W WO 2021060907 A1 WO2021060907 A1 WO 2021060907A1
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polyethylene
group
molecular weight
log
compound
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PCT/KR2020/013051
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English (en)
Korean (ko)
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정철환
이시정
김선미
서의령
최이영
홍복기
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주식회사 엘지화학
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Priority claimed from KR1020200123878A external-priority patent/KR102589954B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/294,896 priority Critical patent/US12006378B2/en
Priority to EP20870137.5A priority patent/EP3865522A4/fr
Priority to CN202080006688.8A priority patent/CN113166316B/zh
Publication of WO2021060907A1 publication Critical patent/WO2021060907A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen

Definitions

  • the present invention has a molecular structure having a low molecular weight and a high polymer content, and thus can improve tensile strength while maintaining excellent processability and Mooney viscosity characteristics when preparing a chlorinated polyethylene compound, and chlorinated polyethylene manufactured using the same. It is about.
  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics.
  • Ziegler Natta catalysts have been widely applied to existing commercial processes since their invention in the 50s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform. In particular, physical properties may be deteriorated due to polymer chains having a relatively low molecular weight due to a wide molecular weight distribution.
  • the metallocene catalyst is composed of a combination of a main catalyst composed of a metallocene compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. , It has properties that can change copolymerization properties, molecular weight, crystallinity, etc.
  • U.S. Patent No. 5,032,562 describes a method of preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is a method of producing a bimodal distribution polymer by supporting a titanium (Ti)-based Ziegler-Natta catalyst producing high molecular weight and a zirconium (Zr)-based metallocene catalyst producing low molecular weight on one support. As a result, the supporting process is complicated, and the morphology of the polymer is deteriorated due to the cocatalyst.
  • U.S. Patent No. 5,525,678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a non-metallocene compound on a carrier.
  • This has a disadvantage in that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.
  • U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle to support each of the metallocene catalysts used on the carrier.
  • chlorinated polyethylene is a product obtained by substituting a portion of hydrogen in polyethylene with chlorine, and is used as an impact modifier for polyvinyl chloride (PVC) or crosslinked to manufacture wire coverings or hoses. .
  • Chlorinated polyethylene which is used as a material for electric wire coating, is used in a heat-crosslinked structure by a peroxide-based crosslinking agent, which is a crosslinking agent.
  • a peroxide-based crosslinking agent which is a crosslinking agent.
  • it In order to prevent damage to the coating when the wire is bent, it must have excellent tensile strength in a crosslinked compound state.
  • the strength of the compound varies depending on the properties of the chlorinated polyolefin.
  • general-purpose chlorinated polyolefins which are widely known at present, since polyolefins using Ziegler-Natta catalysts are applied, the uniformity of chlorine distribution in the polyolefins is poor due to the wide molecular weight distribution, and the impact strength is insufficient when compounded with PVC .
  • HDPE high-density polyethylene
  • Mooney viscosity (MV) of the chlorinated polyethylene and the higher the Mooney viscosity of the compound the higher the tensile strength of the compound, but there is a problem that the workability decreases during compression.
  • the present invention provides a polyethylene having a low molecular weight and a high molecular weight molecular structure that can improve tensile strength while maintaining excellent processability and Mooney viscosity characteristics when preparing a chlorinated polyethylene compound, and a method for manufacturing the same. I want to.
  • the present invention also aims to provide a chlorinated polyethylene prepared using the polyethylene.
  • the invention has a density of 0.945 g/cm 3 or more (measured according to ASTM D-1505), and the log value (log Mw) of the weight average molecular weight (Mw) through gel permeation chromatography analysis is x-axis
  • log Mw log average molecular weight
  • the fraction ratio of the region representing the polymer content of log Mw> 6.0 relative to the total area of the molecular weight distribution curve is 4 To 12%, 4.5 ⁇ log Mw ⁇ 5.0, the fractional ratio of the region representing the medium molecular content is 35 to 50%, the fraction ratio of the region representing the low molecular weight of log Mw ⁇ 4.0 is 10% or less, in Equation 1 below.
  • polyethylene is provided:
  • ⁇ density of polyethylene measured by the method of ASTM D-1505 (kg/m 3 ) X 0.8
  • R is the gas constant of polyethylene (8.314 Pa ⁇ m 3 /mol ⁇ K),
  • T is the absolute temperature value (K) of the measured temperature
  • G N 0 is the plateau elastic modulus of polyethylene, using a rotary rheometer, changing each frequency to 0.05 to 500 rad/s under conditions of 190°C temperature and 0.5% strain, and measuring the storage modulus and loss modulus, respectively, In a region where the storage modulus of polyethylene is greater than the loss modulus, the storage modulus when the loss modulus has a minimum value is taken as the plateau modulus.
  • a chlorinated polyethylene prepared by reacting the polyethylene and chlorine described above.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • High tensile strength is required for chlorinated polyethylene used for covering rubber hoses or wires.
  • 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 compound, but in this case, there is a problem that the extrusion processability is deteriorated. In order to solve such a problem, it is necessary to optimize the molecular structure of polyethylene applied to chlorinated polyethylene, specifically high-density polyethylene.
  • the produced polyethylene has a high polymer content with a minimized low molecular content, and thus the degree of crosslinking increases, and thus excellent processability in the manufacture of a chlorinated polyethylene compound. And while maintaining the Mooney viscosity characteristics, it was confirmed that the tensile strength can be improved, and the present invention was completed.
  • the log value (log Mw) of the weight average molecular weight (Mw) is the x-axis through gel permeation chromatography (GPC) analysis of polyethylene, and the molecular weight distribution (dw/dlog Mw) for the log value
  • log Mw> 6.0 that is, a weight average molecular weight (Mw) greater than 10 6.0 g/mol is defined as a'polymer'
  • log Mw ⁇ 4.0 that is, a weight average molecular weight (Mw) 10 Less than 4.0 g/mol is defined as'low molecular weight', between which 4.0 ⁇ log Mw ⁇ 6.0, that is, weight average molecular weight (Mw) is 10 4.0 g/mol or more, and 10 6.0 g/mol or less as'medium molecule'
  • GPC gel permeation chromatography
  • the content of the polymer and the low molecule is obtained through GPC analysis, respectively, in a graph in which log Mw and dw/dlogMw are respectively X and Y axes, log Mw> 6.0 area or log Mw relative to the total area of the molecular weight distribution curve It can be calculated from the area ratio occupied by the ⁇ 4.0 area, that is, the fraction (%).
  • the molecular weight distribution curve of the polyethylene can be specifically measured using a Waters PL-GPC220 instrument as a GPC device, and a Polymer Laboratories PLgel MIX-B 300 mm long column. At this time, the measurement temperature is 160 °C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) is used as a solvent, and a flow rate of 1 mL/min is applied. Polyethylene samples were each using a GPC analyzer (PL-GP220), and 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% concentration of BHT at 160°C for 10 hours.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are derived from the calibration curve formed. Meanwhile, the weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol , And 10000000 g/mol of 9 types can be used.
  • polyethylene according to an embodiment of the present invention
  • Equation 1 The entanglement molecular weight (M e ) calculated according to Equation 1 defined below is 27,000 to 52,000 g/mol.
  • the content of polymers and low molecules in the polyethylene molecule affects physical properties including the degree of crosslinking of polyethylene.
  • the lower the low molecular weight content in the polyethylene and the higher the polymer content the higher the degree of crosslinking may be.
  • the chlorinated polyethylene compound is prepared, the Mooney viscosity increases, resulting in a decrease in processability.
  • the low molecular weight content in the polyethylene is too high, the low molecular weight component melts and the fluidity increases, which may block pores of the polyethylene particles, thereby lowering the chlorination productivity.
  • the polyethylene according to an embodiment of the present invention has a low molecular weight content of less than 10 4. 0 g/mol in a molecule, that is, a fraction ratio of a region having a low molecular weight of log Mw ⁇ 4.0 in the molecular weight distribution curve is 10% or less, more specifically It is 7% or less, or 5% or less.
  • the fractional ratio of the region having an ultra-low molecular content of less than Mw 10 3.5 g/mol, that is, an ultra-low molecular content of log Mw ⁇ 3.5 in the molecular weight distribution curve is 2% or less, or 1.5% or less, or 1% or less
  • Mw 10 is not less than 3.5 g/mol
  • Mw 10 has a low molecular content of less than 4.0 g/mol, that is, a low molecular content of 3.5 ⁇ log Mw ⁇ 4.0 is 7% or less, or 5% or less, or 4% or less.
  • the polyethylene has a polymer content of more than 10 6. 0 g/mol in a molecule, that is, a fraction ratio of a region showing a polymer content of log Mw> 6.0 in the molecular weight distribution curve is 4 to 12%. If the fractional ratio of the region showing the polymer content is less than 4%, there is a concern that the degree of crosslinking may decrease, and if it exceeds 12%, there is a concern that the Mooney viscosity of the chlorinated polyethylene increases due to an excessively high polymer content, and the resulting decrease in processability. More specifically, in the molecular weight distribution curve of the polyethylene, the fractional ratio of the region representing the polymer content of log Mw> 6.0 may be 5% or more, or 7% or more, 12% or less, or 10% or less.
  • the polyethylene has a structure in which a polymer tail is formed in the molecular weight distribution curve. Accordingly, among the above-described polymers, the polyethylene has an ultrahigh molecular content of 6.5 ⁇ log Mw, more specifically 6.5 ⁇ log Mw ⁇ 7.0.
  • the fractional ratio may be 0.1 to 3%, more specifically 0.1% or more, or 0.5% or more, or 0.7% or more, and 3% or less, or 2% or less, or 1.6% or less.
  • by having a higher ultra-high molecular content than the conventional one it is possible to exhibit more improved crosslinking degree and entanglement characteristics.
  • the polyethylene has a fractional ratio of 35 to 50%, more specifically 35% or more, 50% or less, or 45% or less, and thus excellent chlorinated polyethylene It can maintain excellent processability and Mooney viscosity characteristics.
  • the polyethylene has a high density of 0.945 g/cm 3 or more, or 0.945 to 0.955 g/cm 3. This means that the content of the crystal structure of polyethylene is high and dense, and this has a characteristic that it is difficult to change the crystal structure during the chlorination process.
  • the density of polyethylene can be measured by a method according to ASTM D-1505.
  • the polyethylene is entanglement molecular weight (M e ) Is 27,000 g/mol or more and 52,000 g/mol or less.
  • the entanglement molecular weight represents the average molecular weight between the entanglement points between the ethylene polymer chains, and the lower the entanglement molecular weight, the higher the degree of entanglement of the ethylene polymer chain, which means that the resistance to deformation by external force and crack resistance are excellent.
  • workability and long-term durability are opposite physical properties, and if the melt index or melt flow index is increased to increase workability, long-term durability decreases.
  • the polyethylene in the present invention is in the temperature range of 150 to 230°C, specifically 190°C, and the storage modulus of the polyethylene sample under each frequency (Angular Frequency) of 0.05 to 500 rad/s, and 0.5% strain
  • the hyperloss modulus is measured, and when calculated according to Equation 1 below from the obtained plateau elastic modulus (G N 0 ), it has an entanglement molecular weight in the above-described range, thereby exhibiting excellent long-term durability without deterioration in workability.
  • 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.
  • the entanglement molecular weight (Me) may be calculated according to Equation 1 below.
  • ⁇ density of polyethylene measured by the method of ASTM D-1505 (kg/m 3 ) X 0.8
  • R is the gas constant of polyethylene (8.314 Pa ⁇ m 3 /mol ⁇ K),
  • T means the absolute temperature value (K) of the measured temperature
  • G N 0 is the plateau modulus (G N 0 ) of polyethylene, and each frequency is changed from 0.05 to 500 rad/s under the conditions of 190°C temperature and 0.5% strain using a rotary rheometer.
  • the storage modulus and the loss modulus are measured respectively, and the storage modulus when the loss modulus has a minimum value in the region where the storage modulus of polyethylene is greater than the loss modulus is set as the plateau modulus.
  • the polyethylene is a melt index (MI 5 ; according to ASTM D 1238 at 190 °C and a load of 5.0 kg, considering that it is intended to manufacture a chlorinated polyethylene of MV (Mooney Viscosity) 70 or more in order to prevent the deterioration of the physical properties of the CPE compound. (Measured at) is 3 g/10 min or less, and it is preferable that the melt index is 0.5 g/10 min or more when considering preparing chlorinated polyethylene having an MV of 80 or less in order to prevent deterioration of the processability of the CPE compound.
  • MI 5 melt index
  • MV Mooney Viscosity
  • the melt index MI 5 of the polyethylene is 0.5 to 3 g / 10 min, more specifically 0.5 g / 10 min or more, or 1 g / 10 min or more, 3 g / 10 min or less, or 2.5 g / 10 min or less I can.
  • the polyethylene has a melt flow index (MFRR 21 .6/5 , MFR 21 .6 value measured under a temperature of 190° C. and a load of 21.6 kg according to ASTM D 1238, a temperature of 190° C. and a temperature according to ASTM D 1238, and a load of 21.6 kg).
  • the value divided by the MFR 5 value measured under a load of 5 kg) may be 10 to 20.
  • melt flow index exceeds 20
  • the physical properties of the CPE compound may deteriorate
  • it may be 10 or more, or 10.3 or more, and may be 20 or less, or 15 or less, or 12 or less, or 11 or less.
  • the 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 specifically 150,000 g/mol or more, or 185,000 g/mol or more, 300,000 g/mol or less, or 250,000 g/mol or less to be. Further, 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 is wider than 15, the molecular weight difference between polyethylenes is large, so it is difficult to uniformly distribute chlorine in the chlorinated polyethylene after the chlorination reaction.
  • Mw weight average molecular weight
  • PDI molecular weight distribution
  • the weight average molecular weight and molecular weight distribution (PDI, polydispersity index) of polyethylene are measured by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene using gel permeation chromatography (GPC), The molecular weight distribution can be calculated by dividing the resulting weight average molecular weight by the number average molecular weight.
  • the specific measurement method is as described in the test examples below.
  • the polyethylene may have an MDR torque (M H -M L ) of 7 Nm or more, 10 Nm or more, or 11 Nm or more, or 12 Nm or less, or 11.8 Nm or less.
  • MDR torque M H -M L
  • the MDR torque (M H -M L ) of the polyethylene refers to the degree of crosslinking, and the higher the degree of crosslinking, the higher the M H -M L , and the crosslinking efficiency is excellent when the same crosslinking agent is applied.
  • the MDR torque of the polyethylene may be measured using a moving die rheometer (MDR) as an example, and the M H value and the M L value are measured under conditions of 180°C and 10 min, and from the M H value It can be calculated by subtracting the M L value.
  • M H is the maximum vulcanizing torque measured in full cure
  • M L is the stored minimum vulcanizing torque. The specific measurement method is as described in the test examples below.
  • the polyethylene according to the present invention may be an ethylene homopolymer that does not contain a comonomer.
  • the optimum molecular structure and physical properties of polyethylene as described above including a first transition metal compound of the following formula (1), a second transition metal compound of the following formula (2), and a carrier supporting the first and second transition metal compounds
  • a production method comprising the step of polymerizing an ethylene monomer by introducing hydrogen gas, wherein 1:3 to 3: of the first transition metal compound and the second transition metal compound It is used in a molar ratio of 1. Accordingly, according to another embodiment of the present invention, a method of manufacturing the polyethylene is provided.
  • M 1 is a Group 4 transition metal
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with C 1-20 hydrocarbons;
  • R 11 and R 12 are the same as or different from each other, and each independently hydrogen, C 1-20 alkyl, C 1-20 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 6-20 aryloxy, C From the group consisting of 2-20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, or C 2-20 alkynyl, or N, O and S C 2-20 heteroaryl containing one or more heteroatoms selected;
  • Z 1 is halogen, C 1-20 alkyl, C 2-20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 6-20 aryl, substituted or unsubstituted C 1-20 alkylidene, Substituted or unsubstituted amino group, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy;
  • n 1 or 0;
  • A is carbon or silicon
  • M 2 is a Group 4 transition metal
  • R 21 is C 6-20 aryl substituted with C 1-20 alkyl
  • R 22 is C 3-20 branched alkyl
  • R 23 to R 25 are each independently C 1-20 alkyl
  • Z 21 and Z 22 are each independently halogen or C 1-10 alkyl
  • n is an integer from 1 to 10.
  • the C 1-20 alkyl group includes a linear or branched chain or cyclic alkyl group, and specifically, a methyl group (Me, methyl), an ethyl group (Et, Ethyl), a propyl group (Pr, Propyl), isopropyl group, n -Butyl group (n-Bu, n-Butyl), tert-butyl group (t-Bu, tert-Butyl)), pentyl group (Pt, Pentyl), hexyl group (Hx, Hexyl), heptyl group, octyl group, A cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.
  • the C 1-20 alkylene group includes a linear or branched alkylene group, and specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and the like, but are limited thereto. It is not.
  • the C 4-20 cycloalkyl group refers to a cyclic alkyl group among the alkyl groups as described above, and specifically, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. may be mentioned, but is not limited thereto. .
  • the C 2-20 alkenyl group includes a linear or branched alkenyl group, and specifically, an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like, but are not limited thereto.
  • the C 6-20 aryl group includes a monocyclic or condensed aryl group, and specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but are not limited thereto.
  • Examples of the C 1-20 alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.
  • the C 2-20 alkoxyalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with an alkoxy group, and specifically, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxy Alkoxyalkyl groups such as ethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group; Or an aryloxyalkyl group such as a phenoxyhexyl group, but is not limited thereto.
  • the C 1-20 alkylsilyl group or C 1-20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH 3 are substituted with 1 to 3 alkyl or alkoxy groups as described above, and specifically methylsilyl group, di Alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, dimethylmethylsilyl group, or dimethylpropylsilyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups, such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group, are mentioned, but are not limited thereto.
  • the C 1-20 silylalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with a silyl group, and specifically, -CH 2 -SiH 3 , a methylsilylmethyl group or a dimethylethoxysilylpropyl group, etc. may be mentioned. However, it is not limited to this.
  • the halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • the sulfonate group has a structure of -O-SO 2 -R', and R'may be a C 1-20 alkyl group.
  • the C 1-20 sulfonate group may include a methanesulfonate group or a phenylsulfonate group, but is not limited thereto.
  • the heteroaryl is a C 2-20 heteroaryl containing at least one of N, O, and S as a heterogeneous element, and specific examples include xanthene, thioxanthene, thiophene group, furan group, Pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, Quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group
  • substituents are optionally a hydroxy group within the range of exhibiting the same or similar effect as the desired effect; halogen; An alkyl group or an alkenyl group, an aryl group, an alkoxy group; An alkyl or alkenyl group, an aryl group, or an alkoxy group including at least one hetero atom among the heteroatoms of groups 14 to 16; Silyl group; An alkylsilyl group or an alkoxysilyl group; Phosphine group; Phosphide group; Sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.
  • Group 4 transition metal may include titanium (Ti), zirconium (Zr), hafnium (Hf), and the like, but is not limited thereto.
  • the first transition metal compound exhibits high polymerization activity and is easy to prepare a low molecular weight polymer
  • the second transition metal compound is easier to prepare a high molecular weight polymer compared to the first transition metal compound. Accordingly, by adjusting the mixing ratio of the first and second transition metal compounds in the hybrid supported catalyst, the low molecular weight content in the prepared polymer is minimized, and the molecular weight distribution may be increased due to the high molecular weight characteristics of the second transition metal compound. , In addition, it can be easy to adjust the viscosity.
  • the polyethylene thus prepared may have increased crosslinking degree and entanglement.
  • the first transition metal compound represented by Formula 1 is a non-crosslinked compound containing a ligand of Cp 1 and Cp 2 , and the ligands of Cp 1 and Cp 2 may be the same or different from each other, and each independently cyclo It may be any one selected from the group consisting of pentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals, and these ligands are C 1-20 hydrocarbons, more specifically For example, it may be substituted with 1 or more or 1 to 3 C 1-10 alkyl.
  • the ligands of Cp 1 and Cp 2 may exhibit high polymerization activity by having a non-shared electron pair capable of acting as a Lewis base, and in particular, when the ligands of Cp 1 and Cp 2 are cyclopentadienyl with relatively little steric hindrance , It exhibits high polymerization activity and low hydrogen reactivity, so that low molecular weight olefin polymers can be polymerized with high activity.
  • the ligands of Cp 1 and Cp 2 are, for example, the chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of the olefin polymer prepared by controlling the degree of steric hindrance according to the type of substituted functional group. The properties can be easily adjusted.
  • the ligand of said Cp 1 and Cp 2 are substituted by R 11 and R 12, respectively, at this time, the R 11 and R 12 are the same or different, each independently, hydrogen, C 1-20 alkyl, C It may be 2-20 alkoxyalkyl, C 7-40 arylalkyl, or C 2-12 heteroaryl including one or more heteroatoms selected from the group consisting of N, O and S, and more specifically C 1 -10 alkyl, C 2-10 alkoxyalkyl, C 7-20 arylalkyl, or C 4-12 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S.
  • R 11 and R 12 may each be a substituent as defined above, but at least one of R 11 and R 12 may be C 2-20 alkoxyalkyl or C 2-10 alkoxyalkyl.
  • M 1 (Z 1 ) 3-m exists between the ligands of Cp 1 and Cp 2 , and M 1 (Z 1 ) 3-m may affect the storage stability of the metal complex.
  • Z 1 may each independently be halogen or C 1-20 alkyl, and more specifically, each independently may be F, Cl, Br or I.
  • M 1 may be Ti, Zr or Hf, more specifically Zr or Hf, and even more specifically Zr.
  • M 1 is Ti, Zr or Hf;
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals.
  • R 11 and R 12 are each independently hydrogen, C 1-20 alkyl, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-20 arylalkyl, furanyl, or thiophenyl, wherein At least one of R 11 and R 12 is C 2-20 alkoxyalkyl; Z 1 may be a halogen; phosphorus compound.
  • the first transition metal compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto:
  • M 1 is Zr
  • Cp 1 and Cp 2 are each independently an unsubstituted cyclopentadienyl group or C 1-10 alkyl such as methyl One or more substituted cyclopentadienyl groups
  • R 11 and R 12 are each independently hydrogen, C 1-20 alkyl, C 2-20 alkoxyalkyl, C 7-20 aryl or C 7-20 arylalkyl, , At least one or both of R 11 and R 12 are C 2-20 alkoxyalkyl, more specifically C 2-10 alkoxyalkyl, and more specifically t-butoxyhexyl group
  • m may be a compound of 1.
  • the first transition metal compound represented by Formula 1 may be synthesized by applying known reactions. Specifically, a ligand compound is prepared through various synthesis processes, and then a metal precursor compound is added to perform metallation, but it is not limited thereto, and a more detailed synthesis method may be referred to the Examples. .
  • the second transition metal compound represented by Formula 2 forms a ligand structure in which an indene derivative and an amine derivative are crosslinked by a bridge compound, and a non-shared electron pair capable of acting as a Lewis base in the ligand structure
  • excellent polymerization activity can be exhibited.
  • structurally stable and electronically rich indene structures may exhibit high catalytic activity, and since the bridging group includes a tether group, excellent support stability for a carrier may be exhibited.
  • the second transition metal compound is substituted with a functional group (R 22 ) having a branched structure at position 2 of the indene structure, and by stabilizing beta-hydrogen in the polymer chain in which the nitrogen atom of the amine derivative grows by hydrogen bonding.
  • R 22 a functional group having a branched structure at position 2 of the indene structure
  • R 22 may be a branched alkyl of C 3-12 or C 3-6 such as isopropyl, isobutyl, t-butyl, isopentyl, and the like, and isopropyl, which is more advantageous in terms of steric effects. have.
  • the indene structure has an inductive effect capable of supplying sufficient electrons by bonding of R 21 , specifically, 1 or more, or 1 or 2 substituted C 6-20 aryl with C 1-20 alkyl at position 4 effect) can exhibit higher catalytic activity.
  • R 21 may be phenyl substituted 1 or 2 with C 3-6 branched alkyl such as 4-tert-butyl phenyl and 3,5-ditert-butyl phenyl.
  • R 23 bonded to N in the above formula 2 is C 1- 20 may be a linear or branched alkyl, more specifically one branched alkyl of C 3-12, or C 3-6, such as t- butyl I can.
  • the transition metal compound is stericly stabilized, and the catalyst is stabilized by an electron supply effect, thereby exhibiting higher catalytic activity.
  • R 21 is phenyl substituted with one or two C 3-6 branched alkyl
  • R 22 and R 23 are each independently C 3-6 branched alkyl
  • R 22 may be isopropyl.
  • the bridge group includes a tethered group of -(CH 2 )nOR 25 capable of tethering to the carrier together with the functional group of R 24 . Accordingly, it is possible to exhibit excellent support stability, and to maintain excellent catalytic activity to prepare a high molecular weight polymer.
  • R 24 may be C 1-12 or C 1-6 linear or branched alkyl. More specifically, it may be C 1-4 straight-chain alkyl or methyl, and in the case of a straight-chain structure or methyl as described above, solubility may be increased to improve loading efficiency.
  • R 25 in the tether group may be C 1-12 or C 1-6 linear or branched alkyl. More specifically, it may be C 3-6 branched alkyl or t-butyl, and when it has a branched structure such as t-butyl, it can be easily detached and bonded to the carrier, thereby exhibiting excellent support stability.
  • n in the tether group may specifically be 3 to 8, or 4 to 6, and in this case, the tether group may have an appropriate length and thus stably exhibit catalytic activity with superior support stability.
  • A may be more specifically silicon (Si).
  • A is silicon
  • R 25 is C 3-6 branched alkyl
  • n may be an integer of 4 to 6.
  • the second transition metal compound of Formula 2 may include a Group 4 transition metal such as titanium (Ti), zirconium (Zr), and hafnium (Hf) as the central metal (M 2 ).
  • a Group 4 transition metal such as titanium (Ti), zirconium (Zr), and hafnium (Hf) as the central metal (M 2 ).
  • the catalyst increases the structural openness compared to the case where other Group 4 transition metals such as Zr and Hf are included, so that the catalyst provides more excellent polymerization activity. And can exhibit high molecular weight by stabilizing the catalyst through an electron supply effect.
  • Z 21 and Z 22 are each independently a halogen such as chloro; Or it may be C 1-4 alkyl such as methyl. More specifically, both Z 21 and Z 22 may be methyl, and in this case, Z 21 and Z 22 may exhibit better catalytic activity than when they are halogen.
  • M 2 is titanium, and Z 21 and Z 22 may each independently be C 1-4 alkyl.
  • A is silicon
  • M 2 is titanium
  • R 21 is phenyl substituted with one or two C 3-10 branched alkyl such as t-butyl
  • R 22 Is a C 3-6 branched alkyl such as isopropyl
  • R 23 is a C 3-6 branched alkyl such as t-butyl
  • R 24 is a C 1-4 straight chain alkyl such as methyl
  • R 25 is t- C 3-6 branched alkyl such as butyl
  • Z 21 and Z 22 are each independently C 1-4 alkyl such as methyl
  • n may be a compound having an integer of 4 to 6.
  • Representative examples of the second transition metal compound of Formula 2 include compounds having the following structures, but are not limited thereto:
  • the second transition metal compound described above may be prepared by lithiation (or lithium substitution) of the ligand compound of Formula 3 below, and then reacting with a Group 4 transition metal-containing halide:
  • R 21 to R 25 and n are as defined above.
  • Reaction Scheme 1 below shows a process for preparing the second transition metal compound of Formula 2 according to an embodiment of the present invention.
  • Scheme 1 below is only an example for explaining the present invention, but the present invention is not limited thereto.
  • Reaction Scheme 1 A, M 2 , R 21 to R 25 , Z 21 , Z 22 and n are the same as defined above, and X 1 and X 2 are each independently a halogen group.
  • the compound (2) of Formula 2 is lithiumized by reacting the ligand compound (3) of Formula 3 with alkyl lithium such as n-butyllithium (NBL), and then, TiCl 4 or the like. It can be prepared by reacting with the same Group 4 transition metal-containing halide (4).
  • alkyl lithium such as n-butyllithium (NBL)
  • TiCl 4 or the like it can be prepared by reacting with the same Group 4 transition metal-containing halide (4).
  • X 1 and X 2 in the compound (2) of Formula 2 are each C 1-10 alkyl, after lithiation, an alkylating agent for alkylation of metal M such as MMB (Methyl Magnesium Bromide) is additionally added. Can be put in.
  • MMB Metal Magnesium Bromide
  • the ligand compound (3) used in the preparation of the compound (2) of Formula 2 may be prepared through the same manufacturing process as in Scheme 2 below.
  • Scheme 2 below is only an example for explaining the present invention, but the present invention is not limited thereto.
  • R 21 to R 24 , and n are the same as previously defined, and X 3 and X 4 are each independently a halogen group.
  • the ligand compound (3) comprises the steps of reacting an indene-based compound (5) as a Cp unit with an alkyl lithium such as n-butyllithium (NBL) to make lithium; Reacting the resulting reactant with a raw material 6 for providing a tether group to prepare a compound 7 in which a tether group is bonded to an indene structure; And reacting the compound (7) with a primary amine (8) having a substituent of R 3 such as t-BuNH 2.
  • NBL n-butyllithium
  • the reaction in each step may be performed by applying known reactions, and a more detailed synthesis method may refer to the preparation example described later.
  • the hybrid supported catalyst includes the first and second transition metal compounds, and has a wide molecular weight distribution according to the formation of a polymer tail in a molecular weight distribution curve with a minimized low molecular weight, thereby producing chlorinated polyolefins and compounds.
  • Polyolefin, in particular, high-density polyethylene capable of improving tensile strength according to an increase in crosslinking degree can be produced very effectively.
  • the above-described effect may be further enhanced by controlling the mixing ratio of the first and second transition metal compounds in the hybrid supported catalyst.
  • the mixing molar ratio of the first and second transition metal compounds may be 1:3 to 3:1, or 1:1.5 to 2:1.
  • the first and second transition metal compounds are included in a supported form.
  • the transition metal compound is used in the form of a supported catalyst as described above, the morphology and physical properties of the polyethylene produced may be further improved, and may be suitably used for slurry polymerization, bulk polymerization, and gas phase polymerization processes.
  • a carrier having a highly reactive hydroxy group, silanol group, or siloxane group on the surface may be used, and for this purpose, a carrier having a surface modified by calcination or a surface of which moisture has been removed by drying may be used.
  • a carrier having a surface modified by calcination or a surface of which moisture has been removed by drying may be used.
  • silica prepared by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) Oxide, carbonate, sulfate, and nitrate components such as 2 may be contained.
  • the temperature may be 200 to 600°C, and may be 250 to 600°C.
  • the calcination or drying temperature of the carrier is lower than 200°C, there is a possibility that the moisture on the surface and the cocatalyst may react because there is too much moisture remaining in the carrier. Although the rate may be relatively high, this requires a large amount of cocatalyst.
  • the drying or calcination temperature exceeds 600°C, the surface area decreases as the pores on the surface of the carrier are combined, and a lot of hydroxyl groups or silanol groups disappear on the surface, and only siloxane groups remain, reducing the reaction site with the cocatalyst. There is a fear of doing it.
  • the amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying. If the amount of the hydroxy group is too low, the reaction site with the cocatalyst is small, and if it is too large, it may be due to moisture other than the hydroxy group present on the surface of the carrier particles.
  • the amount of hydroxy groups on the surface of the carrier may be 0.1 to 10 mmol/g or 0.5 to 5 mmol/g.
  • silica especially silica prepared by calcining silica gel, is supported by chemical bonding of the transition metal compound to the silica carrier, so that there is hardly any catalyst released from the surface of the carrier in the propylene polymerization process.
  • the first and second transition metal compounds are the total amount of the first and second transition metal compounds per weight of the carrier, for example, based on 1 g of silica. 10 ⁇ mol or more, or 30 ⁇ mol or more, or 60 ⁇ mol or more, and may be supported in a content range of 120 ⁇ mol or less or 100 ⁇ mol or less. When supported in the above content range, it may be advantageous in terms of maintaining the activity of the catalyst by exhibiting an appropriate supported catalytic activity.
  • the hybrid supported catalyst having the above-described configuration exhibits excellent polymerization activity, and chlorinated polyethylene or polyethylene having a structure optimized to improve the tensile strength of the compound can be prepared.
  • the hybrid supported catalyst may be introduced into the polymerization reaction system by itself, or a C 5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbons such as toluene and benzene. It may be dissolved or diluted in a solvent, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, or chlorobenzene, and then introduced into the reaction system.
  • the solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treating a small amount of alkyl aluminum.
  • the catalyst composition may further include a cocatalyst in terms of improving high activity and process stability.
  • the cocatalyst may include one or more of the compounds represented by the following Chemical Formula 9, Chemical Formula 10, or Chemical Formula 11.
  • R a may be the same as or different from each other, and each independently halogen; Hydrocarbons of C 1-20; Or a halogen-substituted C 1-20 hydrocarbon;
  • n is an integer of 2 or more
  • R b may be the same as or different from each other, and each independently halogen; Hydrocarbons of C 1-20; Or a halogen-substituted C 1-20 hydrocarbon;
  • J is aluminum or boron
  • E is a neutral or cationic Lewis base
  • H is a hydrogen atom
  • Z is a group 13 element
  • Q may be the same as or different from each other, and each independently of one or more hydrogen atoms is substituted or unsubstituted with halogen, C 1-20 hydrocarbon, alkoxy or phenoxy, C 6-20 aryl group or C 1-20 It is an alkyl group.
  • Examples of the compound represented by Formula 9 include C 1-20 alkylaluminoxane-based compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one or two of them Mixtures of the above can be used.
  • examples of the compound represented by Formula 10 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclo Pentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl 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, tributyl boron, and the like. More specifically, it may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.
  • examples of the compound represented by Formula 11 include triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p- Tolyl) boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammony Um tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron,
  • the cocatalyst when considering the fact that it can exhibit more excellent catalytic activity when used with the transition metal compound, is a compound represented by Formula 9, more specifically, C 1 such as methylaluminoxane. It may be an alkylaluminoxane-based compound of -20.
  • the alkylaluminoxane-based compound acts as a scavenger of hydroxyl groups present on the surface of the carrier to improve catalytic activity, and converts the halogen group of the catalyst precursor to a methyl group to promote chain growth during polymerization of polyethylene. .
  • the cocatalyst may be supported in an amount of 0.1 mmol or more, 5 mmol or more, or 8 mmol or more, or 10 mmol or more, 25 mmol or less, or 20 mmol or less per weight of the carrier, for example, based on 1 g of silica.
  • 0.1 mmol or more 5 mmol or more, or 8 mmol or more, or 10 mmol or more, 25 mmol or less, or 20 mmol or less per weight of the carrier, for example, based on 1 g of silica.
  • the catalyst composition may further include an antistatic agent.
  • an antistatic agent an ethoxylated alkyl amine, specifically, a compound represented by the following Formula 12 may be used.
  • the catalyst composition includes an antistatic agent, generation of static electricity is suppressed in the polyethylene polymerization process, so that the physical properties of the polyethylene produced may be further improved.
  • R may be C 8-30 alkyl, and when R includes an alkyl group having a carbon number in the above range, it may exhibit a fine powder reduction effect through an excellent antistatic action without causing an unpleasant odor.
  • the ethoxylated alkylamine may be a compound wherein R in Formula 1 is C 8-22 linear alkyl, or C 10-18 linear alkyl, or C 13-15 linear alkyl, , One of these compounds alone or a mixture of two or more may be used. Specific examples include N,N-bis(2-hydroxyethyl)tridecylamine, or N,N-bis(2-hydroxyethyl)pentadecylamine, and the like, commercially available Atmer 163TM (manufactured by CRODA), and the like may be used.
  • an antistatic agent when further included, 0.5 parts by weight or more, or 1 part by weight or more, or 2 parts by weight or more, 20 parts by weight or less, or 10 parts by weight or less, or It may be included in an amount of 7 parts by weight or less.
  • the cocatalyst and the antistatic agent may be used in combination with the aforementioned hybrid supported catalyst, respectively, or may be used while being supported on a carrier in the hybrid supported catalyst.
  • the catalyst composition includes the steps of supporting a cocatalyst compound on the carrier, and supporting a transition metal compound on the carrier; And injecting an antistatic agent in a slurry state and heat-treating the carrier on which the cocatalyst and the transition metal compound are supported.
  • the loading of the transition metal compound may be carried out after the loading of the first transition metal compound, or may be carried out vice versa.
  • a supported catalyst having a structure determined according to such a supporting sequence may exhibit higher catalytic activity and excellent process stability in the manufacturing process of polyethylene.
  • the catalyst composition may be used in the form of a slurry or diluted in a solvent depending on the polymerization method, or may be used in the form of a mud catalyst mixed with a mixture of oil and grease.
  • the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of propylene monomers, such as pentane, hexane, heptane, nonane, decane, and these Isomers and aromatic hydrocarbon solvents such as toluene and benzene, or hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and any one or a mixture of two or more of them may be used.
  • the catalyst composition may further include the above-described solvent, and a small amount of water or air, which may act as a catalyst poison, may be removed by treating the solvent with a small amount of alkyl aluminum before use.
  • the polymerization reaction for the production of polyethylene may be performed using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
  • the polymerization reaction may be carried out in a slurry phase polymerization in a hydrocarbon-based solvent (eg, an aliphatic hydrocarbon-based solvent such as hexane, butane, and pentane).
  • a hydrocarbon-based solvent eg, an aliphatic hydrocarbon-based solvent such as hexane, butane, and pentane.
  • the first and second transition metal compounds according to the present invention exhibit excellent solubility in aliphatic hydrocarbon-based solvents, they are stably dissolved and supplied to the reaction system, so that the polymerization reaction can proceed effectively.
  • the method for producing polyethylene according to an embodiment of the present invention may be performed in a single-CSTR reactor.
  • polymerization may proceed in the presence of an inert gas such as nitrogen.
  • the inert gas may play a role of prolonging the reaction activity of the metallocene compound contained in the catalyst by suppressing the rapid reaction of the metallocene catalyst at the beginning of the polymerization reaction.
  • the polymerization reaction is carried out under the introduction of hydrogen gas.
  • hydrogen gas introduced during the polymerization reaction activates the inert site of the metallocene catalyst and causes a chain transfer reaction to control the molecular weight and molecular weight distribution.
  • hydrogen gas is 0.001 parts by weight or more, or 0.005 parts by weight or more, 15 parts by weight or less, or 5 parts by weight or less, or 1 part by weight or less, or 0.015 parts by weight based on 100 parts by weight of the ethylene monomer. It may be added in an amount of not more than parts by weight.
  • the temperature during the polymerization reaction may be 70 to 100 °C, or 80 to 90 °C. If the polymerization reaction temperature is too low, it is not appropriate in terms of the polymerization rate and productivity. Conversely, if the polymerization reaction temperature is higher than necessary, fouling in the reactor may be caused.
  • the pressure during the polymerization reaction may be 6.8 to 8.7 kg/cm 2 , or 7.0 to 8.5 kg/cm 2 , or 7.0 to 7.5 kg/cm 2 to secure optimal productivity.
  • the polymerization reaction pressure may be about 6.8 kg/cm 2 or more in terms of preventing blocking due to excessive generation of high molecular weight and optimizing productivity , and about 8.7 kg/cm 2 in consideration of a decrease in ethylene source units under high pressure polymerization conditions. It can be below.
  • an organic solvent may be further used as a reaction medium or diluent in the polymerization reaction.
  • Such an organic solvent may be used in an amount sufficient to properly perform slurry polymerization or the like in consideration of the content of the ethylene-based monomer.
  • trialkyl aluminum such as triethyl aluminum may be optionally further added during the polymerization reaction.
  • alkyl is as defined above, specifically C 1-20 alkyl, and more specifically C 1-6 straight or branched chain alkyl, such as methyl, ethyl, isobutyl, etc. I can.
  • trialkyl aluminum (based on 1M) may be added in an amount of 10 cc or more, 50 cc or less, or 30 cc or less based on 1 kg of the ethylene monomer, and polymerization reaction in the presence of trialkyl aluminum in this content range, Homo polyethylene having excellent strength properties can be more easily produced.
  • Polyethylene which can be improved, is produced.
  • the polyethylene may be a homopolymer of ethylene that does not contain a separate copolymer.
  • the polyethylene is, for example, an ethylene homopolymer, preferably high-density polyethylene (HDPE), the above-described physical properties may be more appropriately satisfied.
  • the high-density polyethylene has excellent softening point, hardness, strength and electrical insulation, and can be used in various containers, packaging films, fibers, pipes, and the like.
  • the method for preparing the chlorinated polyethylene includes a hybrid supported catalyst in which at least one first transition metal compound represented by Formula 1 and at least one second transition metal compound represented by Formula 2 are supported on a carrier. In the presence of a catalyst composition, adding hydrogen and polymerizing an ethylene-based monomer to produce polyethylene; And chlorinating the polyethylene by treating it with chlorine.
  • reaction conditions in the step of polymerizing the ethylene-based monomer to produce the polyethylene are as described above.
  • the chlorine treatment of the polyethylene may be performed by a water phase method in which polyethylene is reacted with chlorine in a suspension state, or by an acid phase method in which polyethylene is reacted with chlorine in an aqueous HCl solution.
  • the aqueous phase method is a method of chlorinating using an emulsifier and a dispersing agent together with water as an example
  • the acid phase method is a method of chlorinating an aqueous acid solution such as an aqueous solution of hydrochloric acid (HCl) using an emulsifier and a dispersant That's the way.
  • the chlorination reaction may consist of dispersing polyethylene with water, an emulsifying agent and a dispersing agent, and then reacting by adding a catalyst and chlorine.
  • the emulsifier is, for example, polyether or polyalkylene oxide.
  • the dispersant is, for example, a polymer salt or an organic acid polymer salt.
  • the organic acid may be, for example, methacrylic acid or acrylic acid.
  • the catalyst is, for example, a chlorination catalyst, and another example is a peroxide or an organic peroxide.
  • the chlorine may be used alone or in combination with an inert gas, for example.
  • the final chlorination reaction temperature may be, for example, 60 to 150°C, or 90 to 140°C, or 120 to 140°C.
  • the chlorination reaction time may be, for example, 10 minutes to 10 hours, or 1 hour to 6 hours, or 2 hours to 4 hours.
  • the chlorination reaction is carried out by dispersing 100 parts by weight of polyethylene, 0.01 to 1.0 parts by weight of emulsifier, or 0.05 to 0.5 parts by weight, and 0.1 to 10 parts by weight of a dispersant, or 0.5 to 5.0 parts by weight in water, and then the catalyst 0.01 to 1.0 Part by weight, or 0.05 to 0.5 parts by weight and 80 to 200 parts by weight of chlorine, or 100 to 150 parts by weight may be added and reacted.
  • the chlorinated polyethylene produced by the above reaction or chlorination process may be obtained as a powdery chlorinated polyethylene through, for example, a neutralization process, washing process, and drying process.
  • the neutralization process may be, for example, a process of neutralizing the reactant through the chlorination process with a base solution at 70 to 90°C or 75 to 80°C for 4 to 8 hours.
  • the chlorinated polyethylene obtained according to the manufacturing method of the above-described embodiment has a high crosslinking degree and an appropriate level of Mooney viscosity, and thus can exhibit excellent tensile strength properties.
  • the chlorinated polyethylene has a Mooney viscosity (MV) of 70 to 80 measured under the condition of 121°C, more specifically 70 or more, 80 or less, or 76 or less.
  • MV Mooney viscosity
  • Mooney viscosity of chlorinated polyethylene can be measured using a Mooney viscometer, specifically, it can be measured by preheating at 121° C. for 1 min, and then rotating the rotor for 4 min. A more specific method will be described in detail in the following test examples.
  • chlorinated polyethylene may be, for example, random chlorinated polyethylene.
  • the chlorinated polyethylene as described above has excellent chemical resistance, weather resistance, flame retardancy, workability, and impact strength reinforcing effect, and thus may be useful for wires or cables.
  • a compound showing excellent tensile strength properties including chlorinated polyethylene prepared by the method as described above.
  • the compound may be a CPE compound including crosslinked chlorinated polyethylene prepared by crosslinking the chlorinated polyethylene in the presence of a perproduct crosslinking agent.
  • the crosslinking reaction may be performed at 140 to 230°C, and a peroxide-based crosslinking agent such as dicumyl peroxide may be used as the crosslinking agent.
  • a peroxide-based crosslinking agent such as dicumyl peroxide
  • an antioxidant may be optionally further added during the crosslinking reaction.
  • the chlorinated polyethylene (CPE) compound is based on 100 parts by weight of chlorinated polyethylene, 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 of a plasticizer , And 1 part by weight to 20 parts by weight of a crosslinking agent.
  • the compound containing the chlorinated polyethylene may exhibit excellent tensile strength properties, and specifically, the tensile strength measured at 500 mm/min according to ASTM D 412 is 12 or more, or 12 to 14.
  • the method of manufacturing a molded article from chlorinated polyethylene according to the present invention can be applied to a conventional method in the art.
  • the chlorinated polyethylene may be roll-mill compounded and extrusion-processed to manufacture a molded article.
  • Polyethylene according to the present invention has a molecular structure having a low molecular weight and a high polymer content, and thus can improve tensile strength while maintaining excellent processability and Mooney viscosity characteristics when preparing a chlorinated polyethylene compound.
  • tert-Butyl-O-(CH 2 ) 6 -Cl was prepared by the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and NaCp was reacted thereto.
  • tert-Butyl-O-(CH 2 ) 6 -C 5 H 5 was obtained (yield 60%, bp 80°C / 0.1 mmHg).
  • tert-Butyl-O-(CH 2 ) 6 -C 5 H 5 was dissolved in THF at -78°C, and normal butyl lithium (n-BuLi) was slowly added, the temperature was raised to room temperature, and then reacted for 8 hours. .
  • the previously synthesized lithium salt solution was slowly added to the suspension solution of ZrCl 4 (THF) 2 (1.70 g, 4.50 mmol)/THF (30 mL) at -78°C again at room temperature. It was further reacted for 6 hours at.
  • the ligand compound 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(4-(3,5-di-tert-butylphenyl) prepared in step 1 -2-isopropyl-1H-inden-1-yl)-1-methylsilanamine (2.4g, 3.9mmol) was added, toluene (13ml) was added, and then cooled to -20°C or less. After sufficiently cooling through stirring for 5 minutes, NBL (5.1ml, 2.5M in Hexane) was added to the resulting mixed solution to perform lithiation. It was confirmed that the color of the mixed solution turned brown after lithiation.
  • Silica (SYLOPOL 948TM, manufactured by Grace Davision) was dehydrated and dried under vacuum at 600° C. for 12 hours.
  • Ethylene homopolymerization was carried out using the hybrid supported catalyst prepared in Synthesis Example 3 under the following conditions.
  • Polyethylene was prepared by changing the hydrogen input amount to 1.5 g/hr under the same conditions as in Example 1.
  • Polyethylene was prepared by changing the hydrogen input amount to 0.5 g/hr under the same conditions as in Example 1.
  • High-density polyethylene (CE2080TM, manufactured by LG Chem.) prepared using a Ziegler-Natta catalyst was used.
  • High-density polyethylene (SC200TM, manufactured by LG Chem.) prepared using a metallocene catalyst was used.
  • High-density polyethylene (SC100ETM, manufactured by LG Chem.) prepared using a metallocene catalyst was used.
  • High-density polyethylene (CE6040XTM, manufactured by LG Chem.) prepared using a Ziegler-Natta catalyst was used.
  • Polyethylene was prepared in the same manner as in Example 1, except that hydrogen gas was not added during the polymerization reaction.
  • Polyethylene was prepared in the same manner as in Example 1, except that the hybrid supported catalyst prepared in Synthesis Example 4 was used.
  • Fraction ratio (Fraction, %): GPC analysis was performed, and the resulting molecular weight distribution curve was calculated as the area (%) occupied by log Mw section relative to the total area. The sum of the fractions is 100 ⁇ 1, which may not be exactly 100.
  • the GPC analysis was specifically performed under the following conditions.
  • a Waters PL-GPC220 instrument was used as the GPC device, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160 °C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) was used as a solvent, and the flow rate was 1 mL/min. Polyethylene samples according to Examples and Comparative Examples were pretreated by dissolving in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT for 10 hours at 160° C.
  • Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen.
  • the weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g 9 types of /mol were used.
  • Weight average molecular weight (Mw, g/mol) and molecular weight distribution (PDI, polydispersity index) GPC analysis was performed in the same manner as in Test Example 1, and the weight average molecular weight (Mw) and number average After measuring the molecular weight (Mn), respectively, the molecular weight distribution (PDI) was calculated from the ratio of Mw/Mn.
  • MI 5. 0 Melt Index of the polyethylene prepared in Examples and Comparative Examples (MI 5. 0) is according to ASTM D1238 (condition E, 190 °C, 5.0 kg load) Standards It was measured.
  • the melt flow rate ratio (MFRR 21.6/5 ) for polyethylene was calculated by dividing MFR 21.6 by MFR 5 , and MFR 21.6 was measured under a temperature of 190°C and a load of 21.6 kg according to ASTM D 1238.
  • MFR 5 was measured under a temperature of 190° C. and a load of 5.0 kg according to ASTM D 1238.
  • Density The density (g/cm 3 ) of polyethylene was measured by the method of ASTM D-1505.
  • MDR torque (MH-ML): To evaluate the degree of crosslinking of polyethylene, the MDR torque value of each polyethylene sample was measured using Alpha Technologies Production MDR (Moving Die Rheometer).
  • M H and M L values were measured under conditions of 180° C. and 10 min using a moving die rheometer (MDR) for the prepared sample sheet.
  • MDR torque M H -M L was calculated by subtracting the M L value from the measured M H value.
  • M H is the maximum vulcanizing torque measured in full cure
  • M L is the stored minimum vulcanizing torque.
  • Entangling molecular weight (Me, entanglement): The entanglement molecular weight (Me, entanglement) was calculated from the storage modulus and loss modulus measured using a rotary rheometer.
  • ⁇ density of polyethylene measured by the method of ASTM D-1505 (kg/m 3 ) X 0.8,
  • R is the gas constant of polyethylene (8.314 Pa ⁇ m 3 /mol ⁇ K),
  • T is the absolute temperature value (K) of the measured temperature
  • G N 0 is the plateau elastic modulus (G N 0 ) of polyethylene, using a rotary rheometer, changing each frequency to 0.05 to 500 rad/s at 190°C temperature and 0.5% strain, and storage modulus The and loss modulus are measured respectively, and the storage modulus when the loss modulus has a minimum value in a region where the storage modulus of polyethylene is greater than the loss modulus is taken as the plateau modulus.
  • Chlorinated polyethylene was prepared using the polyethylene prepared in the above Examples and Comparative Examples, and the physical properties of the prepared chlorinated polyethylene were evaluated by the following method. The results are shown in Table 3.
  • Mooney viscosity Wrap the rotor in the Mooney viscometer with CPE sample and close the die. After preheating at 121° C. for 1 min, the rotor was rotated for 4 min to measure MV (Mooney viscosity, 121° C., ML1+4).
  • Test Example 3 a CPE compound was prepared using polyethylene in Examples and Comparative Examples, and physical properties were evaluated.
  • the CPE compounds prepared using the polyethylene of Examples 1 to 3 exhibited improved tensile strength characteristics while maintaining excellent Mooney viscosity characteristics as compared to the comparative examples.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne : un polyéthylène qui a une structure moléculaire ayant une faible teneur en petites molécules et une teneur élevée en polymère dans les molécules, et peut ainsi améliorer la résistance à la traction tout en conservant une excellente aptitude au traitement et des caractéristiques de viscosité Mooney pendant la production d'un composé polyéthylène chloré ; et un polyéthylène chloré produit à l'aide de celui-ci.
PCT/KR2020/013051 2019-09-27 2020-09-25 Polyéthylène et polyéthylène chloré associé WO2021060907A1 (fr)

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CN112088176A (zh) * 2018-12-10 2020-12-15 Lg化学株式会社 聚乙烯及其氯化聚乙烯
EP3778664A4 (fr) * 2018-12-10 2021-08-11 Lg Chem, Ltd. Polyéthylène et polyéthylène chloré associé
CN112088176B (zh) * 2018-12-10 2023-02-28 Lg化学株式会社 聚乙烯及其氯化聚乙烯
US11834528B2 (en) 2018-12-10 2023-12-05 Lg Chem, Ltd. Polyethylene and chlorinated polyethylene thereof

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