WO2020122563A1 - Polyéthylène et polyéthylène chloré associé - Google Patents

Polyéthylène et polyéthylène chloré associé Download PDF

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WO2020122563A1
WO2020122563A1 PCT/KR2019/017400 KR2019017400W WO2020122563A1 WO 2020122563 A1 WO2020122563 A1 WO 2020122563A1 KR 2019017400 W KR2019017400 W KR 2019017400W WO 2020122563 A1 WO2020122563 A1 WO 2020122563A1
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Prior art keywords
polyethylene
alkyl
formula
group
aryl
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PCT/KR2019/017400
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English (en)
Korean (ko)
Inventor
이시정
홍복기
박성현
김선미
최이영
정철환
이진석
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주식회사 엘지화학
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Priority claimed from KR1020190163114A external-priority patent/KR102431339B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/051,983 priority Critical patent/US11834528B2/en
Priority to EP19895368.9A priority patent/EP3778664B1/fr
Priority to CN201980031063.4A priority patent/CN112088176B/zh
Publication of WO2020122563A1 publication Critical patent/WO2020122563A1/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

Definitions

  • the present invention relates to polyethylene and its chlorinated polyethylene, which can produce chlorinated polyethylene having excellent processability during extrusion while improving tensile strength by realizing a high and medium molecular region in the molecular structure.
  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed to suit each characteristic.
  • the Ziegler Natta catalyst has been widely applied to existing commercial processes since it was invented in the 50s, but because it is a multi-site catalyst with multiple active sites, the molecular weight distribution of the polymer is characterized by a wide range of comonomers. There is a problem that there is a limit to securing the desired physical properties because the composition distribution of the is not uniform.
  • the metallocene catalyst is composed of a combination of a main catalyst having a transition metal compound as a main component and a cocatalyst having an organometallic compound having aluminum as a main component.
  • a catalyst is a homogeneous complex catalyst, and is a single-site catalyst.
  • the molecular weight distribution is narrow according to the properties of a single active point, and a polymer having a uniform composition distribution of the comonomer is obtained, and the stereoregularity of the polymer, copolymerization characteristics, and molecular weight are obtained by changing the ligand structure of the catalyst and changing polymerization conditions. It has properties that can change the crystallinity, etc.
  • 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 in preparing the supported catalyst. , There was a hassle of supporting the metallocene catalyst to be used, respectively.
  • Republic of Korea Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by polymerizing while changing the combination of catalysts in a reactor by supporting a dual-nuclear metallocene catalyst and a single-nuclear metallocene catalyst on an carrier with an activator, have.
  • this method has a limitation in simultaneously implementing the characteristics of each catalyst, and also has a disadvantage in that the metallocene catalyst portion is liberated from the carrier component of the finished catalyst, causing fouling in the reactor.
  • chlorinated polyethylene produced by reacting polyethylene with chlorine is known to have improved physical and mechanical properties compared to polyethylene, and is particularly resistant to harsh external environments. Used as material.
  • 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 chlorinated polyethylene (CPE)
  • CPE chlorinated polyethylene
  • polyethylene is reacted with chlorine in a suspension, or polyethylene is an aqueous HCl solution. It can be prepared by reacting with chlorine.
  • CPE compound product excellent tensile strength is required, but the strength of the compound varies depending on the properties of chlorinated polyethylene.
  • the present invention is to provide a polyethylene and its chlorinated polyethylene that can implement a high-middle molecular region in the molecular structure, improve tensile strength with a narrow molecular weight distribution, and can produce chlorinated polyethylene with excellent processability during extrusion.
  • the present invention is to provide a method for producing the polyethylene.
  • the entanglement molecular weight (Me) is 9500 g/mol to 13000 g/mol
  • a polyethylene having a melt index measured at load divided by a melt index measured at 190 ° C and a 5 kg load) is 16 to 25 and a molecular weight distribution (MWD, Mw/Mn) of 5.5 to 10 is provided.
  • the present invention provides a method for producing the polyethylene.
  • the present invention provides a chlorinated polyethylene produced by reacting the polyethylene with chlorine.
  • Polyethylene according to the present invention by implementing a high-middle molecular region in the molecular structure, and reacting it with chlorine to produce a chlorinated polyethylene excellent in chlorination productivity and thermal stability.
  • 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.
  • a polyethylene capable of producing a chlorinated polyethylene having excellent processability upon extrusion while improving tensile strength by realizing a molecular structure with a high molecular weight region is provided.
  • the polyethylene, the entanglement molecular weight (Me) is 9500 g / mol to 13000 g / mol
  • the melt index divided by the melt index measured at 190 o C, 5 kg load) is 16 to 25
  • the molecular weight distribution (MWD, Mw/Mn) is 5.5 to 10.
  • 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 smaller and uniform the overall size of the chlorinated polyethylene particles the easier it is for chlorine to penetrate to the center of the polyethylene particles, so the degree of chlorine substitution in the particles can be uniform to show excellent physical properties.
  • the polyethylene according to the present invention is used in the molecular structure. Since the molecular region is high, it is possible to provide chlorinated polyethylene having excellent tensile strength and excellent workability during extrusion.
  • the polyethylene of the present invention is characterized by having a high molecular weight region in the molecular structure, excellent entanglement molecular weight (Me), and high crosslinking degree with a narrow molecular weight distribution.
  • Mo entanglement molecular weight
  • the crosslinked polyethylene elongation viscosity (210 o C, 0.5 s) of polyethylene increases, and chlorinated polyethylene having excellent chlorination productivity, thermal stability and mechanical properties can be produced.
  • the polyethylene according to the present invention may be an ethylene homopolymer that does not contain a separate copolymer.
  • the polyethylene may have an entanglement molecular weight (Me) of about 9500 g/mol to about 13000 g/mol.
  • the entanglement molecular weight (Me) may be about 9600 g/mol to about 12800 g/mol or about 9800 g/mol to about 12600 g/mol.
  • the entanglement molecular weight (Me) should be about 9500 g/mol or more in terms of processability when extruding, and about 13000 g/mol or less in terms of securing excellent mechanical properties and sufficient strength in processing molded articles.
  • the entanglement molecular weight (Me) of the polyethylene is when one polymer chain is entangled with the surrounding polymer or itself to form an entanglement functioning as a physical crosslink, between these entanglement points.
  • the average molecular weight the higher the molecular weight of the polymer, the longer the length of the polymer chain increases, so the probability of entanglement is increased, so the tangled molecular weight decreases. Since the degree of entanglement of the polymer increases as the molecular weight of the entanglement decreases, the resistance to external force increases.
  • the entanglement molecular weight (Me) is a rotational rheometer, 150 o C to 230 o C temperature, 0.05 rad/s to 500 rad/s of each frequency (Angular Frequency), 0.5% strain (Strain) ) Can be calculated using the plateau modulus (G N 0 ) obtained from the storage modulus and loss modulus of polyethylene measured under conditions.
  • the plateau elastic modulus (G N 0 ) is a storage elastic modulus when the loss modulus has a minimum value in a region where the storage modulus is greater than the loss modulus.
  • the method for measuring the tangle molecular weight of the polyethylene is as described in Test Example 1, which will be described later, and the specific measurement method will be omitted.
  • the polyethylene is prepared by optimizing a specific metallocene catalyst as described below, and the melt flow index (MFRR 21.6/5 , ASTM D 1238) along with the entanglement molecular weight (Me) 190 o C, the melt index measured at 21.6 kg load divided by the melt index measured at 190 o C, 5 kg load) and the molecular weight distribution (MWD, Mw/Mn) are optimized to increase the number of used molecules in the molecular structure. By doing so, the tensile strength of the CPE compound can be improved.
  • the polyethylene has a melt flow index (MFRR 21.6/5 , melt index measured at 190 o C, 21.6 kg load by the method of ASTM D 1238 divided by the melt index measured at 190 o C, 5 kg load). 16 to about 25. Specifically, the melt flow index may be about 17 to about 23 or about 18 to about 22.
  • the melt flow index should be about 16 or more in terms of processability during extrusion, and should be about 25 or less in terms of securing excellent mechanical properties by increasing Mooney viscosity (MV) of CPE.
  • the melt flow index (MFRR 21.6/5 ) is a value obtained by dividing the melt index measured at 190 ° C and 21.6 kg load by the method of ASTM D 1238 by the melt index measured at 190 ° C and 5 kg load.
  • the melt index MI 5 measured under the conditions of temperature 190 o C and load 5 kg by the method of ASTM D 1238 is from about 0.6 g/10min to about 1.1 g/10min, or from about 0.65 g/10min to about 1.0 g/10min Or about 0.7 g/10min to about 0.95 g/10min.
  • temperature and 21.6 kg load by the method of ASTM D 1238 is from about 12 g/10min to about 20 g/10min, or from about 13 g/10min to about 18.5 g/10min. Or from about 14 g/10min to about 17.5 g/10min.
  • the polyethylene of the present invention is characterized by optimizing the molecular weight distribution (MWD, Mw/Mn) while simultaneously showing the entanglement molecular weight (Me) and the melt flow index in an optimal range.
  • the molecular weight distribution of the polyethylene may be about 5.5 to about 10, or about 6 to about 9, or about 6.5 to about 8. 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 long column can be used.
  • the measurement temperature is 160 o 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 o C, 10 hours in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT using a GPC analyzer (PL-GP220), and 10 mg/10 mL of After preparation at a concentration, it can be 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 150000 g/mol to about 200000 g/mol, or about 153000 g/mol to about 190000 g/mol, or about 155000 g/mol to about 185000 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 polyethylene may have a density of about 0.953 g/cm 3 to 0.957 g/cm 3 , or about 0.954 g/cm 3 to 0.956 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, the crosslinked polyethylene elongation viscosity (210 o C, 0.5 s) is about 750000 Pa ⁇ s or more or about 750000 Pa ⁇ s to about 1200000 Pa ⁇ s, or about 800000 Pa ⁇ s or more or about 800000 Pa ⁇ s to It can be about 1000000 Pa ⁇ s.
  • the crosslinked PE elongation viscosity may be about 750000 Pa ⁇ s or more in terms of securing excellent mechanical properties.
  • the method for measuring the crosslinked polyethylene elongation viscosity (210 o C, 0.5 s) of the polyethylene is as described in Test Example 1 described later.
  • the crosslinked polyethylene elongation viscosity of the polyethylene refers to the elongation viscosity of a compound sheet cross-linked with polyethylene under 190 o C, 10 min conditions. entanglement) and has a meaning of indicating a molecular structure with excellent crosslinking degree.
  • the cross-linked polyethylene elongation viscosity (210 o C, 0.5 s) can be measured by pulling the molten sample under the condition of elongation strain rate (Hencky Rate) 0.1 / s at 210 o C, specifically ARES of TA Instruments It can be measured using a G2 instrument and an EVF (Elongation Viscosity Fixture) accessory.
  • the polyethylene, MDR torque (Torque, MH-ML, 180 o C, 10min measurement) is about 6.5 Nm or more or about 6.5 Nm to about 9.5 Nm, or about 6.8 Nm or more or about 6.8 Nm to about 8.5 Nm, Or about 7 Nm or more or about 7 Nm to about 8 Nm.
  • the MDR torque (Torque) may be about 6.5 Nm or more in terms of securing excellent mechanical properties.
  • the MDR Torque of the polyethylene refers to the degree of crosslinking, the higher the degree of crosslinking, the higher the MH-ML, and the better the crosslinking efficiency when the same crosslinking agent is applied.
  • the MDR torque (Torque) of the polyethylene can be measured using, for example, a MDR (Moving die rheometer), and the MH value and the ML value are measured under 180 o C and 10 min conditions, and the ML value is the MH value. By subtracting, MDR torque (MH-ML) can be calculated.
  • MH is the maximum vulcanizing torque measured in full cure
  • ML is the minimum vulcanizing torque stored.
  • the method of measuring the MDR torque (Torque) of the polyethylene is as described in Test Example 1 to be described later, a specific measurement method is omitted.
  • 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 3 below.
  • 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;
  • C 1 and One of C 2 is represented by the following Chemical Formula 2a or Chemical Formula 2b, and C 1 and One of C 2 is represented by the following Chemical Formula 2c, Chemical Formula 2d, or Chemical Formula 2e;
  • R 1 to R 31 and R 1 'to R 13' are the same or different and each is independently hydrogen, halogen, C 1-20 alkyl each other, 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, and C 7-40 alkyl and aryl, with the proviso that, R 9 to R 13 and R 9 'to R 13' has one or more of C 1-20 haloalkyl,
  • R 14 to R 31 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;
  • ⁇ represents sites that bind to A 1 and M 1 ;
  • At least one of R 32 to R 39 is -(CH 2 ) n -OR, where R is C 1-6 straight or branched chain alkyl, n is an integer from 2 to 6,
  • At least one of R 32 to R 39 is -(CH 2 ) n -OR, where R is C 1-6 straight or branched chain alkyl, n is an integer from 2 to 4,
  • R 32 to R 39 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 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;
  • n is an integer of 0 or 1.
  • 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 the following Chemical Formula 1-1.
  • Q 1 , Q 2 , A 1 , M 1 , X 1 , X 2 , R 3 , and R 9 to R 21 are as defined in Formula 1 above.
  • Q 1 and Q 2 may be C 1-3 alkyl, or C 2-12 alkoxyalkyl, respectively, and preferably methyl or tert-butoxyhexyl.
  • 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), preferably zirconium (Zr).
  • the R 9 to R 13 and R 9 'to R 13' may be each may be hydrogen, or C 1-6 haloalkyl, or each represents hydrogen, or C 1-3 haloalkyl.
  • the R 9 to R 12 or R 9 'to R 12' is hydrogen, R 13 or R 13 'is the methyl, preferably trihaloalkyl is trifluoromethyl.
  • R 3 may be C 1-6 linear or branched alkyl, or C 1-3 linear or branched alkyl, preferably methyl.
  • R 14 to R 21 may each be hydrogen, or C 1-20 alkyl, or C 1-10 alkyl, or C 1-6 alkyl, or C 1-3 alkyl. Alternatively, two or more adjacent R 14 to R 21 may be connected to each other to form an aliphatic or aromatic ring of C 6-20 substituted with C 1-3 .
  • R 22 to R 27 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 1 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
  • the first metallocene compound represented by the above structural formula can be synthesized by applying known reactions, and a more detailed synthesis method can refer to Examples.
  • At least one first metallocene compound represented by Chemical Formula 1 or Chemical Formula 1-1 as described above is used together with at least one second metallocene compound described later.
  • the second metallocene compound may be represented by any one of the following Chemical Formulas 3-1 to 3-4.
  • Q 3 and Q 4 may be C 1-3 alkyl, respectively, and preferably methyl.
  • X 3 and X 4 may each be halogen, preferably chloro.
  • a 2 may be silicon (Si).
  • the M 2 may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).
  • R 32 to R 39 are each 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 34 and R 37 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, respectively.
  • C 4-6 alkyl may be n-butyl, n-pentyl, n-hexyl, tert-butoxy butyl, or tert-butoxy hexyl.
  • R 32 , R 33 , R 35 , R 36 , R 38 , and R 39 may be hydrogen.
  • the compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • 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 co-catalyst may be one or more selected from the group consisting of compounds represented by the following Chemical Formulas 4 to 6:
  • R 41 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 51 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 5 mmol to 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 200 o C to 800 o C, more preferably 300 o C to 600 o C, and most preferably 300 o C to 400 o C.
  • the drying temperature of the carrier is less than 200 o C, there is too much moisture so that the surface moisture and the co-catalyst react, and when it exceeds 800 o C, the surface area decreases as the pores of the carrier surface are combined and hydroxy on the surface. 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 0.1 mmol/g to 10 mmol/g, and more preferably 0.5 mmol/g to 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 0.1 mmol/g, there are few reaction sites with the cocatalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.
  • the mass ratio of the total transition metal to the carrier contained in the metallocene catalyst may be 1: 10 to 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 1:1 to 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 Formula 3, it may be prepared by homopolymerizing ethylene.
  • the weight ratio of the first metallocene compound and the second metallocene compound is, for example, about 45:55 to about 60:40, or about 48:52 to about 58:42, or about 48:52 to about 55 :45, or about 53:47 to about 55:45.
  • the weight ratio of the catalyst precursor is to implement a high-middle molecular region in the molecular structure, improve tensile strength and at the same time to produce a chlorinated polyethylene excellent in processability during extrusion, in terms of realizing a high-middle molecular region in the molecular structure. It may be the weight ratio as described above.
  • the weight ratio may be about 45:55 or more in terms of securing MFRR (21.6/5) to 16 or more when the melt index MI 5 of polyethylene is 0.6 to 1.1 g/10min, and MFRR (21.6/ 5) can be about 60:40 or less in terms of being optimized to 25 or less.
  • 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 70 to 120 ppm, or about 80 to 110 ppm.
  • the injection amount of the hydrogen gas may be maintained in the range as described above in terms of allowing the polyethylene obtained after polymerization to simultaneously exhibit the melt flow index and molecular weight distribution in an optimal range.
  • a polymerization reaction solvent for example, a wax content in hexane increases, and thus a problem in that particles are aggregated during a chloride reaction may occur.
  • the wax content is maintained to be lower than 20%, and the hydrogen input amount can be controlled. can do.
  • the wax content may be measured by separating a polymerization product using a centrifugal separator, sampling the remaining hexane solvent for 100 mL, and settling for 2 hours to determine the volume ratio occupied by the wax.
  • the polymerization temperature may be about 25 o C to about 500 o C, preferably about 25 o C to about 200 o C, more preferably about 50 o C to about 150 o 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 o C to about 150 o C, or about 70 o C to about 145 o C, or about 80 o C to about 140 o C, and the reaction time is about 10 minutes to about Preference is given to 10 hours, or about 1 hour to about 9 hours, or about 2 hours to about 8 hours.
  • 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 exhibits excellent chlorine distribution uniformity in the chlorinated polyethylene due to the polyethylene having a narrow molecular weight distribution, for example, chlorine in a slurry (water or HCl aqueous solution) condition under about 60 o C to about 150 o C.
  • the Mooney viscosity (MV) measured under 121 o C conditions ranged from about 60 or more to less than about 85, or from about 62 or more to about 82 or less, or from about 65 or more to about 80 or less
  • the pattern viscosity of the chlorinated polyethylene exceeds about 85, the surface is not smooth and rough when processing CPE compounds for wires and cables, etc. through compounding with inorganic additives and crosslinking agents as described below. Poor gloss may cause poor appearance.
  • the chlorinated polyethylene has a tensile strength measured by the method of ASTM D 412 of about 12 MPa or more or about 12 MPa to about 30 MPa, or about 12.5 MPa or more, or about 12.3 MPa to about 20 MPa, or It may be about 12.5 MPa or more or about 12.5 MPa to about 15 MPa.
  • the chlorinated polyethylene has a tensile elongation of about 500% or more or about 500% to about 2000%, or about 700% or more or about 700% to about 1500%, or about 900 as measured by the method of ASTM D 412. % Or more, or about 900% to about 1200%.
  • the pattern viscosity (MV, Mooney viscosity), tensile strength, tensile elongation, about 500 kg to about 600 kg of polyethylene in a slurry (water or HCl aqueous solution) state from about 75 o C to about 85 o C to about 120 o C to the final temperature of about 140 o C of about 15 o C / hr to about 18.5 o C / hr after the speed was raised to about 120 o C to from the final temperature of about 140 o C for about 2 hours to about 5 hours It may be a value measured for chlorinated polyethylene obtained by performing a chlorination reaction with chlorine in the gas phase.
  • 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 650 kg to about 750 kg. have.
  • the method for measuring the pattern viscosity (MV, Mooney viscosity), tensile strength (Tensile strength), and tensile elongation (Tensile elongation) of the chlorinated polyethylene is as described in Test Example 2 described below, and a specific measurement method is omitted. .
  • the chlorinated polyethylene may have, for example, a chlorine content of about 20% to about 50% by weight, about 31% to about 45% by weight, or about 35% to about 40% 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 a combustion IC (ICS-5000/AQF-2100H) device equipped with an IonPac AS18 (4 x 250 mm) column, and an internal device temperature of 900 o C, external The outlet temperature can be measured under a flow rate of 1 mL/min using KOH (30.5 mM) as eluent at a combustion temperature of 1000 o C.
  • the device conditions and the measurement conditions for measuring the chlorine content are as described in Test Example 2, which will be omitted.
  • the chlorinated polyethylene according to the present invention has a chlorine content of 35% to 40% by weight under the condition that the above-described pattern viscosity (MV, Mooney viscosity) is about 65 to about 80, tensile strength (Tensile strength) Is about 12.5 MPa or more or about 12.5 MPa to about 15 MPa, and the tensile elongation may be about 900% or more or about 900% to about 1200%.
  • MV pattern viscosity
  • Mooney viscosity tensile strength
  • 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 the like, and is widely used for electric wires and cables.
  • CPE chlorinated polyethylene
  • the chlorinated polyethylene (CPE) compound of the present invention optimizes both the entangled molecular weight (Me) range of the polyethylene and the melt flow index (MFRR 21.6/5 ) and realizes high crosslinking degree with a narrow molecular weight distribution, minimizing processability degradation during extrusion.
  • CPE chlorinated polyethylene
  • the chlorinated polyethylene (CPE) compound is mainly used for wire and cable applications, and has excellent features such as processability, surface condition and gloss of molded products, and tensile strength of crosslinked compounds.
  • the chlorinated polyethylene (CPE) compound contains about 1% to about 80% by weight, about 10% to about 70% by weight, about 20% to about 60% by weight of chlorinated polyethylene prepared by the method as described above. Can be achieved.
  • the chlorinated polyethylene (CPE) compound is 100 parts by weight to 280 parts by weight of an inorganic additive such as talc or carbon black, and 1 part to 40 parts by weight of a crosslinking agent with respect to 100 parts by weight of chlorinated polyethylene. It may be included.
  • an inorganic additive such as talc or carbon black
  • a crosslinking agent with respect to 100 parts by weight of chlorinated polyethylene. It may be included.
  • the chlorinated polyethylene (CPE) compound is 25% to 50% by weight of chlorinated polyethylene, and 50% to 70% by weight of inorganic additives such as talc and carbon black, and 0.5% by weight of the crosslinking agent It may be to include 10% by weight.
  • the chlorinated polyethylene (CPE) compound is, for example, inorganic additives (for example, Talc, Carbon black, etc.), a plasticizer, a crosslinking agent to prepare a CPE compound, and then crosslinked at 140 o C to 200 o C conditions, 100 o
  • the Mooney viscosity (MV) measured by a Mooney viscometer under C conditions may be about 30 to about 70, or about 35 to about 68, or about 45 to about 65.
  • the chlorinated polyethylene (CPE) compound has a tensile strength measured by the method of ASTM D 412 of about 8.5 MPa or more or about 8.5 MPa to about 30 MPa, or about 12 MPa or more or about 12 MPa to about 20 MPa, or about 12.3 MPa or more or about 12.3 MPa to about 15 MPa.
  • the chlorinated polyethylene has a tensile elongation of about 300% or more or about 300% to about 1000%, or about 350% or more or about 350% to about 800%, or about 380 measured by the method of ASTM D 412. % Or about 380% to about 600%.
  • a method for 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 extruded to produce a molded article.
  • fluorene 1.2 g (7.4 mmol) was also dissolved in 100 mL of tetrahydrofuran (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 at room temperature overnight.
  • THF tetrahydrofuran
  • 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice/acetone bath and stirred at room temperature overnight.
  • ZrCl 4 (THF) 2 3.0 g (8.0 mmol) was prepared by adding 80 mL of toluene as a slurry. The 80 mL toluene slurry of ZrCl 4 (THF) 2 was transferred to a ligand-Li solution in a dry ice/acetone bath and stirred at room temperature overnight.
  • 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 o C/0.1 mmHg).
  • 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, but the amount of hydrogen input to 99 ppm, 93 ppm, 80 ppm, 86 ppm, 110 ppm, and 95 ppm, respectively, in the form of powder Examples 1-2 to 1 A high-density polyethylene of -7 was prepared.
  • HDPE high-density polyethylene
  • HDPE high-density polyethylene
  • Example 1-1 Prepared in the same manner as in Example 1-1, 20 ppm of hydrogen was injected to prepare a high-density polyethylene in powder form using the supported catalyst prepared in Comparative Preparation Example 1 instead of the supported catalyst prepared in Preparation Example 1.
  • Example 2 It was prepared in the same manner as in Example 1-1, by introducing 30 ppm of hydrogen, to prepare a high-density polyethylene in powder form using the supported catalyst prepared in Comparative Preparation Example 2.
  • HDPE high-density polyethylene
  • MI Melt Index
  • MI 21.6 The melt index (MI 5 , MI 21.6 ) was measured under the conditions of 5 kg, and 21.6 kg, respectively, at a temperature of 190 o C by the method of ASTM D 1238, and 10 min. It is expressed as the weight (g) of the polymer melted during.
  • melt flow index (MFRR, MI 21.6/5 ) As the method of ASTM D 1238, the melt index measured at 190 o C, 21.6 kg load divided by the melt index measured at 190 o C, 5 kg load The melt flow 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.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • a Waters PL-GPC220 instrument was used as a gel permeation chromatography (GPC) device, and a Polymer Laboratories PLgel MIX-B 300 mm length column was used. At this time, the measurement temperature is 160 o C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) was used as a solvent, and the flow rate was 1 mL/min.
  • the polyethylene samples according to Examples and Comparative Examples were pretreated by dissolving in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT for 160 o C for 10 hours using a GPC analyzer (PL-GP220), respectively.
  • the values of Mw and Mn were 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 types of /mol were used.
  • ⁇ is the density of polyethylene (kg/m 3 )
  • 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 represents the plateau elastic modulus of polyethylene (G N 0 ).
  • the plateau elastic modulus (G N 0 ) of Equation 1 is a storage elastic modulus when the loss elastic modulus has a minimum value in a region where the storage elastic modulus is greater than the loss elastic modulus.
  • MDR Torque (MH-ML, Nm): MDR torque values of each sample of polyethylene according to Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-5 are Alpha Technologies Production MDR (Moving Die Rheometer) It was measured using.
  • the entangled molecular weight (Me) is 9800 g/mol to 12600 g/mol
  • the melt flow index (MFRR 21.6/5 ) is 18.1 to 20.2
  • 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 o C to 132 o C at a rate of 17.3 o C/hr, the final temperature was chlorinated with chlorine in the gas phase at 132 o C for 3 hours. At this time, in the chlorination reaction, gasoline chlorin was injected at a pressure of 0.3 MPa at the same time as the temperature was raised, and the total amount of chlorine injected was 700 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
  • polyethylenes prepared in Examples 1-2 to 1-7 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.
  • Examples 2-1 to 2-7 and Comparative Examples 2-1 to 2 prepared using the polyethylenes prepared in Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-5, The physical properties of the chlorinated polyethylene of -5 were measured in the following manner, and the results are shown in Table 2 below.
  • CPE chlorine content (%): was measured using a combustion ion chromatography (Combustion IC, Ion Chromatography) analysis.
  • combustion IC combustion ion chromatography
  • Humidification amount 0.23 mL/min, internal standard (PO43-): 20 mg/kg
  • MV Mooney viscosity of CPE: The rotor in the Mooney viscometer is wrapped with a CPE sample and the die is closed. After preheating to 121 o C for 1 min, the rotor was rotated for 4 min to measure MV (Mooney viscosity, 121 o C, ML1+4).
  • Examples of CPE have a Mooney viscosity (MV) of 65 to 80 and a tensile strength of 12.5 MPa to 13.7 MPa, thereby ensuring very good mechanical properties. have.
  • Examples 2-1 and 2-4 can secure high tensile strength at MV (Mooney viscosity) equal to or less than the level, which can prevent the workability from deteriorating during extrusion. have.
  • chlorinated polyethylene prepared using the polyethylenes prepared in Examples 1-1 to 1-7 and Comparative Examples 1-1, 1-2 and 1-5, talc, and carbon black CPE compound specimens of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-2 were prepared by mixing 50 to 70% by weight of an inorganic additive such as black, and 0.5 to 10% by weight of a crosslinking agent, and then processing them. Did.
  • Examples 3-1 to 376 and comparisons including chlorinated polyethylene made from the polyethylenes prepared in Examples 1-1 to 1-7 and Comparative Examples 1-1, 1-2 and 1-5,
  • Examples 3-1 to 376 and comparisons including chlorinated polyethylene made from the polyethylenes prepared in Examples 1-1 to 1-7 and Comparative Examples 1-1, 1-2 and 1-5,
  • CPE compounds of Examples 3-1, 3-2, and 3-5 physical properties were measured in the following manner, and the results are shown in Table 3 below.
  • MV Mooney viscosity of CPE compound
  • the rotor in the MV device is wrapped with a sample of CPE compound and the die is closed. After preheating 1 min to 100 o C, the rotor was rotated 4 min to measure MV (Mooney viscosity, 100 o C, ML1+4).
  • the examples have a MPE viscosity (Mooney viscosity) of 48 to 61 of the CPE compound, and the tensile strength is also 12.4 MPa to 13.8 MPa, which is very good mechanical and effective for electric wires and cables. It can be seen that physical properties can be secured. Particularly, when compared with Comparative Example 3-1, Examples 3-1 and 3-7 can secure high tensile strength at an Mooney viscosity (MV) equal to or lower, minimizing processability degradation during extrusion and high strength. It can provide rubber hoses, electric wire coverings, and the like.
  • Mooney viscosity Mooney viscosity

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Abstract

La présente invention concerne un polyéthylène qui présente une région intramoléculaire élevée de poids moléculaire moyen à élevé et peut être mis à réagir avec du chlore pour préparer du polyéthylène chloré présentant une excellente résistance à la traction et une excellente aptitude au traitement lors de l'extrusion. Un composé CPE contenant ce polyéthylène peut être préparé.
PCT/KR2019/017400 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé WO2020122563A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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US20210230323A1 (en) * 2018-12-10 2021-07-29 Lg Chem, Ltd. Polyethylene and Chlorinated Polyethylene Thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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