WO2020122562A1 - Polyéthylène et polyéthylène chloré associé - Google Patents

Polyéthylène et polyéthylène chloré associé Download PDF

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WO2020122562A1
WO2020122562A1 PCT/KR2019/017399 KR2019017399W WO2020122562A1 WO 2020122562 A1 WO2020122562 A1 WO 2020122562A1 KR 2019017399 W KR2019017399 W KR 2019017399W WO 2020122562 A1 WO2020122562 A1 WO 2020122562A1
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Prior art keywords
polyethylene
alkyl
formula
group
particle size
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PCT/KR2019/017399
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English (en)
Korean (ko)
Inventor
이시정
김선미
정철환
최이영
홍복기
박성현
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020190163115A external-priority patent/KR102427755B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US17/052,724 priority Critical patent/US11905345B2/en
Priority to CN201980030760.8A priority patent/CN112088174B/zh
Priority to EP19897421.4A priority patent/EP3778665B1/fr
Publication of WO2020122562A1 publication Critical patent/WO2020122562A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a polyethylene having a short stress relaxation time and having a uniform particle size and a chlorinated polyethylene thereof, which can produce chlorinated polyethylene having a low glass transition temperature (Tg) so as to improve the impact strength of the PVC compound.
  • Tg glass transition temperature
  • 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.
  • a polymer having a narrow molecular weight distribution according to a single active point property and a uniform composition distribution of a comonomer is obtained, and the stereoregularity, copolymerization property, molecular weight, and crystallinity of the polymer are changed by changing the ligand structure and polymerization conditions of the catalyst. It has properties that can change the back.
  • 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.
  • Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by polymerizing while changing the combination of catalysts in the reactor by supporting a dual nuclear metallocene catalyst and a single nuclear metallocene catalyst with an activator on a carrier. It is disclosed. However, 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 used as an impact reinforcing material such as PVC window profiles and pipes because it is known to have improved impact resistance with rubber-like properties compared to polyethylene (soft, rubbery).
  • PVC compound product excellent impact strength is required, but the strength of the compound varies depending on the properties of chlorinated polyethylene.
  • general-purpose chlorinated polyethylene which is currently widely known, since polyethylene using a Ziegler-Natta catalyst is applied, the molecular weight distribution is wide and the ultra-high molecular weight content is large. It has the disadvantage of insufficient impact strength.
  • the present invention is to provide a polyethylene and chlorinated polyethylene thereof, a PVC composition comprising the same, which can produce a chlorinated polyethylene having a low glass transition temperature in order to improve the impact strength of the PVC compound with a short stress relaxation time and a uniform particle size.
  • the present invention is to provide a method for producing the polyethylene.
  • polyethylene satisfying the following conditions 1) to 4) is provided.
  • the stress relaxation time is less than 2 seconds
  • melt index MI 5 melt index of polyethylene measured under the conditions of 190° C. temperature and 5 kg load by the method of ASTM D 1238) is 0.75 g/10min to 1.2 g/10min,
  • Melt flow index (MFRR 21.6/5 , ASTM D 1238 method, melt index measured at 190°C, 21.6 kg load divided by melt index measured at 190°C, 5 kg load) is 9.5 to 12.5,
  • 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 short stress relaxation time and a uniform particle size, and can react with chlorine to produce chlorinated polyethylene having excellent chlorination productivity and glass transition temperature.
  • 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 glass transition temperature is provided so that the stress relaxation time is short and the particle size is uniform, thereby improving the impact strength of the PVC compound.
  • the polyethylene is characterized by satisfying the following conditions 1) to 4).
  • the stress relaxation time is less than 2 seconds
  • melt index MI 5 melt index of polyethylene measured under the conditions of 190° C. temperature and 5 kg load by the method of ASTM D 1238) is 0.75 g/10min to 1.2 g/10min,
  • Melt flow index (MFRR 21.6/5 , ASTM D 1238 method, melt index measured at 190°C, 21.6 kg load divided by melt index measured at 190°C, 5 kg load) is 9.5 to 12.5,
  • 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 change because the atomic volumes of hydrogen and chlorine are different, but the crystal structure in the polyethylene disappears, resulting in rubber-like properties, which increases the impact resistance.
  • the polyethylene of the present invention has a small molecular weight distribution, a low molecular weight content in the molecular structure, a small particle size, and uniform uniformity of chlorine substitution in the chlorination process, thereby applying chlorinated polyethylene to have excellent physical properties. Can provide.
  • the polyethylene of the present invention is characterized in that the low molecular weight content in the molecular structure is small, the particle size distribution is uniform in the existing polyethylene, and the stress relaxation time is short. As a result, chlorinated polyethylene having excellent chlorination productivity and glass transition temperature can be produced, thereby improving impact strength when applied as an impact modifier to PVC compounds.
  • 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 seconds or less or about 0.5 seconds to about 2 seconds. Specifically, the relaxation time may be about 0.6 seconds to about 1.5 seconds, or about 0.7 seconds to about 1.3 seconds, or about 0.8 seconds to about 1.1 seconds, or about 0.9 seconds to about 1.1 seconds.
  • 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 using a rotational rheometer ARES-G2 from 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 1 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),
  • the ⁇ and m are parameters that fit 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 1,
  • 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 is manufactured by optimizing a specific metallocene catalyst as described below, so that the melt index (MI 5 ) of the polyethylene is optimized and the stress relaxation time is short and the particle size is uniform through a molecular structure with a narrow molecular weight distribution. It is characterized by showing.
  • melt index MI 5 of about 0.75 g/10min to about 1.2 g/10min, or about 0.8 g/10min to, measured under conditions of 190° C. temperature and 5 kg load by the method of ASTM D 1238 as described above. About 1.1 g/10min, or about 0.84 g/10min to about 1.0 g/10min.
  • the melt index MI 5 of the polyethylene should maintain the above-described range in terms of optimizing the pattern viscosity (MV, Mooney Viscosity) of chlorinated polyethylene to improve the processability while preventing deterioration of properties of the PVC compound.
  • 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 9.5 to about 12.5, or about 10 to about 12, or about 10.5 to about 12, or about 10.7 to about 11.5.
  • the melt flow index (MFRR 21.6/5 ) should be about 12.5 or less in terms of preventing degradation of PVC properties, and should be about 9.5 or more in terms of preventing degradation of processability of PVC compounds.
  • the polyethylene of the present invention is characterized by having a dense density, together with the characteristics of the relaxation time and the melt index and melt cloudiness index as described above.
  • the density of the polyethylene is about 0.947 g/cm 3 to 0.954 g/cm 3 , specifically about 0.948 g/cm 3 to 0.954 g/cm 3 , or about 0.949 g/cm 3 to 0.953 g/cm 3 have. 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 about 4.4 or less or about 2 to about 4.4, or about 4.0 or less or about 2.5 to about 4.0, or about 3.5 or less or about 2.5 to about 3.5. This means that the molecular weight distribution of polyethylene is narrow. When the molecular weight distribution is wide, since the molecular weight difference between the polyethylenes is large, it is difficult to uniformly distribute the chlorine in the chlorinated polyethylene after the chlorination reaction. In addition, since 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. However, in the present invention, 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 140000 g/mol to about 200000 g/mol, or about 150000 g/mol to about 170000 g/mol.
  • the integral value of the region where the log MW value is 4 or less is about 3% or less of the total integral value or about 1% to about 3%. , Or about 2.8% or less or about 1% to about 2.8%, or about 2.5% or less or about 1% to about 2.5%.
  • the polyethylene is characterized by having a low molecular weight in the molecular structure, and in particular, a content of a low molecular weight component of less than 10 4 g/mol in weight average molecular weight (Mw) of about 3% by weight or less. Since such a low molecular weight component has high fluidity when melted, it is desirable to be about 3% by weight or less in terms of blocking pores of polyethylene particles and deteriorating chlorination productivity.
  • the integral value of a region having a log MW value of 5.5 or more is about 12% or more of the total integral value or about 12% to about 20%. , Or about 13% or more or about 13% to about 19%, or about 14.5% or more or about 14.5% to about 18%.
  • the polyethylene has a number of characteristics of the polymer content in the molecular structure, in particular, the weight average molecular weight (Mw) 10 5.5 g / mol or more of the content of the high molecular weight component has a feature of at least about 12% by weight. Since such a high molecular weight component has low fluidity, it is desirable to be about 12% by weight or more in terms of minimizing the change in the shape of polyethylene particles during the chlorination reaction.
  • the polyethylene particle size analyzer from the cumulative particle size distribution based on the volume measured by the Tyler method, the value of the particle size D 90 , D 10 , and D 50 corresponding to 90%, 10%, 50% of the total volume of the polyethylene sample, respectively.
  • the particle size distribution (Span) according to the following Equation 1 according to the following Equation 1 is about 1.1 or less or about 0.5 to about 1.1, or about 1.0 or less or about 0.6 to about 1.0, or about 0.9 or less or about 0.7 to about 0.9.
  • the particle size distribution (Span) may be about 1.1 or less in terms of uniform chlorine distribution of chlorinated polyethylene.
  • D 90 , D 10 , and D 50 are particle sizes corresponding to 90%, 10%, and 50% of the total volume of the polyethylene sample, respectively, from the cumulative particle size distribution measured by the particle size analyzer Tyler (micrometer, ⁇ m). It shows.
  • the particle size of the polyethylene can be measured by mounting a total of nine Sieves (about 63-850 ⁇ m) in an auto shaker of the particle size analyzer Tyler.
  • the particle size (D 50 ) corresponding to 50% of the total volume of the polyethylene may be about 120 ⁇ m to about 200 ⁇ m, or about 150 ⁇ m to about 190 ⁇ m, or about 160 ⁇ m to about 180 ⁇ m.
  • the polyethylene is preferably maintained in a particle size (D 50 ) in the range as described above in terms of chlorination productivity and glass transition temperature.
  • 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.
  • the stress relaxation time and the particle size of the polyethylene can be optimized to ensure high productivity in the CPE process described later and excellent impact strength during PVC compound processing.
  • 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 second metallocene compound represented by the above structural formulas can be synthesized by applying known reactions, and more detailed synthesis methods can be referred to the Examples.
  • 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 about 200 o C to about 800 o C, more preferably about 300 o C to about 600 o C, and most preferably about 300 o C to about 400 o C.
  • the drying temperature of the carrier is less than about 200 o C, there is too much moisture so that the surface moisture and the co-catalyst react, and when it exceeds about 800 o C, the surface area decreases as the pores on the surface of the carrier merge and the surface It is not preferable because the hydroxy group disappears and only the siloxane group remains, thereby reducing the reaction site with the cocatalyst.
  • the amount of hydroxy groups on the surface of the carrier is preferably about 0.1 mmol/g to about 10 mmol/g, and more preferably about 0.5 mmol/g to about 5 mmol/g.
  • the amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than about 0.1 mmol/g, there are fewer reaction sites with the co-catalyst, and if it exceeds about 10 mmol/g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. It is not desirable.
  • the mass ratio of the total transition metal to the carrier contained in the metallocene catalyst may be about 1: 10 to about 1: 1000.
  • the carrier and the metallocene compound are included in the mass ratio, an optimal shape may be exhibited.
  • the mass ratio of the co-catalyst compound to the carrier may be from about 1:1 to about 1:100.
  • the ethylene polymerization reaction may be performed using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.
  • the polyethylene according to the present invention at least one first metallocene compound represented by Formula 1; And in the presence of at least one second metallocene compound selected from the compounds represented by Formula 3, it may be prepared by homopolymerizing ethylene.
  • the weight ratio of the first metallocene compound and the second metallocene compound is about 80:20 to about 87:13, or about 82:18 to about 85:15.
  • the weight ratio of the catalyst precursor, to improve the impact strength of the PVC compound, to produce a chlorinated polyethylene excellent in chlorination productivity and glass transition temperature has a narrow particle distribution, low molecular weight content, low molecular weight to realize a molecular structure with high polymer content It may be a weight ratio as described above in terms of.
  • 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 10 ppm to about 30 ppm, or about 20 ppm to about 30 ppm, relative to ethylene.
  • the input amount of the hydrogen gas may be about 10 ppm to 35 ppm in terms of securing the melt index MI 5 of 0.75 to 1.2 g/10min, while minimizing the wax content after the polymerization process as described above.
  • 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, in a slurry (water or HCl aqueous solution) condition under the conditions of about 60 o C to about 150 o C.
  • the Mooney viscosity (MV) measured under 121 o C conditions may be from about 85 or more to about 140 or less, or from about 85 or more to about 110 or less.
  • the chlorinated polyethylene has a glass transition temperature (Tg) measured using a differential scanning calorimeter (Differential Scanning Calorimeter, DSC, TA2000) of about -25 o C to about -15 o C, or about -22 o C to About -15.5 o C, or about -21 o C to about -16 o 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 the 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 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 the pattern viscosity (MV, Mooney viscosity) as described above under the condition that the chlorine content is 33% to 38% by weight is about 85 to about 140, the glass transition temperature (Tg) May be about -25 o C to about -15 o C.
  • the chlorinated polyethylene has a particle size (D 50 ) corresponding to a total volume of 50% of the sample from a volume-based cumulative particle size distribution measured by the particle size analyzer Tyler as described above, about 120 ⁇ m to about 210 ⁇ m, or about It may be from 150 ⁇ m to about 200 ⁇ m.
  • the chlorinated polyethylene maintains uniformity of chlorine distribution, and when compounding with PVC, it is preferable that the particle size (D 50 ) is maintained in the range as described above in terms of securing excellent impact strength.
  • the chlorinated polyethylene (CPE), drying at 120 o C conditions to minimize the drying time (minutes, min) it takes to reach the final water content of 0.4% by weight of the total weight of the sample and features improved workability and productivity may be about 180 minutes or less or about 20 minutes to about 180 minutes, or about 170 minutes or less or about 60 minutes to about 170 minutes when dried at 120 o C conditions.
  • 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 5 parts by weight to about 600 parts by weight of an inorganic additive solution such as TiO 2 , CaCO 3 , and complex stearate (Ca, Zn-stearate) with respect to 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.
  • an inorganic additive solution such as TiO 2 , CaCO 3 , and complex stearate (Ca, Zn-stearate) with respect to 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 80 seconds.
  • the PVC composition for example, when blended with vinyl chloride polymer (PVC) under the conditions of 160 o C to 190 o C, Charpy impact strength measured under room temperature conditions by ASTM E 23 method is about 22 kJ/m 2 or more, or about 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 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, the input of hydrogen was changed to 25 ppm and 30 ppm, to prepare high-density polyethylene 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. .
  • MI Melt Index
  • the melt index (MI 2.16 , MI 5 , MI 21.6 ) was measured under the conditions of load 2.16 kg, 5 kg, and 21.6 kg at a temperature of 190 o C, respectively, by the method of ASTM D 1238, and the weight of the polymer melted for 10 minutes. (g).
  • the melt flow index (MFRR, MI 21.6/5 ) was calculated by dividing the melt index measured at 190 o C, 21.6 kg load by the method of ASTM D 1238 by the melt index measured at 190 o C, 5 kg load. .
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene are measured using gel permeation chromatography (GPC, manufactured by Water), and the molecular weight distribution (MWD) is divided by the weight average molecular weight divided by the number average molecular weight. ) was calculated.
  • 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 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.
  • the log MW value is 4 or less in the GPC curve graph with the x-axis being log MW and the y-axis being dw/dlogMw (ie, Mw 10 4 or less) and 5.5 or more (ie, Mw 10 5.5 or more) are shown in Table 1 below by calculating the percentage (%) of the integral values of the total integral values, respectively.
  • the density (g/cm 3 ) of polyethylene was measured by the method of ASTM D 1505.
  • the stress relaxation time (seconds) of polyethylene was measured at 190° C. for each frequency 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 1 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),
  • the ⁇ and m are parameters that fit 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 1,
  • 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.
  • HDPE polyethylene
  • a total of nine Sieves 63-850 ⁇ m were mounted on a particle size analyzer Tyler type auto shaker to measure the particle size and particle size distribution of the polyethylene sample. So from the obtained cumulative particle size distribution on a volume basis particle size corresponding to 50% of the total volume of sample [D 50, ⁇ m] save, In addition, the particle size corresponding to 10% and 90% of the total volume of sample [D 10, D 90 , ⁇ m], respectively, and then the particle size distribution (Span) was obtained according to Equation 1 below.
  • both the polystyrene melt index (MI 5 ) and the melt flow index (MFRR) are high, and when chlorinated polyethylene is produced, the pattern viscosity (MV) is significantly lowered and the glass transition temperature of the CPE (Tg). Is high and may cause unsuitable problems for use as a PVC impact modifier.
  • 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 1-4 also produced chlorinated polyethylene in powder form in the same manner as above.
  • CPE chlorinated polyethylene
  • the drying time for chlorinated polyethylene (CPE) is, after chlorination, the product is dried at 120 o C, and the time it takes for the final moisture content in CPE to reach 0.4% by weight relative to the total weight of chlorinated polyethylene (CPE) (min, min).
  • the final moisture content included in the CPE was confirmed by considering the time when there is no weight change due to evaporation of moisture by using an IR moisture content meter.
  • the rotor in a 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).
  • the temperature was increased from -70 o C to 150 o C at 10 o C/min using a TA Scanning (Differential Scanning Calorimeter, DSC, TA2000) , After maintaining at this temperature for 1 min, lowered from 150 o C to -70 o C to 10 o C/min and maintained for 1 min.
  • the glass transition temperature (Tg, o C) was measured while heating at -70 o C to 150 o C at 10 o C/min (2nd cycle).
  • chlorinated polyethylenes of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-4 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 to 3-4 were prepared.
  • Charpy impact strength (kJ/m 2 ) of the PVC compound was measured under room temperature conditions by a method according to ASTM E23.
  • the examples have short stress relaxation time of high-density polyethylene and uniform particle size, thereby realizing a low glass transition temperature after chlorination to obtain an excellent effect of significantly improving the impact strength of the PVC compound.
  • Table 3 in comparison with the comparative examples, the examples have short stress relaxation time of high-density polyethylene and uniform particle size, thereby realizing a low glass transition temperature after chlorination to obtain an excellent effect of significantly improving the impact strength of the PVC compound. was confirmed.

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Abstract

Le polyéthylène, selon la présente invention, a un temps de relaxation de contrainte court et une taille de particule uniforme, et ainsi, il est possible de produire du polyéthylène chloré ayant une excellente productivité de chloration et une température de transition vitreuse par réaction de celui-ci avec du chlore, et de préparer une composition de PVC ayant une résistance au choc améliorée comprenant celui-ci.
PCT/KR2019/017399 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé Ceased WO2020122562A1 (fr)

Priority Applications (3)

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US17/052,724 US11905345B2 (en) 2018-12-10 2019-12-10 Polyethylene and chlorinated polyethylene thereof
CN201980030760.8A CN112088174B (zh) 2018-12-10 2019-12-10 聚乙烯及其氯化聚乙烯
EP19897421.4A EP3778665B1 (fr) 2018-12-10 2019-12-10 Polyéthylène et polyéthylène chloré associé

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KR10-2018-0158328 2018-12-10
KR20180158328 2018-12-10
KR20190121170 2019-09-30
KR10-2019-0121170 2019-09-30
KR10-2019-0163115 2019-12-09
KR1020190163115A KR102427755B1 (ko) 2018-12-10 2019-12-09 폴리에틸렌 및 이의 염소화 폴리에틸렌

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WO2020122562A1 true WO2020122562A1 (fr) 2020-06-18

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US20220135712A1 (en) * 2019-02-20 2022-05-05 Lg Chem, Ltd. Polyethylene Having High Pressure Resistance and Crosslinked Polyethylene Pipe Comprising the Same
CN116648466A (zh) * 2020-11-30 2023-08-25 株式会社Lg化学 聚乙烯及其制备方法
US12122903B2 (en) 2019-02-20 2024-10-22 Lg Chem, Ltd. Crosslinked polyethylene pipe having excellent physical properties
US12173142B2 (en) 2019-02-20 2024-12-24 Lg Chem, Ltd. Polyethylene having high degree of crosslinking and crosslinked polyethylene pipe comprising the same

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220135712A1 (en) * 2019-02-20 2022-05-05 Lg Chem, Ltd. Polyethylene Having High Pressure Resistance and Crosslinked Polyethylene Pipe Comprising the Same
US12065514B2 (en) * 2019-02-20 2024-08-20 Lg Chem, Ltd. Polyethylene having high pressure resistance and crosslinked polyethylene pipe comprising the same
US12122903B2 (en) 2019-02-20 2024-10-22 Lg Chem, Ltd. Crosslinked polyethylene pipe having excellent physical properties
US12173142B2 (en) 2019-02-20 2024-12-24 Lg Chem, Ltd. Polyethylene having high degree of crosslinking and crosslinked polyethylene pipe comprising the same
CN116648466A (zh) * 2020-11-30 2023-08-25 株式会社Lg化学 聚乙烯及其制备方法

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