WO2020122561A1 - Polyéthylène et polyéthylène chloré associé - Google Patents

Polyéthylène et polyéthylène chloré associé Download PDF

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WO2020122561A1
WO2020122561A1 PCT/KR2019/017398 KR2019017398W WO2020122561A1 WO 2020122561 A1 WO2020122561 A1 WO 2020122561A1 KR 2019017398 W KR2019017398 W KR 2019017398W WO 2020122561 A1 WO2020122561 A1 WO 2020122561A1
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polyethylene
formula
alkyl
group
aryl
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Korean (ko)
Inventor
정철환
이시정
홍복기
박성현
김선미
최이영
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020190163116A external-priority patent/KR102252430B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US17/051,031 priority Critical patent/US12304976B2/en
Priority to CN202311260736.8A priority patent/CN117050215A/zh
Priority to EP19894608.9A priority patent/EP3778663B1/fr
Priority to CN201980030754.2A priority patent/CN112088173B/zh
Publication of WO2020122561A1 publication Critical patent/WO2020122561A1/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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • C08F8/22—Halogenation by reaction with free halogens
    • 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 halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention maintains a stable crystal structure at a high temperature and secures excellent chlorine distribution uniformity, so as to improve the impact strength of the PVC compound, chlorinated polyethylene excellent in chlorination productivity and thermal stability, polyethylene and its chlorinated polyethylene It is about.
  • Chlorinated polyethylene produced by reacting polyethylene with chlorine is known to have improved physical and mechanical properties compared to polyethylene, and is particularly suitable for packing materials such as various containers, fibers, pipes, and heat transfer materials because it can withstand harsh external environments. Is used.
  • Chlorinated polyethylene is generally prepared by placing polyethylene in suspension and then reacting with chlorine, or by placing polyethylene in an aqueous HCl solution and reacting with chlorine to replace the hydrogen in the polyethylene with chlorine.
  • chlorinated polyethylene such as CPE (Chlorinated Polyethylene) is often used for the purpose of impact modifiers of pipes and window profiles through compounding with PVC, and is generally produced by reacting polyethylene with chlorine in suspension.
  • Polyethylene can be prepared by reacting with chlorine in an aqueous HCl solution. In the case of such a PVC compound product, excellent impact strength is required, but the strength of the compound varies depending on the properties of chlorinated polyethylene.
  • the impact strength of the final product is excellent, and for this, it is desirable to uniformly distribute chlorine in the HDPE chain.
  • general-purpose chlorinated polyethylene which is currently known, since polyethylene using a Ziegler-Natta catalyst is applied, the molecular weight distribution is wide and the ultra-high molecular weight content is large, resulting in poor uniformity of chlorine distribution in polyethylene and impact when compounded with PVC. There is a disadvantage of insufficient strength.
  • CPE when CPE is produced, it undergoes a process of chlorination, deoxidation, dehydration, and drying. If the crystal structure of HDPE is not maintained stably, the crystal structure collapses during high temperature chlorination and pores of polyethylene (PE) particles Can be blocked. In the post-deoxidation process, washing with water is required to remove residual HCl in the PE particles, but when the pores are blocked, the overall production time due to the deoxidation time delay is delayed and the chlorination productivity decreases.
  • PE polyethylene
  • the present invention provides a polyethylene and its chlorinated polyethylene capable of producing chlorinated polyethylene excellent in chlorination productivity and thermal stability to maintain a stable crystal structure at high temperature and secure excellent chlorine distribution uniformity, to improve the impact strength of the PVC compound. I want to.
  • the present invention is to provide a method for producing the polyethylene.
  • a high temperature corresponding to the elution temperature or higher of a point at which a peak intensity between the two peaks having the highest peak intensity is the minimum peak intensity is indicated.
  • Polyethylene is provided in which the ratio of the high crystal region, which represents the percentage value of the graph area of the crystal region divided by the total graph area, is 12.5% or less.
  • the present invention provides a method for producing the polyethylene.
  • the present invention provides a chlorinated polyethylene produced by reacting the polyethylene with chlorine.
  • the polyethylene according to the present invention maintains a stable crystal structure at high temperature and secures excellent chlorine distribution uniformity, and reacts with chlorine to produce chlorinated polyethylene having excellent chlorination productivity and thermal stability.
  • Example 1 is a diagram illustrating a temperature rise elution fractionation (TREF) graph for polyethylene of Example 1-2 according to an embodiment of the present invention, and a high crystal region on the temperature rise elution fractionation (TREF) graph.
  • TREF temperature rise elution fractionation
  • first and second are used to describe various components, and the terms are used only to distinguish one component from another component.
  • part by weight refers to the relative concept of the weight of the rest of the material based on the weight of a certain material. For example, in a mixture containing material A having a weight of 50 g, material B having a weight of 20 g, and material C having a weight of 30 g, the amount of material B and material C based on 100 parts by weight of material A is 40 It is parts by weight and 60 parts by weight.
  • % by weight means the absolute concept of the weight of the weight of a certain substance in the total weight.
  • the contents of substances A, B, and C in 100% of the total weight of the mixture are 50%, 20%, and 30% by weight, respectively. At this time, the sum of the content of each component does not exceed 100% by weight.
  • polyethylene capable of producing chlorinated polyethylene having excellent chlorination productivity and heat stability so as to maintain a stable crystal structure at high temperature and secure excellent chlorine distribution uniformity, thereby improving the impact strength of the PVC compound.
  • the polyethylene is a graph of a high crystal region corresponding to the elution temperature of the point at which the minimum peak intensity is indicated among the two peaks having the highest peak intensity on the temperature rise elution fractionation (TREF) graph. It is characterized in that the proportion of the high crystal region representing the percentage value of the area divided by the total graph area is 12.5% or less.
  • chlorinated polyethylene is produced by reacting polyethylene with chlorine, which means that a part of hydrogen in polyethylene is replaced with chlorine.
  • chlorine which means that a part of hydrogen in polyethylene is replaced with chlorine.
  • the properties of polyethylene are changed because the atomic volumes of hydrogen and chlorine are different.
  • chlorination productivity and thermal stability are increased more.
  • the overall size of the chlorinated polyethylene particles is smaller and more uniform, chlorine is more easily permeated to the center of the polyethylene particles, so the degree of chlorine substitution in the particles is uniform, and thus, the polyethylene according to the present invention has an alpha transition temperature. It is possible to provide a chlorinated polyethylene having high chlorination productivity and thermal stability due to a high ratio of high crystal region according to a temperature rise elution fractionation (TREF) analysis.
  • TEZ temperature rise elution fractionation
  • the polyethylene of the present invention is characterized in that the content of the high crystal region in the molecular structure is low, thereby increasing the elongation of CPE through uniform chlorine substitution.
  • the polyethylene of the present invention has a high alpha transition temperature so that the crystal structure can be stably maintained even at high temperatures. Through this, it is possible to shorten the deoxidation time and improve the chlorination productivity by improving the pore clogging phenomenon of the polyethylene particles while maintaining the crystal structure during the chloride reaction at high temperature.
  • the polyethylene of the present invention can produce chlorinated polyethylene having excellent chlorination productivity and thermal stability, and can increase the CPE elongation through uniform chlorine substitution to improve the impact strength when applied as an impact modifier to PVC compounds. have.
  • the polyethylene according to the present invention may be an ethylene homopolymer that does not contain a separate copolymer.
  • the polyethylene may have an alpha transition temperature of about 120°C or higher or about 120°C to about 145°C, or 122°C or higher or about 122°C to about 145°C, or 125°C or higher, or about 125°C to about 145°C.
  • the alpha transition temperature means the temperature at which the crystal arrangement changes while the lamella structure forming the crystal is maintained, and can be measured through thermal analysis of polyethylene. Specifically, the alpha transition temperature was lowered to -60°C using a DMA (Dynamic Mechanical Analyzer), maintained at that temperature for 5 minutes, and then increased to 140°C to bring the top of the tan ⁇ curve to the alpha transition temperature. It was measured.
  • DMA Dynamic Mechanical Analyzer
  • the change in the arrangement of polyethylene crystals before and after the alpha transition temperature appears, and the polyethylene of the present invention means that the change in crystal arrangement occurs at a higher temperature because the alpha transition temperature is closer to the melting temperature of 120°C or higher, which is During the chlorination process, the morphology of polyethylene particles is difficult to change. Accordingly, high chlorination productivity can be secured.
  • the polyethylene of the present invention is characterized by a high alpha transition temperature and a small proportion of a high crystal region on a temperature rise elution fractionation (TREF) graph.
  • TEZ temperature rise elution fractionation
  • the ratio of the high crystal region may be less than about 12.5% or less than about 5% to about 12.5% on the temperature rise elution fractionation (TREF) graph. Specifically, the proportion of the high crystal region may be about 12% or less or about 5% to about 12%, or about 11.8% or less or about 5% to about 11.8%. Specifically, the lower the proportion of the high crystal region, the more easily the chlorine molecule penetrates into the crystal and should be about 12% or less in terms of uniform chlorination. However, when the ratio of the high crystal region is excessively low, the ratio of the high crystal region may be about 5% or more in view of the possibility that the alpha transition temperature may also drop.
  • TEZ temperature rise elution fractionation
  • the ratio of the high crystal region may be obtained from a temperature rise elution fractionation (TREF) graph for polyethylene, as illustrated in one embodiment of FIG. 1.
  • a point indicating the minimum peak intensity among the two peaks having the highest peak intensity among the peaks on the TREF graph (minimum value)
  • the region above the elution temperature is referred to as a high crystal region with the elution temperature of the portion as a reference for the high crystal region, and the elution temperature point of the minimum value portion as a reference and a vertical axis. From this, the graph area of the high crystal region corresponding to the elution temperature of the minimum value portion was measured, and the percentage value divided by the total graph area was expressed as the ratio of the high crystal region (%).
  • a temperature rise elution fractionation (TREF) graph of polyethylene can be obtained through Agilent Technologies 7890A instrument of PolymerChar.
  • TEZ temperature rise elution fractionation
  • the temperature rise elution fractionation (TREF) graph of the polyethylene thus obtained shows the elution temperature (° C.) on the X-axis and the amount of elution at that temperature on the Y-axis (dW/dt), as illustrated by one embodiment of FIG. 1. ).
  • a region occupied by a graph corresponding to a temperature equal to or higher than a temperature at a portion where two peaks appearing on the temperature rise elution fractionation (TREF) graph is called a high crystal region. That is, the value obtained by integrating the area of the graph corresponding to the temperature higher than the elution temperature corresponding to the minimum value between the two peaks as the vertical axis can be referred to as the area of the high crystal region. It can be said that the percentage value of the area of the high crystal region divided by the total graph area is the ratio of the high crystal region.
  • the polyethylene is manufactured by optimizing a specific metallocene catalyst, and as described above, has a high alpha transition temperature as described above and a small proportion of a high crystal region according to a temperature rise elution fractionation (TREF) analysis.
  • the polyethylene according to the present invention has the characteristics of exhibiting better chlorination productivity and thermal stability when producing chlorinated polyethylene.
  • melt index MI 5 of about 0.1 g/10min to about 1.5 g/10min, or about 0.15 g/10min to, measured under conditions of temperature 190° C. and load 5 kg by the method of ASTM D 1238 as described above.
  • the melt index MI 5 may be less than about 1.5 g/10min in terms of excellent thermal stability due to less change in PE particle shape in a high-temperature slurry state for chlorination as the viscosity increases with a lower MI.
  • the melt index MI 5 may be 0.1 g/10 min or more in terms of improved workability due to lower viscosity as the MI increases.
  • the polyethylene the melt flow index (MFRR 21.6/5 , ASTM D 1238 method, the melting index measured at 190 °C, 21.6 kg load divided by the melting index measured at 190 °C, 5 kg load) is about 10 to about 20, or about 11 to about 18.
  • the density of the polyethylene may be about 0.947 g/cm 3 to about 0.957 g/cm 3 or about 0.948 g/cm 3 to about 0.954 g/cm 3 . This means that the content of the crystalline structure of polyethylene is high and dense, and it has a feature that it is difficult to change the crystalline structure during the chlorination process.
  • the polyethylene according to the present invention may have a molecular weight distribution of 2 to 10, or 3 to 7, or 3.5 to 6. This means that the molecular weight distribution of polyethylene is narrow.
  • the molecular weight distribution is wide, since the molecular weight difference between polyethylenes is large, the chlorine content between polyethylenes may vary after the chlorination reaction, making uniform distribution of chlorine difficult.
  • the fluidity is high when the low molecular weight component is melted, the pores of the polyethylene particles can be blocked, thereby reducing chlorination productivity.
  • chlorine since it has the molecular weight distribution as described above, since the molecular weight difference between polyethylenes is not large after the chlorination reaction, chlorine may be uniformly substituted.
  • the molecular weight distribution is measured by weight permeation molecular weight (Mw) and number average molecular weight (Mn) of polyethylene using gel permeation chromatography (GPC). It can be calculated by dividing the weight average molecular weight by the number average molecular weight.
  • a Waters PL-GPC220 instrument is used as a gel permeation chromatography (GPC) device, and a Polymer Laboratories PLgel MIX-B 300 mm length column can be used.
  • the measurement temperature is 160 °C
  • 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, and the flow rate can be applied at 1 mL/min.
  • Each of the polyethylene samples was pretreated by dissolving at 160° C.
  • trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT using a GPC analyzer (PL-GP220), and the concentration of 10 mg/10 mL. It can be prepared and then supplied in an amount of 200 microliters ( ⁇ L).
  • the values of Mw and Mn can be derived using an assay 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 kinds of /mol can be used.
  • the polyethylene may have a weight average molecular weight of about 160000 to about 260000 g/mol, or about 170000 to about 250000 g/mol, or about 180000 to about 240000 g/mol. This means that the molecular weight of polyethylene is high and the content of the high molecular weight component is high, which causes an effect of increasing the content of the linking molecule to be described later.
  • the method for producing polyethylene according to the present invention includes: at least one first metallocene compound represented by Formula 1 below; And polymerizing ethylene in the presence of at least one second metallocene compound selected from compounds represented by Formula 2 below.
  • At least one of R 1 to R 8 is -(CH 2 ) n -OR, where R is C 1-6 straight or branched chain alkyl, n is an integer from 2 to 6,
  • R 1 to R 8 are the same or different from each other, and each independently, hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-40 alkylaryl, C 7- 40 arylalkyl is a functional group selected from the group consisting of, or two or more adjacent to each other may be connected to each other to form an aliphatic or aromatic ring of C 6-20 unsubstituted or substituted with a C 1-10 hydrocarbyl group, ,
  • Q 1 and Q 2 are the same or different from each other, and each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-40 alkyl Aryl, C 7-40 arylalkyl;
  • a 1 is carbon (C), silicon (Si), or germanium (Ge);
  • M 1 is a Group 4 transition metal
  • X 1 and X 2 are the same as or different from each other, and each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, nitro group, amido group, C 1-20 alkylsilyl, C 1-20 alkoxy, or C 1-20 sulfonate group;
  • n is an integer of 0 or 1
  • Q 3 and Q 4 are the same or different from each other, and each independently hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkoxyalkyl, C 6-20 aryl, C 7-40 alkyl Aryl, C 7-40 arylalkyl;
  • a 2 is carbon (C), silicon (Si), or germanium (Ge);
  • M 2 is a Group 4 transition metal
  • X 3 and X 4 are the same or different from each other, and each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, nitro group, amido group, C 1-20 alkylsilyl, C 1-20 alkoxy, or C 1-20 sulfonate group;
  • C One And C 2 One of the is represented by the following formula 3a or formula 3b, C One And C 2 And the other one is represented by the following Chemical Formula 3c, Chemical Formula 3d, or Chemical Formula 3e;
  • R 9 to R 39 and R 17' to R 21' are the same or different from each other, and each independently hydrogen, halogen, C 1-20 alkyl, C 1-20 Haloalkyl, C 2-20 alkenyl, C 1-20 alkylsilyl, C 1-20 silylalkyl, C 1-20 alkoxysilyl, C 1-20 alkoxy, C 6-20 aryl, C 7-40 alkylaryl, C 7-40 arylalkyl, provided that at least one of R 17 to R 21 and R 17' to R 21' is C 1-20 haloalkyl,
  • Two or more adjacent R 22 to R 39 may be connected to each other to form a C 6-20 aliphatic or aromatic ring substituted or unsubstituted with a C 1-10 hydrocarbyl group;
  • Halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
  • the hydrocarbyl group is a monovalent functional group in which hydrogen atoms are removed from the hydrocarbon, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkylaryl group, an alkenylaryl group, and an alkyl group And a nilaryl group.
  • the hydrocarbyl group having 1 to 30 carbon atoms may be a hydrocarbyl group having 1 to 20 carbon atoms or 1 to 10 carbon atoms.
  • the hydrocarbyl group can be straight chain, branched chain, or cyclic alkyl.
  • the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, n-hex Straight-chain, branched-chain, or cyclic alkyl groups such as a silyl group, n-heptyl group, and cyclohexyl group; Or an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl.
  • alkylaryl such as methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, or an arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, or naphthylmethyl.
  • alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, and pentenyl.
  • alkyl having 1 to 20 carbon atoms may be straight chain, branched chain, or cyclic alkyl.
  • alkyl having 1 to 20 carbons is linear alkyl having 1 to 20 carbons; Straight-chain alkyl having 1 to 15 carbons; Straight-chain alkyl having 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbons; Or it may be a branched or cyclic alkyl having 3 to 10 carbon atoms.
  • the alkyl having 1 to 20 carbon atoms is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl , Cyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.
  • alkenyl having 2 to 20 carbon atoms examples include straight-chain or branched-chain alkenyl, and specifically, allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, and the like. It is not limited.
  • alkoxy having 1 to 20 carbon atoms examples include a methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, and cyclohexyloxy groups, but are not limited thereto. .
  • the alkoxyalkyl group having 2 to 20 carbon atoms is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with alkoxy, specifically methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, and alkoxyalkyls such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl. It is not limited to this.
  • aryloxy having 6 to 40 carbon atoms examples include phenoxy, biphenoxyl, and naphthoxy, but are not limited thereto.
  • the aryloxyalkyl group having 7 to 40 carbon atoms (C 7-40 ) is a functional group in which one or more hydrogens of the aforementioned alkyl are substituted with aryloxy, and specifically, phenoxymethyl, phenoxyethyl, and phenoxyhexyl may be mentioned. , It is not limited to this.
  • alkylsilyl such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl group or dimethylpropylsilyl
  • alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl
  • Alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl, but is not limited thereto.
  • Silylalkyl having 1 to 20 carbon atoms is a functional group in which one or more hydrogens of alkyl as described above are substituted with silyl, specifically -CH 2 -SiH 3 , methylsilylmethyl or dimethylethoxysilylpropyl, etc. However, it is not limited to this.
  • alkylene having 1 to 20 carbon atoms (C 1-20 ) is the same as the above-mentioned alkyl except that it is a divalent substituent, specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, hep Styrene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the like, but is not limited thereto.
  • a divalent substituent specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, hep Styrene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the like, but is not limited thereto.
  • Aryl having 6 to 20 carbon atoms may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon.
  • the aryl having 6 to 20 carbon atoms (C 6-20 ) may include phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, and the like, but is not limited thereto.
  • the alkylaryl having 7 to 20 carbon atoms (C 7-20 ) may mean a substituent in which one or more hydrogens of the hydrogens of the aromatic ring are substituted by the aforementioned alkyl.
  • the alkylaryl having 7 to 20 carbon atoms (C 7-20 ) may include methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, and the like, but is not limited thereto.
  • the arylalkyl having 7 to 20 carbon atoms may mean a substituent in which one or more hydrogens of the aforementioned alkyl are substituted by the aryl.
  • the arylalkyl having 7 to 20 carbon atoms (C 7-20 ) may include phenylmethyl, phenylethyl, biphenylmethyl, and naphthylmethyl, but is not limited thereto.
  • arylene having 6 to 20 carbon atoms (C 6-20 ) is the same as the aryl described above, except that it is a divalent substituent, specifically phenylene, biphenylene, naphthylene, anthracenylene, and phenanthrenylene , Fluorenylene, and the like, but is not limited thereto.
  • the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherfordium (Rf).
  • titanium (Ti), zirconium (Zr), or hafnium (Hf) It may be, and more specifically, may be zirconium (Zr) or hafnium (Hf), but is not limited thereto.
  • the group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), specifically boron (B), or aluminum (Al). And is not limited to this.
  • the first metallocene compound may be represented by any one of the following Chemical Formulas 1-1 to 1-4.
  • Q 1 and Q 2 may each be C 1-3 alkyl, and preferably methyl.
  • each of X 1 and X 2 may be halogen, preferably chloro.
  • a 1 may be silicon (Si).
  • the M 1 may be zirconium (Zr) or hafnium (Hf).
  • each of R 1 to R 8 is hydrogen, or C 1-20 alkyl, or C 1-10 alkyl, or C 1-6 alkyl, or C 2-6 alkyl substituted with C 1-6 alkoxy, or C 1-4 alkoxy may be substituted C 4-6 alkyl.
  • two or more adjacent R 32 to R 39 may be connected to each other to form an aliphatic or aromatic ring of C 6-20 substituted with C 1-3 .
  • R 3 and R 6 are each C 1-6 alkyl, or C 2-6 alkyl substituted with C 1-6 alkoxy, or C 4-6 alkyl or C 1-4 alkoxy are respectively substituted.
  • C 4-6 alkyl may be n-butyl, n-pentyl, n-hexyl, tert-butoxy butyl, or tert-butoxy hexyl.
  • R 1 , R 2 , R 4 , R 5 , R 7 , and R 8 may be hydrogen.
  • the compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • the first metallocene compound represented by the above structural formulas can be synthesized by applying known reactions, and detailed examples of synthesis can be referred to Examples.
  • the method for producing polyethylene according to the present invention includes one or more of the first metallocene compounds represented by Chemical Formula 1 or Chemical Formulas 1-1, 1-2, 1-3, and 1-4 as described above.
  • the alpha transition temperature of polyethylene is high and the ratio of the high crystal region according to the temperature rise elution fractionation (TREF) analysis is simultaneously optimized, resulting in high productivity and PVC compound in the CPE process described below. Excellent impact strength can be ensured during processing.
  • TEZ temperature rise elution fractionation
  • the second metallocene compound may be represented by the following Chemical Formula 2-1.
  • Q 3 , Q 4 , A 2 , M 2 , X 3 , X 24 , R 11 , and R 17 to R 29 are as defined in Chemical Formula 2.
  • Q 3 and Q 4 may be C 1-3 alkyl, or C 2-12 alkoxyalkyl, respectively, and preferably methyl or tert-butoxyhexyl.
  • each of X 3 and X 4 may be halogen, and specifically, chloro.
  • a 2 may be silicon (Si),
  • the M 2 may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).
  • R 17 to R 21 and R 17' to R 21' may each be hydrogen, or C 1-6 haloalkyl, or hydrogen or C 1-3 haloalkyl, respectively.
  • R 17 to R 20 or R 17' to R 20' are hydrogen, and R 21 or R 21' is trihalomethyl, preferably trifluoromethyl.
  • each of R 11 and R 11' may be C 1-6 straight-chain or branched-chain alkyl, or C 1-3 straight-chain or branched-chain alkyl, and preferably methyl.
  • R 22 to R 29 may each be hydrogen, or C 1-20 alkyl, or C 1-10 alkyl, or C 1-6 alkyl, or C 1-3 alkyl.
  • two or more adjacent R 22 to R 29 may be connected to each other to form an aliphatic or aromatic ring of C 6-20 substituted with C 1-3 .
  • R 30 to R 35 may each be hydrogen, or C 1-20 alkyl, or C 1-10 alkyl, or C 1-6 alkyl, or C 1-3 alkyl.
  • R 26 to R 29 may each be hydrogen, or C 1-20 alkyl, or C 1-10 alkyl, or C 1-6 alkyl, or C 1-3 alkyl.
  • the compound represented by Chemical Formula 2 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
  • the second metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and detailed examples of synthesis can be referred to Examples.
  • the method for preparing the metallocene compound was specifically described in Examples to be described later.
  • the metallocene catalyst used in the present invention may be supported on a carrier together with a co-catalyst compound.
  • the co-catalyst supported on the carrier is an organometallic compound containing a Group 13 metal, and polymerizes olefins under a general metallocene catalyst. It is not particularly limited as long as it can be used.
  • the cocatalyst is an organometallic compound containing a Group 13 metal, and is not particularly limited as long as it can be used when polymerizing ethylene under a general metallocene catalyst.
  • the cocatalyst may be one or more selected from the group consisting of compounds represented by the following Chemical Formulas 4 to 6:
  • R 40 are each independently halogen, C 1-20 alkyl or C 1-20 haloalkyl,
  • c is an integer greater than or equal to 2
  • D is aluminum or boron
  • R 41 are each independently hydrogen, halogen, C 1-20 hydrocarbyl or C 1-20 hydrocarbyl substituted with halogen,
  • L is a neutral or cationic Lewis base
  • Q is Br 3+ or Al 3+
  • E are each independently C 6-20 aryl or C 1-20 alkyl, wherein the C 6-20 aryl or C 1-20 alkyl is unsubstituted or halogen, C 1-20 alkyl, C 1-20 alkoxy and It is substituted with one or more substituents selected from the group consisting of phenoxy.
  • the compound represented by Chemical Formula 4 may be, for example, alkyl aluminoxane such as modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like.
  • alkyl aluminoxane such as modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like.
  • the alkyl metal compound represented by the formula (5) is, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro Aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl 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.
  • the compound represented by the formula (6) is, for example, triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p- Tolyl)boron, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra (p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethylanilin
  • the supported amount of the co-catalyst may be about 5 mmol to about 20 mmol based on 1 g of the carrier.
  • a carrier containing a hydroxy group on the surface may be used as the carrier, preferably having a highly reactive hydroxy group and a siloxane group that has been dried to remove moisture on the surface. Any carrier can be used.
  • silica dried at high temperature silica-alumina, and silica-magnesia can be used, and these are usually oxides, carbonates, such as Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) 2 , Sulfate, and nitrate components.
  • the drying temperature of the carrier is preferably about 200 °C to about 800 °C, more preferably about 300 °C to about 600 °C, and most preferably about 300 °C to 400 °C.
  • the drying temperature of the carrier is less than about 200 °C, there is too much moisture so that the surface moisture and the co-catalyst react, and when it exceeds about 800 °C, the surface area decreases as the pores of the carrier surface are combined and the surface is hydroxy. It is not preferable because many groups disappear and only siloxane groups remain, thereby reducing the reaction site with the cocatalyst.
  • the amount of hydroxy groups on the surface of the carrier is preferably about 0.1 mmol/g to about 10 mmol/g, and more preferably about 0.5 mmol/g to about 5 mmol/g.
  • the amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than about 0.1 mmol/g, there are fewer reaction sites with the co-catalyst, and if it exceeds about 10 mmol/g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. It is not desirable.
  • the mass ratio of the total transition metal to the carrier contained in the metallocene catalyst may be about 1: 10 to about 1: 1000.
  • the carrier and the metallocene compound are included in the mass ratio, an optimal shape may be exhibited.
  • the mass ratio of the co-catalyst compound to the carrier may be from about 1:1 to about 1:100.
  • the ethylene polymerization reaction may be performed using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.
  • the polyethylene according to the present invention at least one first metallocene compound represented by Formula 1; And in the presence of at least one second metallocene compound selected from the compounds represented by the formula (2), it can be prepared by homopolymerizing ethylene.
  • the weight ratio of the first metallocene compound and the second metallocene compound is about 40:60 to about 75:25, or about 42:58 to about 65:35.
  • the polyethylene may be prepared while introducing hydrogen gas under the metallocene catalyst as described above.
  • the hydrogen gas may be introduced in an amount of about 30 ppm to about 60 ppm, or about 30 ppm to about 45 ppm, or about 30 ppm to about 40 ppm, relative to ethylene.
  • the polymerization temperature may be about 25 °C to about 500 °C, preferably about 25 °C to about 200 °C, more preferably about 50 °C to about 150 °C.
  • the polymerization pressure is about 1 kgf/cm 2 to about 100 kgf/cm 2 , preferably about 1 kgf/cm 2 to about 50 kgf/cm 2 , more preferably about 5 kgf/cm 2 to about 30 kgf /cm 2 can be.
  • the supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene and benzene, such as dichloromethane and chlorobenzene. It can be injected by dissolving or diluting a hydrocarbon solvent substituted with a chlorine atom.
  • the solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkyl aluminum, and it is also possible to further use a cocatalyst.
  • chlorinated polyethylene using polyethylene as described above is provided.
  • the chlorinated polyethylene according to the present invention can be prepared by polymerizing ethylene in the presence of the supported metallocene catalyst described above and then reacting it with chlorine.
  • the reaction with the chlorine can be reacted by dispersing the prepared polyethylene with water, an emulsifier and a dispersant, and then introducing a catalyst and chlorine.
  • polyether or polyalkylene oxide may be used as the emulsifier.
  • a polymer salt or an organic acid polymer salt may be used as the dispersant, and methacrylic acid or acrylic acid may be used as the organic acid.
  • the catalyst may use a chlorination catalyst used in the art, for example, benzoyl peroxide.
  • the chlorine may be used alone, but may be used by mixing with an inert gas.
  • the chlorination reaction is preferably performed at about 60 °C to about 150 °C, or about 70 °C to about 145 °C, or about 80 °C to about 140 °C, and the reaction time is about 10 minutes to about 10 hours, or about 1 Hours to about 9 hours, or about 2 hours to about 8 hours are preferred.
  • the chlorinated polyethylene produced by the above reaction can further apply a neutralization process, a cleaning process and/or a drying process, and thus can be obtained in the form of a powder.
  • the chlorinated polyethylene because the polyethylene maintains a stable crystal structure at a high temperature and has a small high crystal region, exhibits excellent uniformity in chlorine distribution in the chlorinated polyethylene and shows high elongation.
  • the chlorinated polyethylene may have an elongation measured by a method according to ASTM D-412 of about 1000% or more, or about 1100% or more.
  • the elongation of the chlorinated polyethylene can be measured under 500 mm/min condition. Specifically, after preparing the chlorinated polyethylene by reacting the polyethylene with chlorine under a condition of about 60° C. to about 150° C.
  • the CPE elongation is from about 75 °C to about 85 °C polyethylene to about 500 kg to about 600 kg to about 15 °C / hr from about 75 °C to about 85 °C to a final temperature of about 120 °C to about 140 °C It may be a value measured for chlorinated polyethylene obtained by performing a chlorination reaction with gaseous chlorine for about 2 hours to about 5 hours at a final temperature of about 120° C. to about 140° C. after heating at a rate of about 18.5° C./hr.
  • the chlorination reaction is carried out by injecting chlorine in the gas phase while maintaining the pressure in the reactor at about 0.2 MPa to about 0.4 MPa at the same time as the temperature rise, and the total input amount of the chlorine is about 550 kg to about 650 kg. have.
  • the chlorinated polyethylene may have, for example, a chlorine content of about 20% to about 45% by weight, about 31% to about 40% by weight, or about 33% to about 38% by weight.
  • the chlorine content of the chlorinated polyethylene can be measured using combustion ion chromatography (Combustion IC, Ion Chromatography) analysis.
  • the combustion ion chromatography analysis method uses an IonPac AS18 (4 x 250 mm) column equipped combustion IC (ICS-5000/AQF-2100H) device, an internal device temperature of 900°C, an external device Temperature (Outlet temperature) It can be measured under a flow rate of 1 mL/min using KOH (30.5 mM) as eluent at a combustion temperature of 1000 °C.
  • the device conditions and measurement conditions for measuring the chlorine content are as described in Test Example 2, which will be omitted.
  • the chlorinated polyethylene may be, for example, random chlorinated polyethylene.
  • the chlorinated polyethylene produced according to the present invention is excellent in chemical resistance, weather resistance, flame retardancy, processability, and impact strength reinforcement effect, and thus is widely used as an impact modifier for PVC pipes and window profiles.
  • a method for manufacturing a PVC molded article or the like with the 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 extruded to produce a molded article.
  • 6-Chlorohexanol was used to prepare t-butyl-O-(CH 2 ) 6 -Cl in the manner described in Tetrahedron Lett. 2951 (1988), where NaCp was reacted to react t-butyl-O. -(CH 2 ) 6 -C 5 H 5 was obtained (yield 60%, bp 80° C./0.1 mmHg).
  • t-butyl-O-(CH 2 ) 6 -C 5 H 5 was dissolved in tetrahydrofuran (THF) at -78 °C, n-BuLi was slowly added, and then the temperature was raised to room temperature, followed by reaction for 8 hours. .
  • the synthesized lithium salt solution was slowly added to the suspension solution of ZrCl 4 (THF) 2 (170 g, 4.50 mmol)/THF (30 mL) at ⁇ 78° C. again, and further reacted at room temperature for 6 hours. . All volatiles were removed by vacuum drying and hexane was added to the resulting oily liquid material to filter.
  • fluorene 1.2 g (7.4 mmol) was also dissolved in 100 mL of THF, and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice/acetone bath and stirred overnight at room temperature.
  • 11 g of the ligand compound synthesized in 3-1 was dissolved in a mixed solvent of 80 mL of toluene and 5 mL of Methyl Tertiary Butyl Ether (MTBE), and 16.7 mL (41.6 mmol) of a 2.5 M n-butyl lithium hexane solution was added dropwise at room temperature. It was stirred. Then, 7.5 g (19.8 mmol) of ZrCl 4 (THF) 2 was added to 80 mL of toluene to prepare a slurry, and then transferred to a dry ice/acetone bath and stirred overnight at room temperature.
  • MTBE Methyl Tertiary Butyl Ether
  • the slurry was filtered to remove LiCl, and the toluene of the filtrate was removed by vacuum drying, followed by adding 100 mL of hexane and sonication for 1 hour. Thereafter, the slurry was filtered to obtain 4.5 g of a filtered solid phosphorus metallocene compound (yield 62.3 mol%, yellow solid).
  • a hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, but using the metallocene compound of Synthesis Example 3 instead of the metallocene compound of Synthesis Example 2.
  • a hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, using the metallocene compound of Synthesis Example 4 instead of the metallocene compound of Synthesis Example 2.
  • the supported catalyst prepared in Preparation Example 1 was introduced into a single slurry polymerization process to produce high-density polyethylene.
  • Example 1-1 Prepared in the same manner as in Example 1-1, the input amount of hydrogen was changed to 40 ppm, to prepare a high density polyethylene in powder form.
  • Example 1-1 Prepared in the same manner as in Example 1-1, the input of hydrogen was varied to 35 ppm, to prepare a high density polyethylene in powder form.
  • Example 1-2 Prepared in the same manner as in Example 1-2, using the supported catalyst prepared in Comparative Preparation Example 1 instead of the supported catalyst prepared in Preparation Example 1 to prepare a high density polyethylene in powder form.
  • Example 1-1 Prepared in the same manner as in Example 1-1, using the supported catalyst prepared in Comparative Preparation Example 2 instead of the supported catalyst prepared in Preparation Example 1 to prepare a high density polyethylene in powder form.
  • MI Melt Index
  • g/10 min The melt index (MI 2.16 , MI 5 , MI 21.6 ) was measured under the conditions of 5 kg, and 21.6 kg at a temperature of 190°C, respectively, by the method of ASTM D 1238, 10 It is expressed as the weight (g) of the polymer melted for a minute.
  • Melt flow index (MFRR, MI 21.6/5 ) melt flow divided by the melt index measured at 190°C and 21.6kg load by the method of ASTM D 1238 divided by the melt index measured at 190°C and 5 kg load The index (MFRR, MI 21.6/5 ) was calculated.
  • Density The density (g/cm 3 ) of polyethylene was measured by the method of ASTM D 1505.
  • High crystal area ratio (%) After obtaining a temperature rise elution fractionation (TREF) graph by measuring for polyethylene, of the peaks on the TREF graph where the two peaks with the highest peak intensity are divided (minimum value) Based on the elution temperature as a reference for the vertical axis at which the high crystal region starts, the graph area of the high crystal region corresponding to the elution temperature of the minimum value portion is measured, and the percentage value divided by the total graph area is the high crystal region ratio (% ).
  • a temperature rise elution fractionation (TREF) graph of polyethylene was obtained through Agilent Technologies 7890 A instrument of PolymerChar.
  • Alpha transition temperature (°C): Using DMA (Dynamic Mechanical Analyzer, manufactured by TA), the temperature was lowered to -60 °C, maintained at that temperature for 5 minutes, and then increased to 140 °C to increase the tan ⁇ curve. The top was measured with alpha transition temperature.
  • DMA Dynamic Mechanical Analyzer
  • the H 2 input (ppm) during polymerization represents the hydrogen gas content based on the ethylene input.
  • Chlorinated polyethylene was prepared using the polyethylenes prepared in Examples and Comparative Examples.
  • Example 1-1 After introducing 5000 L of water and 550 kg of high-density polyethylene prepared in Example 1-1 into the reactor, sodium polymethacrylate as a dispersing agent, oxypropylene and oxyethylene copolyether as an emulsifying agent, and benzoyl peroxide as a catalyst, After heating from 80°C to 132°C at a rate of 17.3°C/hr, the final temperature was chlorinated with chlorine in the gas phase at 132 °C for 3 hours. At this time, at the same time as the temperature rise, while maintaining the pressure in the reactor at 0.3 MPa, chlorine in the gas phase was injected, and the total amount of chlorine was 610 kg. The chlorinated reactant was added to NaOH to neutralize for 4 hours, washed again with flowing water for 4 hours, and finally dried at 120° C. to prepare chlorinated polyethylene in powder form.
  • sodium polymethacrylate as a dispersing agent
  • oxypropylene and oxyethylene copolyether as an
  • polyethylenes prepared in Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-5 were also prepared in the same manner as described above, respectively, in the form of powdered chlorinated polyethylene.
  • Elongation (%) of CPE Elongation (%) of chlorinated polyethylene under 500 mm/min was measured by a method according to ASTM D-2240.
  • Deoxidation time of CPE (min): During the chlorinated polyethylene manufacturing process, deoxidation is performed based on the time when the solution is deoxidized by adding water until the pH of the solution becomes 6.0 or higher. Was measured. At this time, the deoxidation time of the CPE is preferably 550 minutes or less, and when it exceeds 550 minutes, the time of the entire chlorination process is delayed, which may cause a problem that the CPE productivity decreases.

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Abstract

Le polyéthylène selon la présente invention maintient la structure cristalline stable à haute température et garde une excellente uniformité dans la répartition du chlore. Ainsi, en faisant réagir celui-ci avec du chlore, du polyéthylène chloré présentant une excellente productivité de chlore et une excellente stabilité thermique, et, en raison de l'inclusion du polyéthylène chloré, un composé de PVC présentant une résistance aux chocs améliorée peut être fabriqué.
PCT/KR2019/017398 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé Ceased WO2020122561A1 (fr)

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EP19894608.9A EP3778663B1 (fr) 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé
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