WO2020122560A1 - Polyéthylène et polyéthylène chloré associé - Google Patents

Polyéthylène et polyéthylène chloré associé Download PDF

Info

Publication number
WO2020122560A1
WO2020122560A1 PCT/KR2019/017397 KR2019017397W WO2020122560A1 WO 2020122560 A1 WO2020122560 A1 WO 2020122560A1 KR 2019017397 W KR2019017397 W KR 2019017397W WO 2020122560 A1 WO2020122560 A1 WO 2020122560A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyethylene
formula
alkyl
group
aryl
Prior art date
Application number
PCT/KR2019/017397
Other languages
English (en)
Korean (ko)
Inventor
이시정
홍복기
박성현
김선미
최이영
정철환
이진석
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020190163117A external-priority patent/KR102427756B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201980030785.8A priority Critical patent/CN112088175B/zh
Priority to CN202311185254.0A priority patent/CN117229436A/zh
Priority to US17/048,418 priority patent/US11643483B2/en
Priority to EP19896315.9A priority patent/EP3770187B1/fr
Publication of WO2020122560A1 publication Critical patent/WO2020122560A1/fr

Links

Classifications

    • 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 compounds containing halogen
    • 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 relates to polyethylene and its chlorinated polyethylene capable of producing chlorinated polyethylene excellent in chlorination productivity and thermal stability so as to improve the impact strength of a PVC compound by realizing a narrow particle distribution and a molecular structure with a low ultra-high molecular weight. will be.
  • 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 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 present invention implements a molecular structure with a narrow particle distribution and a low ultra-high molecular weight content, which can produce chlorinated polyethylene having excellent chlorination productivity and thermal stability to improve the impact strength of PVC compounds, including polyethylene and its chlorinated polyethylene. It is intended to provide a PVC composition.
  • the present invention is to provide a method for producing the polyethylene.
  • polyethylene having a crystal structure transition temperature of 110° C. or higher and a stress relaxation time (s) satisfying Equation 1 below is provided.
  • T is a value representing the relaxation time (s) of polyethylene in seconds
  • M is the melt index (MI 5 , melt index, g/10min) of polyethylene measured under the conditions of temperature 190° C. and load 5 kg by the method of ASTM D 1238.
  • 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 present invention provides a PVC composition comprising the chlorinated polyethylene and vinyl chloride polymer (PVC).
  • the polyethylene according to the present invention has a narrow particle distribution and realizes a molecular structure with a low ultra-high molecular weight, minimizing the change in crystal structure, and reacting it with chlorine to produce chlorinated polyethylene having excellent 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 chlorinated polyethylene having excellent chlorination productivity and thermal stability is provided so as to improve the impact strength of a PVC compound by realizing a molecular structure with a narrow particle distribution and ultra high molecular content. do.
  • the polyethylene characterized in that the crystal structure transition temperature is 110 °C or more, and the stress relaxation time (Relaxation time, s) satisfies the following equation (1).
  • T is a value representing the relaxation time (s) of polyethylene in seconds
  • M is the melt index (MI 5 , melt index, g/10min) of polyethylene measured under the conditions of temperature 190° C. and load 5 kg by the method of ASTM D 1238.
  • 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 more 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 that the degree of chlorine substitution in the particles can be uniform, thereby exhibiting excellent physical properties.
  • the polyethylene of the present invention has less ultra-high molecular weight in the molecular structure, and the lower the melt index (MI) in the existing polyethylene, the longer the stress relaxation time (relaxation time) is, and the same melt index (MI) as in Equation 1 above. ) Is characterized by a short stress relaxation time.
  • MI melt index
  • the polyethylene according to the present invention may be an ethylene homopolymer that does not contain a separate copolymer.
  • the polyethylene may have a stress relaxation time of about 2.0 seconds or less or about 0.5 seconds to about 2.0 seconds. Specifically, the relaxation time may be about 1.8 seconds or less or about 0.6 seconds to about 1.8 seconds, or about 1.5 seconds or less, or about 0.7 seconds to about 1.5 seconds.
  • the stress relaxation time (Relaxation time) lowers the ultra-high molecular weight (molecular weight of 10 6 or more) content of the product to 2.1% or less, and lowers the Mp value to 100000 g/mol or less, so that the stress relaxation time is about 2.0 seconds despite low MI. It can be:
  • the relaxation time of the polyethylene (Relaxation time), using a rotary rheometer, after measuring the viscosity of the polyethylene under the temperature (Angular Frequency) conditions of 190 °C temperature and 0.05 rad / s to 500 rad / s, This viscosity can be determined by using a specific cross model to calculate the stress relaxation time (seconds) of polyethylene.
  • the method for measuring the stress relaxation time of the polyethylene is as described in Test Example 1 described later.
  • the stress relaxation time of the polyethylene is each frequency at 190 °C by using a rotational rheometer ARES-G2 of TA Instruments (TA Instruments) (New Castle, Del.) (Angular Frequency) Measure the viscosity at 0.05 rad/s to 500 rad/s, and calculate the stress relaxation time (seconds) using the cross model of Equation 2 below from the measured viscosity value. can do.
  • the ⁇ is the viscosity of polyethylene measured under a temperature of 190° C. and an angle of 0.05 rad/s to 500 rad/s using an rotatable rheometer.
  • the ⁇ ⁇ is an infinite shear viscosity
  • the ⁇ 0 is the zero point shear viscosity
  • the shear rate is a shear rate applied to polyethylene and is the same value as each frequency (Angular Frequency),
  • ⁇ and m are the parameters of fitting a log-log graph with each frequency (Angular Frequency) as the x-axis and the viscosity measurement value ⁇ as the y-axis as a cross model in Equation 2,
  • the ⁇ is the reciprocal of each frequency (Angular Frequency) at which the viscosity ⁇ begins to decrease with the stress relaxation time (seconds) of polyethylene.
  • the m is the slope of the viscosity ⁇ in the region where the viscosity ⁇ decreases.
  • the polyethylene satisfies the correlation between the melt index as shown in Equation 1 and the stress relaxation time by optimizing and preparing a specific metallocene catalyst as described below, and the specific melt index MI 5 It is characterized by a short stress relaxation time in the same melt index range as a reference.
  • This is a characteristic that the polyethylene according to the present invention appears with a narrow molecular weight distribution and an ultrahigh molecular weight in the molecular structure.
  • the polyethylene of the present invention exhibits a high weight average molecular weight (Mw) of about 1600000 g/mol or more, while the integral area of the ultrahigh molecular weight region of the region where Mw is 1 ⁇ 10 6 g/mol or higher in the GPC curve is integrated over the entire graph. It may be about 2.1% or less of the area.
  • These polyethylenes have a melt index MI 5 of about 0.55 g/10min or less, or 0.15 g/10min to 0.55 g/10min, or about 195 g/min, measured under conditions of 190° C. temperature and 5 kg load, as described above. 0.45 g/10min or less or 0.15 g/10min to 0.45 g/10min, or about 0.35 g/10min or less or 0.15 g/10min to 0.35 g/10min.
  • the melting index MI 5 may be less than about 0.55 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 lower the MI, the higher the viscosity.
  • 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 18, or about 12 to about 16.
  • the polyethylene of the present invention is characterized by having a high crystal structure transition temperature (CRT), as well as a relaxation time time characteristic as described above.
  • CRT crystal structure transition temperature
  • the crystal structure transition temperature of the polyethylene is about 110 °C or higher or about 110 °C to about 145 °C, or 115 °C or higher or about 115 °C to about 145 °C, or 120 °C or higher, or about 120 °C to about 145 °C.
  • the transition temperature of the crystal structure refers to the temperature at which the crystal arrangement changes while the lamella structure forming the crystal is maintained. The temperature is lowered to -60°C using a DMA (Dynamic Mechanical Analyzer), and the temperature for 5 minutes. It was maintained at, and then the temperature was increased to 140° C., and the top of the tan ⁇ curve was measured as the crystal structure transition temperature.
  • DMA Dynamic Mechanical Analyzer
  • Changes in the arrangement of the polyethylene crystals before and after the crystal structure transition temperature appear, and the polyethylene of the present invention means that the change in the crystal arrangement occurs at a higher temperature because the crystal structure transition temperature is close to the melting temperature of 110° C. or higher. , It has a characteristic that the morphology of the polyethylene particles is difficult to change during the chlorination process. Accordingly, high chlorination productivity can be secured.
  • the density of the polyethylene may be about 0.947 g/cm 3 to 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 g/mol to about 250,000 g/mol, or about 170000 g/mol to about 250,000 g/mol, or about 180000 g/mol to about 250,000 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 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,
  • 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.
  • CRT crystal structure transition temperature
  • MI 5 melt index
  • 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 cocatalyst 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°C to 800°C, more preferably 300°C to 600°C, and most preferably 300°C to 400°C.
  • the drying temperature of the carrier is less than 200 °C, there is too much moisture, and the surface moisture and the co-catalyst react, and when it exceeds 800 °C, the surface area decreases as the pores on the carrier surface are combined, and there are many hydroxyl groups on the surface. It is not preferable because the reaction site with the co-catalyst decreases because it disappears and only siloxane groups remain.
  • the amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.5 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 about 65:35 to 75:25, or about 68:32 to about 72 It can be :28.
  • the hydrogen input in the polymerization process may be reduced to about 35 ppm or less, and the wax content is 10. It can be kept low below %.
  • 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 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 35 ppm or less or about 10 ppm to about 35 ppm, or about 30 ppm or less or about 20 ppm to about 30 ppm, relative to ethylene.
  • the input amount of the hydrogen gas may be less than about 35 ppm in terms of securing the melt index MI 5 of 0.55 g/10min or less while minimizing the wax content after the polymerization process as described above.
  • 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 exhibits excellent uniformity in chlorine distribution in the chlorinated polyethylene due to the polyethylene having a narrow molecular weight distribution.
  • the polyethylene and the polyethylene under conditions of about 60° C. to about 150° C. in a slurry (water or HCl aqueous solution) state.
  • the Mooney viscosity (MV) measured under the condition of 121°C is from about 85 to about 140, or from about 88 to about 130, or from about 90 to about 110 Can be up to.
  • the chlorinated polyethylene has a glass transition temperature (Tg) of about -25 °C to about -15 °C, or about -22 °C to about -15.5, measured using a differential scanning calorimeter (DSC, TA2000). It is characterized in that the temperature is about -20°C to about -16°C.
  • Tg glass transition temperature
  • 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 method for measuring the pattern viscosity (MV, Mooney viscosity) and glass transition temperature (Tg) of the chlorinated polyethylene is as described in Test Example 2, which will be omitted.
  • 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 according to the present invention the pattern viscosity (MV, Mooney viscosity) as described above under the condition that the chlorine content is 33% to 38% by weight is about 90 to about 110, the glass transition temperature (Tg) May be about -20 °C to about -16 °C.
  • 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 PVC composition comprising chlorinated polyethylene and vinyl chloride polymer (PVC) as described above is provided.
  • the PVC composition may include, for example, about 5% to about 20% by weight of chlorinated polyethylene as described above and about 50% to about 95% by weight of polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • the chlorinated polyethylene may be, for example, about 5% to about 20% by weight, or about 5% to about 10% by weight.
  • the vinyl chloride polymer (PVC) may be, for example, about 50% to about 95% by weight, or about 60% to about 90% by weight.
  • the PVC composition is about 5 parts by weight to about 600 parts by weight of inorganic additives such as TiO 2 , CaCO 3 , and complex stearate (Ca, Zn-stearate), based on 100 parts by weight of chlorinated polyethylene as described above, or It may further include about 10 parts by weight to about 200 parts by weight.
  • inorganic additives such as TiO 2 , CaCO 3 , and complex stearate (Ca, Zn-stearate), based on 100 parts by weight of chlorinated polyethylene as described above, or It may further include about 10 parts by weight to about 200 parts by weight.
  • the PVC composition is about 5% to about 20% by weight of chlorinated polyethylene as described above, about 60% to about 90% by weight of vinyl chloride polymer (PVC), about 1% to about 10% by weight of TiO 2 Weight %, CaCO 3 about 1% to about 10% by weight and composite stearate (Ca, Zn-stearate) about 1% to about 10% by weight.
  • the PVC composition may have a plasticization time of about 170 seconds or less, about 150 seconds or less, or about 150 seconds to about 100 seconds.
  • the PVC composition for example, 160 °C to 190
  • Charpy impact strength measured under room temperature conditions by ASTM E 23 method may be 24 kJ/m 2 or more. Within this range, there is an effect of excellent physical property balance and productivity.
  • the method for measuring the Charpy impact strength of the PVC composition is as described in Test Example 3 described below, and a specific measurement method is omitted.
  • 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° 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, the input of hydrogen was varied to 25 ppm and 30 ppm, respectively, to prepare high density polyethylenes of Examples 1-2 and 1-3 having a powder form.
  • Example 1-1 Prepared in the same manner as in Example 1-1, 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 of Comparative Example 1-4 having a 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 of Comparative Example 1-6 having a powder form. .
  • MI Melt Index
  • Melt flow index (MFRR, MI 21.6/5 ) melt flow divided by the melt index measured at 190°C and 21.6 kg 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.
  • 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 300mm length column was used. At this time, the measurement temperature was 160°C, and 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 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.
  • Crystal relaxation temperature The temperature is lowered to -60°C using DMA (Dynamic Mechanical Analyzer, manufactured by TA), maintained at that temperature for 5 minutes, and then the temperature is raised to 140°C. By increasing, the top of the tan ⁇ curve was measured as the crystal structure transition temperature.
  • DMA Dynamic Mechanical Analyzer
  • Equation 1 is “satisfied”. It was expressed as "dissatisfied” in the case where it was equal to or greater than the value obtained from the correlation with MI 5 according to Equation 1 below.
  • T is a value representing the relaxation time (s) of polyethylene in seconds
  • M is the melt index (MI 5 , melt index, g/10min) of polyethylene measured under the conditions of temperature 190° C. and load 5 kg by the method of ASTM D 1238.
  • the stress relaxation time (seconds) of polyethylene was each frequency at 190° C. using ARES-G2, a rotational rheometer manufactured by TA Instruments (New Castle, Delaway, USA). Angular Frequency) The viscosity at 0.05 rad/s to 500 rad/s was measured, and the stress relaxation time (seconds) was calculated from the measured viscosity value using the cross model of Equation 2 below. .
  • the ⁇ is the viscosity of polyethylene measured under a temperature of 190° C. and an angle of 0.05 rad/s to 500 rad/s using an rotatable rheometer.
  • the ⁇ ⁇ is an infinite shear viscosity
  • the ⁇ 0 is the zero point shear viscosity
  • the shear rate is a shear rate applied to polyethylene and is the same value as each frequency (Angular Frequency),
  • ⁇ and m are the parameters of fitting a log-log graph with each frequency (Angular Frequency) as the x-axis and the viscosity measurement value ⁇ as the y-axis as a cross model in Equation 2,
  • the ⁇ is the reciprocal of each frequency (Angular Frequency) at which the viscosity ⁇ begins to decrease with the stress relaxation time (seconds) of polyethylene.
  • the m is the slope of the viscosity ⁇ in the region where the viscosity ⁇ decreases.
  • 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 injected was 610 kg. The chlorinated reactant was added to NaOH to neutralize for 4 hours, washed again with running 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
  • polyethylenes prepared in Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-7 also produced chlorinated polyethylene in powder form in the same manner as above.
  • CPE chlorine content (%): was measured using a combustion ion chromatography (Combustion IC, Ion Chromatography) analysis.
  • combustion IC combustion ion chromatography
  • Combustion temperature Inlet temperature 900 °C, Outlet temperature 1000 °C
  • 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° C. for 1 min, the rotor was rotated for 4 min to measure MV (Mooney viscosity, 121° C., ML1+4).
  • CPE glass transition temperature Tg, °C: TA Instruments (TA Instruments, New Castle, Inc.), differential scanning calorimeter (Differential Scanning Calorimeter, DSC, TA2000) temperature at -70 °C The temperature was raised to 10C/min to 150C and maintained at this temperature for 1 min, then lowered from 150C to -70C to 10C/min and held for 1 min. The glass transition temperature was measured while heating from -70°C to 150°C at 10°C/min (2nd cycle).
  • CPE productivity was evaluated as "predominant" in the chlorinated polyethylene production section for 4 hours or less based on the drying time of 120°C, and "inferior" when it exceeded 4 hours.
  • the drying time exceeds 4 hours, the CPE particle morphology is deformed and the porosity is reduced. If the time exceeds 4 hours, it is determined that the continuous process is difficult, and the amount of production per day decreases, resulting in a significant drop in CPE productivity.
  • chlorinated polyethylenes of Examples 2-1 to 2-3 and Comparative Examples 2-1 and 2-2 prepared by using the polyethylenes prepared in Examples and Comparative Examples were blended with a vinyl chloride polymer (PVC) to prepare Examples.
  • Chlorinated polyethylene PVC compounds of 3-1 to 3-3 and Comparative Examples 3-1 and 3-2 were prepared.
  • Fusion time of PVC compound (Fusion time, second): At a speed of 40 rpm at 160°C using an extruder, 6.5% by weight of chlorinated polyethylene and 81.6% by weight of vinyl chloride polymer (PVC), as described above. 500 g of a mixture of TiO 2 3.2 wt%, CaCO 3 4.1 wt%, and complex stearate (Ca, Zn) 4.5 wt% was added, and a torque change was measured through a connected rheometer. The time to start maintaining a constant torque (Fusion time, seconds) of the PVC compound (compound) was measured.
  • the examples show a low glass transition temperature after chlorination based on a narrow molecular weight distribution of high-density polyethylene and a molecular structure with low ultra-high molecular weight, which significantly improves the impact strength of the PVC compound. It has been confirmed that the melting time (Fusion time) is lowered to obtain an excellent effect that is easy to process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un polyéthylène qui présente une distribution granulométrique étroite et une structure moléculaire ayant une faible teneur en domaine de poids moléculaire ultra-haut et qui peut être mis à réagir avec du chlore pour préparer du polyéthylène chloré ayant une productivité de chloration et une stabilité thermique excellentes. Une composition de PVC contenant ce polyéthylène pourvue d'une résistance au choc améliorée peut être préparée.
PCT/KR2019/017397 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé WO2020122560A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201980030785.8A CN112088175B (zh) 2018-12-10 2019-12-10 聚乙烯及其氯化聚乙烯
CN202311185254.0A CN117229436A (zh) 2018-12-10 2019-12-10 聚乙烯及其氯化聚乙烯
US17/048,418 US11643483B2 (en) 2018-12-10 2019-12-10 Polyethylene and chlorinated polyethylene thereof
EP19896315.9A EP3770187B1 (fr) 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2018-0158328 2018-12-10
KR20180158328 2018-12-10
KR10-2019-0163117 2019-12-09
KR1020190163117A KR102427756B1 (ko) 2018-12-10 2019-12-09 폴리에틸렌 및 이의 염소화 폴리에틸렌

Publications (1)

Publication Number Publication Date
WO2020122560A1 true WO2020122560A1 (fr) 2020-06-18

Family

ID=71077447

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/017397 WO2020122560A1 (fr) 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé

Country Status (2)

Country Link
CN (1) CN117229436A (fr)
WO (1) WO2020122560A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5914289A (en) 1996-02-19 1999-06-22 Fina Research, S.A. Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution
WO1999050316A1 (fr) * 1998-03-31 1999-10-07 The B.F. Goodrich Company Polyolefines chlorees en bloc, procede de formation et d'utilisation en tant qu'agent de compatibilite modifiant-choc pour pvc ou cpvc
KR200312308Y1 (ko) 2003-02-06 2003-05-09 주식회사 제일 유브이 유턴형 컨베이어 자외선 경화기
US20050085602A1 (en) * 2003-10-15 2005-04-21 Sandor Nagy Olefin polymerization process
KR20090088620A (ko) * 2008-02-15 2009-08-20 삼성토탈 주식회사 염소화폴리에틸렌 수지
KR20160123123A (ko) * 2015-04-15 2016-10-25 주식회사 엘지화학 가공성이 우수한 에틸렌/알파-올레핀 공중합체 공중합체
KR101723774B1 (ko) * 2016-07-28 2017-04-18 한화케미칼 주식회사 혼성 담지 메탈로센 촉매를 이용한 고가공성 고밀도 에틸렌계 중합체 및 제조방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5914289A (en) 1996-02-19 1999-06-22 Fina Research, S.A. Supported metallocene-alumoxane catalysts for the preparation of polyethylene having a broad monomodal molecular weight distribution
WO1999050316A1 (fr) * 1998-03-31 1999-10-07 The B.F. Goodrich Company Polyolefines chlorees en bloc, procede de formation et d'utilisation en tant qu'agent de compatibilite modifiant-choc pour pvc ou cpvc
KR200312308Y1 (ko) 2003-02-06 2003-05-09 주식회사 제일 유브이 유턴형 컨베이어 자외선 경화기
US20050085602A1 (en) * 2003-10-15 2005-04-21 Sandor Nagy Olefin polymerization process
KR20090088620A (ko) * 2008-02-15 2009-08-20 삼성토탈 주식회사 염소화폴리에틸렌 수지
KR20160123123A (ko) * 2015-04-15 2016-10-25 주식회사 엘지화학 가공성이 우수한 에틸렌/알파-올레핀 공중합체 공중합체
KR101723774B1 (ko) * 2016-07-28 2017-04-18 한화케미칼 주식회사 혼성 담지 메탈로센 촉매를 이용한 고가공성 고밀도 에틸렌계 중합체 및 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TETRAHEDRON LETT., vol. 2951, 1988

Also Published As

Publication number Publication date
CN117229436A (zh) 2023-12-15

Similar Documents

Publication Publication Date Title
WO2017188602A1 (fr) Catalyseur hybride de type métallocène supporté et résine polyoléfinique présentant une excellente aptitude au traitement et l'utilisant
WO2015046931A1 (fr) Procédé de préparation de polymère à base d'oléfine et polymère à base d'oléfine préparé en faisant appel à celui-ci
WO2016072783A1 (fr) Composé de ligand, composé de métal de transition, et composition de catalyseur les contenant
WO2019212303A1 (fr) Copolymère d'éthylène-acétate de vinyle et son procédé de préparation
WO2019212307A1 (fr) Copolymère d'éthylène/alpha-oléfine et procédé pour sa préparation
WO2019212310A1 (fr) COMPOSITION ADHÉSIVE CONTENANT UN COPOLYMÈRE D'ETHYLÈNE/α-OLÉFINE
WO2020130718A1 (fr) Polyoléfine
WO2019212304A1 (fr) Copolymère d'éthylène/alpha-oléfine et son procédé de préparation
WO2019132471A1 (fr) Polymère oléfinique
WO2020122562A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2020130719A1 (fr) Polyoléfine
WO2020122561A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2020122563A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2019234637A1 (fr) Mélange de polymère d'éthylène, son procédé de préparation et article moulé l'utilisant
WO2022071744A1 (fr) Copolymère d'éthylène/hex-1-ène présentant d'excellentes propriétés de constructibilité et d'aptitude au traitement
WO2021060907A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2020046051A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2020122560A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2022030768A1 (fr) Catalyseur métallocène supporté hybride et procédé de préparation de polypropylène l'utilisant
WO2021251766A1 (fr) Polyéthylène et son polyéthylène chloré
WO2019212302A1 (fr) Copolymère à base d'oléfine, et son procédé de préparation
WO2022114710A1 (fr) Composite de polyoléfine hybride organique-inorganique et son procédé de préparation
WO2021071226A1 (fr) Polyéthylène et polyéthylène chloré associé
WO2021060908A1 (fr) Catalyseur hybride supporté et procédé de préparation de polyoléfine faisant appel à celui-ci
WO2019132477A1 (fr) Polymère à base d'oléfine

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19896315

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019896315

Country of ref document: EP

Effective date: 20201020

NENP Non-entry into the national phase

Ref country code: DE