WO2020046051A1 - Polyéthylène et polyéthylène chloré associé - Google Patents

Polyéthylène et polyéthylène chloré associé Download PDF

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WO2020046051A1
WO2020046051A1 PCT/KR2019/011171 KR2019011171W WO2020046051A1 WO 2020046051 A1 WO2020046051 A1 WO 2020046051A1 KR 2019011171 W KR2019011171 W KR 2019011171W WO 2020046051 A1 WO2020046051 A1 WO 2020046051A1
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polyethylene
alkyl
group
aryl
alkenyl
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PCT/KR2019/011171
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English (en)
Korean (ko)
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박성현
이시정
홍복기
최이영
이명한
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주식회사 엘지화학
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Priority claimed from KR1020190105962A external-priority patent/KR102219312B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19853688.0A priority Critical patent/EP3770185A4/fr
Priority to US17/052,726 priority patent/US11702488B2/en
Priority to CN201980030726.0A priority patent/CN112105653B/zh
Publication of WO2020046051A1 publication Critical patent/WO2020046051A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—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
    • 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

Definitions

  • the present invention relates to polyethylene and its chlorinated polyethylene, which can produce a chlorinated polyethylene having a narrow particle distribution and minimizing the change in crystal structure, which is excellent in chlorination productivity and thermal stability.
  • Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics.
  • the Ziegler-Natta catalyst has been widely applied to existing commercial processes since the invention in the 50s, but is characterized by a wide molecular weight distribution of the polymer because it is a multi-site catalyst having multiple active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution is not uniform.
  • the metallocene catalyst is composed of a combination of a main catalyst mainly composed of a transition metal compound and a cocatalyst composed of an organic metal compound composed mainly of aluminum, and such a catalyst is a single-site catalyst as a homogeneous complex catalyst.
  • the molecular weight distribution is narrow according to the characteristics of the single active site, and the homogeneous composition of the comonomer is obtained, and the stereoregularity, polymerization characteristics, and molecular weight of the polymer are changed according to the ligand structure modification of the catalyst and the change of polymerization conditions. , Crystallinity and so on.
  • U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support each of the metallocene catalysts to be used on the carrier was followed.
  • Korean Patent Application No. 2003-12308 discloses a method of controlling a molecular weight distribution by supporting a double-nucleated metallocene catalyst and a mononuclear metallocene catalyst on a carrier together with an activator to polymerize by changing a combination of catalysts in a reactor. have.
  • this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage that the metallocene catalyst portion in the carrier component of the finished catalyst is liberated 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 in particular, it is able to withstand harsh external environments and chemicals, and thus, flame retardant of PVC and flame retardant of ABS. Used as a material for additives, wire coating, oil hoses, etc.
  • Chlorinated polyethylene is generally prepared by making polyethylene in suspension and then reacting with chlorine, or by replacing polyethylene with hydrogen in chlorine and replacing it with chlorine.
  • the chlorine In order to fully express the properties of chlorinated polyethylene, the chlorine must be uniformly substituted for polyethylene, which is affected by the properties of polyethylene reacting with chlorine. In particular, it is affected by the polymer structure and heat resistance properties of polyethylene, and if the change of crystal structure increases or the heat resistance property decreases according to the polymer structure, the polyethylene particles are aggregated and the overall particle size increases, resulting in increased reaction efficiency with chlorine. It is difficult to uniformly replace chlorine. When this aggregated shape occurs, it is difficult for chlorine to penetrate to the center of the polyethylene particles, thereby increasing the time required to achieve the desired level of chlorine substitution.
  • the present invention aims to provide polyethylene, which has a narrow particle distribution and minimizes the change in crystal structure, thereby producing chlorinated polyethylene having excellent chlorination productivity and thermal stability.
  • the molecular weight distribution (Mw / Mn) is 2 to 10
  • the tie molecule fraction (Tie molecule fraction) is 3% or more
  • the crystal structure transition temperature is 108 °C or more
  • the endothermic onset temperature is 125
  • Polyethylene is provided, which is at least C.
  • the present invention also provides a chlorinated polyethylene prepared by reacting the polyethylene with chlorine.
  • the polyethylene according to the present invention has a narrow particle distribution, minimizes the change in crystal structure, and reacts with chlorine to produce chlorinated polyethylene having excellent chlorination productivity and thermal stability.
  • 1 is a schematic diagram showing the change of polyethylene crystal arrangement before and after the crystal structure transition temperature in the present invention.
  • Figure 2 is a SEM photograph of the surface after completion of the chlorination process using the polyethylene of Example 1 according to an embodiment of the present invention.
  • first and second are used to describe various components, which terms are used only for the purpose of distinguishing one component from other components.
  • a polyethylene having a narrow particle distribution and minimizing the change in the crystal structure of the initial stage of the chlorination reaction to produce a chlorinated polyethylene having excellent chlorination productivity and thermal stability is provided.
  • the polyethylene according to the invention may be an ethylene homopolymer which does not comprise a separate copolymer.
  • the polyethylene has a molecular weight distribution (Mw / Mn) of 2 to 10, a tie molecule fraction of 3% or more, a crystal structure transition temperature of 108 ° C or more, and an endothermic initiation temperature of 125 ° C or more. It is done.
  • chlorinated polyethylene is prepared by reacting polyethylene with chlorine, which means that a part of hydrogen of polyethylene is substituted with chlorine.
  • the properties of polyethylene are changed because the atomic volume of hydrogen and chlorine is different.
  • the crystal structure of polyethylene is reduced, the rigidity is decreased and the impact strength is further increased.
  • the smaller and uniform the overall size of the chlorinated polyethylene particles the more easily the chlorine penetrates to the center of the polyethylene particles, so that the degree of chlorine substitution in the particles can be excellent, thereby exhibiting excellent physical properties.
  • the crystal structure decreases, the melting temperature of the polyethylene decreases, and the surface structure of the polyethylene particles may change during the chlorination reaction, or the particles may stick together, thereby increasing the total size of the particles.
  • the polyethylene according to the present invention may provide a chlorinated polyethylene having a low molecular weight distribution and minimizing the change in the crystal structure of the polyethylene at the initial stage of the chlorination reaction to have better chlorination productivity and thermal stability.
  • the polyethylene according to the present invention has a molecular weight distribution of about 2 to about 10, or about 2 to about 7, or about 3 to about 7, or about 3.4 to about 6.9, or about 3.4 to about 4.5. This means that the molecular weight distribution of polyethylene is narrow. If the molecular weight distribution is wide, the molecular weight difference between the polyethylene is large, so that the chlorine content between the polyethylene after the chlorination reaction can vary, so that the uniform distribution of chlorine is difficult. In addition, when the low molecular weight component is melted, since fluidity is high, the pores of the polyethylene particles can be prevented to reduce chlorination productivity. However, in the present invention, since the molecular weight distribution as described above, the molecular weight difference between polyethylene after the chlorination reaction is not large, chlorine can be uniformly substituted.
  • the molecular weight distribution (Mw / Mn) of the polyethylene is measured by gel permeation chromatography (GPC, gel permeation chromatography, Agilent) to measure the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer
  • GPC gel permeation chromatography
  • Mn number average molecular weight
  • the weight average molecular weight can be obtained by dividing by the number average molecular weight.
  • a gel permeation chromatography (GPC) apparatus may use an Agilent PL-GPC220 instrument and a Polymer Laboratories PLgel MIX-B 300 mm length column. At this time, the measurement temperature is 160 °C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, the flow rate can be applied at 1 mL / min. Samples of polyethylene were dissolved in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% of BHT for 10 hours using a GPC analyzer (PL-GP220), and pretreated for 10 hours, respectively, at a concentration of 10 mg / 10 mL.
  • GPC gel permeation chromatography
  • the weight average molecular weight of the polystyrene standard specimens 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 has a weight average molecular weight of about 50000 g / mol to about 250000 g / mol, or about 100000 g / mol to about 250000 g / mol, or about 160000 g / mol to about 250000 g / mol, or about 161000 g / mol to about 250000 g / mol, or about 163000 g / mol to about 250000 g / mol, or about 201000 g / mol to about 250000 g / mol.
  • This means that the molecular weight of polyethylene is high and the content of the high molecular weight component is high, which causes an effect of increasing the content of the linking molecule to be described later.
  • the polyethylene according to the present invention is characterized by increasing the content of the linking molecule (Tie molecule fraction) and increasing the crystal structure transition temperature in terms of minimizing the change in crystal structure with a narrow particle distribution as described above .
  • the 'Tie molecule' refers to a molecule connecting them between one lamellar crystal in polyethylene and another lamellar crystal.
  • the polyethylene is a semi-crystalline polymer in a spherulite form in which a plurality of lamellas formed by bundles of chains of folded polymers are gathered in three dimensions, and include a crystalline portion and an amorphous portion. Is done.
  • the crystalline portion refers to the lamellar crystal inside
  • the amorphous portion refers to the portion outside the lamellar crystal.
  • the amorphous portion includes i) cilia, where the chain starts at the crystalline portion and ends at the amorphous portion, ii) a loose loop in which the chain connects one lamellar crystal, and iii) an inter-lamellar in which the chain connects two lamellar crystals.
  • cilia where the chain starts at the crystalline portion and ends at the amorphous portion
  • a loose loop in which the chain connects one lamellar crystal
  • an inter-lamellar in which the chain connects two lamellar crystals.
  • One molecule that consists of a link and connects two lamellar crystals among these inter-lamellar links is called a linking molecule.
  • the polyethylene comprises a linking molecule which connects them in the amorphous part, ie between one lamellar crystal and the other lamellar crystal. This is particularly important because the higher the content of the linking molecule, the more the binding force of the crystalline portion increases, thereby reducing the change in crystal structure and improving the physical properties of the entire polymer.
  • the present invention is characterized by providing a polyethylene having a narrow molecular weight distribution in order to minimize the crystal structure change of the polyethylene in the initial stage of the chlorination reaction, and at the same time increase the content of the linking molecule connecting the lamellar crystal structures in the polyethylene.
  • the content of the linking molecule is increased, the crystalline portions may be well bound, and even if they have the same molecular weight, it is possible to suppress the change of the physical properties of the polyethylene, in particular the crystal structure at the beginning of the chlorination reaction.
  • the polyethylene according to the invention has a tie molecule fraction of at least about 3%.
  • the polyethylene has a linking molecule content of less than 3%, a change in crystal structure may occur during the chlorination reaction, which may cause clogging of pores on the surface of the particles or a change in morphology.
  • the linking molecule content may be at least about 3.1%, or at least about 3.2%, or at least about 3.3%, or at least about 3.4%, or at least about 3.5%.
  • the polyethylene molecular fraction of the polyethylene is about 6.0% or less, or about 5.9% or less, or about 5.8% or less, or about 5.7% or less.
  • connection molecule content of the polyethylene can be measured through a Tie molecule fraction distribution graph of log Mw on the x axis and nPdM on the y axis.
  • the Tie molecule fraction distribution graph can be obtained from the data of the GPC curve graph in which the x axis is log Mw and the y axis is dw / dlogMw and the DSC measurement result.
  • Mw means weight-average molecular weight
  • w means weight fraction.
  • the log Mw of the x-axis in the Tie molecule fraction distribution graph is the same as the x-axis of the GPC curve graph.
  • the nPdM of the y-axis in the Tie molecule fraction distribution graph may be calculated from data obtained from a GPC curve graph.
  • n is the number of polymers having a molecular weight of M, which can be obtained as (dw / dlog Mw) / M from GPC curve data, and P can be calculated from Equation 1 as a probability of generating a connecting molecule.
  • dM is dlogMw ⁇ x-axis data of the GPC curve, X n + 1> -dlogMw ⁇ x-axis data of the GPC curve, Xn>.
  • r is the end-to-end distance of a random coil
  • a is the amorphous layer thickness.
  • Equation 1 l c may be calculated from Equation 2 below, wherein Tm is a melting temperature of polyethylene.
  • T m 0 is 415K
  • ⁇ e is 60.9 ⁇ 10 -3 Jm -2
  • ⁇ h m is 2.88 ⁇ 10 3 Jm -3
  • Equation 1 l a may be calculated from Equation 3 below.
  • ⁇ c is the density of crystalline, 1000 kg / m 3 ,
  • ⁇ a is the density of amorphous phase, 852 kg / m 3 ,
  • ⁇ c is weight fraction crystallinity and can be measured by DSC.
  • a tie molecule fraction (Tie molecule fraction; ) Can be calculated.
  • nPdM is as described above with respect to Equation 1,
  • P is a value obtained from the above equation (1).
  • the polyethylene has a melting temperature (Tm) of about 130 ° C. or more or about 130 ° C. to about 140 ° C., or about 135 ° C. or more or about 135 ° C. to about 140 ° C., or about 135.6 ° C. or more or about 135.6 ° C. to about 140 ° C, or at least 136 ° C or from about 136 ° C to about 140 ° C.
  • Tm melting temperature
  • the melting temperature (Tm) can be measured using a differential scanning calorimeter (DSC, device name: Q20, manufacturer: TA Instruments). Specifically, the polyethylene was heated to 190 ° C. by raising the temperature, and then maintained at that temperature for 5 minutes, then down to 50 ° C., and then increased again to the top of the DSC (Differential Scanning Calorimeter, TA) curve. Let corresponding temperature be melting point (Tm). At this time, the rate of temperature rise and fall is 10 °C / min, the melting point (Tm) is shown as a result measured in the section where the second temperature rises.
  • DSC differential scanning calorimeter
  • the polyethylene has a crystallinity of about 55% or more, or about 55.5% or more, or about 55.8% or more, or about 56% or more, or about 56.5% or more, or about 57% or more. This means that the content of the polyethylene crystal structure is high and dense, which is characterized by a hard change of the crystal structure during the chlorination process.
  • DSC differential scanning calorimeter
  • the polyethylene according to the invention is characterized in that to increase the linking molecule content and to increase the crystal structure transition temperature as described above.
  • the crystal structure transition temperature of the polyethylene may be at least about 108 ° C, or at least about 108.2 ° C, or at least about 115 ° C, or at least about 120 ° C, or at least about 120.5 ° C, or at least about 122 ° C.
  • the crystal structure transition temperature of the polyethylene may be about 132 ° C or less, or about 130 ° C or less, or about 128 ° C or less.
  • the crystal structure transition temperature means a temperature at which a change in the crystal arrangement occurs while the lamellar structure forming the crystal is maintained.
  • the crystal structure transition temperature may be measured using a dynamic thermal analyzer (DMA: Dynamic Mechanical Analyzer, device name: Q800, manufacturer: TA Instruments).
  • DMA Dynamic Mechanical Analyzer
  • the temperature is lowered to -60 ° C, maintained at that temperature for 5 minutes, and then the temperature is increased to 140 ° C, whereby the top of the tan ⁇ curve is determined at the transition temperature of the crystal structure.
  • DMA Dynamic Mechanical Analyzer
  • the temperature is lowered to -60 ° C, maintained at that temperature for 5 minutes, and then the temperature is increased to 140 ° C, whereby the top of the tan ⁇ curve is determined at the transition temperature of the crystal structure.
  • FIG. 1 the change of the polyethylene crystal arrangement before and after the crystal structure transition temperature is shown.
  • the polyethylene of the present invention means that the crystal structure transition temperature is close to the melting temperature of 108 ° C. or more, so that the change in crystal arrangement takes place at a higher temperature, which has a characteristic that the morphology of the polyethylene particles is hard to change during the chlorination process. .
  • the polyethylene has an endothermic onset temperature of about 125 ° C. or more or about 125 ° C. to about 134 ° C., or about 126 ° C. or more or about 126 ° C. to about 132 ° C., or about 126.3 ° C. or more or about 126.3 ° C. to about 132 ° Or about 126.5 ° C. or more or about 126.5 ° C. to about 130 ° C., or about 126.8 ° C. or more or about 126.8 ° C. to about 130 ° C.
  • the endothermic initiation temperature of the polyethylene is the temperature at which the polymer folding constituting the lamella begins to unwind, and is measured by the temperature at which the onset of the melting temperature peak occurs in the DSC analysis result.
  • This endothermic onset temperature represents the temperature at which melting begins to occur, and the polyethylene of the present invention is close to the melting temperature at endothermic onset temperature of 125 ° C. or higher, which means that melting occurs at a higher temperature, which means that surface melting during the chlorination process occurs. This has a feature that is difficult to occur.
  • the endothermic onset temperature of the polyethylene may be about 134 °C or less, or about 132 °C or less, or about 130 °C or less.
  • the endothermic onset temperature can be measured using a differential scanning calorimeter (DSC, device name: Q20, manufacturer: TA Instruments). Specifically, by heating the polyethylene to 190 °C to maintain the temperature for 5 minutes, then down to 50 °C, and then increase the temperature again of the DSC (Differential Scanning Calorimeter, TA) analysis results obtained
  • DSC Different Scanning Calorimeter
  • the polyethylene has a density of at least about 0.940 g / cm 3 or about 0.940 g / cm 3 to about 0.960 g / cm 3 , or at least about 0.945 g / cm 3 or about 0.945 g / cm 3 to about 0.960 g / cm 3 , or about 0.951 g / cm 3 or more, or about 0.951 g / cm 3 to about 0.960 g / cm 3 .
  • ASTM American Society for Testing Materials
  • the melt index (MI) of the polyethylene ie, the melt index measured under the conditions of 230 ° C. and a load of 5 kg by the method of American Society for Testing Materials (ASTM) D 1238, is about 0.1. g / 10 min to about 10 g / 10 min, or about 0.1 g / 10 min to about 5 g / 10 min, or about 0.1 g / 10 min to about 2 g / 10 min, or about 0.1 g / 10 min to about 0.95 g / 10 min Can be.
  • ASTM American Society for Testing Materials
  • the polyethylene according to the present invention can be produced by polymerizing ethylene under a metallocene catalyst comprising at least one member selected from the group consisting of compounds represented by the following formulas (1) to (4).
  • M 1 is a Group 4 transition metal
  • Cp 1 and Cp 2 are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals One, they may be substituted with a hydrocarbon of 1 to 20 carbon atoms;
  • R a and R b are the same as or different from each other, and each independently hydrogen, C 1-20 alkyl, C 1-10 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 6-10 aryloxy, C 2-20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, or C 2-10 alkynyl;
  • Z 1 is a halogen atom, C 1-20 alkyl, C 2-10 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 6-20 aryl, substituted or unsubstituted C 1-20 alkylidene , Substituted or unsubstituted amino, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy;
  • n 1 or 0;
  • M 2 is a Group 4 transition metal
  • Cp 3 and Cp 4 are the same as or different from each other, and each independently one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals They may be substituted with a hydrocarbon having 1 to 20 carbon atoms;
  • R c and R d are the same as or different from each other, and each independently hydrogen, C 1-20 alkyl, C 1-10 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 6-10 aryloxy, C 2-20 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 8-40 arylalkenyl, or C 2-10 alkynyl;
  • Z 2 is a halogen atom, C 1-20 alkyl, C 2-10 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 6-20 aryl, substituted or unsubstituted C 1-20 alkylidene , Substituted or unsubstituted amino, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy;
  • B 1 is one or more of a carbon, germanium, silicon, phosphorus or nitrogen atom containing radical which crosslinks the Cp 3 R c ring and the Cp 4 R d ring or crosslinks one Cp 4 R d ring to M 2 Or a combination thereof;
  • n 1 or 0;
  • M 3 is a Group 4 transition metal
  • Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radicals, which may be substituted with hydrocarbons having 1 to 20 carbon atoms Can be;
  • R e is hydrogen, C 1-20 alkyl, C 1-10 alkoxy, C 2-20 alkoxyalkyl, C 6-20 aryl, C 6-10 aryloxy, C 2-20 alkenyl, C 7-40 alkylaryl , C 7-40 arylalkyl, C 8-40 arylalkenyl, or C 2-10 alkynyl;
  • Z 3 is a halogen atom, C 1-20 alkyl, C 2-10 alkenyl, C 7-40 alkylaryl, C 7-40 arylalkyl, C 6-20 aryl, substituted or unsubstituted C 1-20 alkylidene , Substituted or unsubstituted amino, C 2-20 alkylalkoxy, or C 7-40 arylalkoxy;
  • B 2 is at least one or a combination of carbon, germanium, silicon, phosphorus or nitrogen atom containing radicals which crosslink the Cp 5 R e ring and J;
  • J is any one selected from the group consisting of NR f , O, PR f and S, wherein R f is C 1-20 alkyl, C 2-10 alkenyl, C 2-20 alkoxyalkyl, or C 6-20 aryl ego;
  • R 1 to R 17 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 7-20 alkylaryl, or C 7-20 Arylalkyl,
  • L is C 1-10 straight or branched alkylene
  • D is -O-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C 1 -20 alkyl, C 2-20 alkenyl, or C 6-20 aryl,
  • A is hydrogen, halogen, C 1-20 alkyl, C 2-20 alkenyl, C 6-20 aryl, C 7-20 alkylaryl, C 7-20 arylalkyl, C 1-20 alkoxy, C 2-20 alkoxy Alkyl, C 2-20 heterocycloalkyl, or C 5-20 heteroaryl,
  • Q is carbon (C), silicon (Si) or germanium (Ge),
  • M 4 is a Group 4 transition metal
  • X 1 and X 2 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.
  • the C 1-20 alkyl includes linear or branched alkyl, and specifically methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and the like. However, this is not limiting.
  • the C 2-20 alkenyl includes straight or branched alkenyl, and specifically may include allyl, ethenyl, propenyl, butenyl, pentenyl, and the like, but is not limited thereto.
  • the C 6-20 aryl includes monocyclic or condensed aryl, and specifically includes phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, and the like, but is not limited thereto.
  • the C 5-20 heteroaryl includes monoaryl or condensed heteroaryl and includes carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, triazine, tetra Hydropyranyl, tetrahydrofuranyl, and the like, but are not limited thereto.
  • Examples of the C 1-20 alkoxy include a methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, cyclohexyloxy, and the like, but are not limited thereto.
  • Examples of the C 6-10 aryloxy include phenoxy, biphenoxy, naphthoxy, and the like, but are not limited thereto.
  • Halogen may include fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and the like, but is not limited thereto.
  • Group 4 transition metal examples include titanium (Ti), zirconium (Zr), hafnium (Hf), and the like, but are not limited thereto.
  • substituents are optionally a hydroxy group within the range to exhibit the same to similar effects as the desired effect; halogen; Alkyl or alkenyl, aryl, alkoxy; Alkyl or alkenyl, aryl, alkoxy comprising one or more heteroatoms of group 14 to 16 hetero atoms; Silyl; Alkylsilyl or alkoxysilyl; Phosphine groups; Phosphide groups; Sulfonate groups; And it may be substituted with one or more substituents selected from the group consisting of sulfone groups.
  • metallocene catalyst for carrying out the ethylene polymerization of the present invention one containing at least one selected from the group consisting of compounds represented by Formulas 1 to 4 as a catalyst precursor may be used.
  • M 1 may be zirconium (Zr) or hafnium (Hf), preferably may be zirconium (Zr).
  • Cp 1 and Cp 2 may each be cyclopentadienyl, indenyl, or fluorenyl.
  • R a and R b may each be hydrogen, C 1-6 alkyl, C 7-12 arylalkyl, C 2-12 alkoxyalkyl, C 6-12 aryl, or C 2-6 alkenyl, preferably Hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, butenyl, phenyl, phenyl substituted methyl, phenyl substituted butyl, or tert-butoxyhexyl.
  • Z 1 may be each halogen atom, preferably chlorine (Cl).
  • n may be 1.
  • the compound represented by Chemical Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • ph represents a phenyl group.
  • M 2 may be zirconium (Zr) or hafnium (Hf), preferably may be zirconium (Zr).
  • B 1 may be a radical containing carbon (C), germanium (Ge), or silicon (Si), preferably a radical containing carbon (C) or silicon (Si), and the carbon (C) or silicon (Si) may be substituted with one or more of C 1-6 alkyl and C 2-12 alkoxyalkyl. More specifically, B 1 may be dimethylsilyl, diethylsilyl, methyl (tert-butoxyhexyl) silyl, dimethylmethylene, cyclohexylene).
  • Cp 3 and Cp 4 may be cyclopentadienyl, indenyl, or fluorenyl, respectively.
  • R c and R d may each be hydrogen, C 1-6 alkyl, C 7-12 arylalkyl, C 2-12 alkoxyalkyl, C 6-12 aryl, or C 2-6 alkenyl, preferably Hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, butenyl, phenyl, phenyl substituted methyl, phenyl substituted butyl, or tert-butoxyhexyl.
  • each Z 2 may be a halogen atom, preferably chlorine (Cl).
  • m may be 1.
  • the compound represented by Formula 2 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.
  • ph represents a phenyl group.
  • M 3 may be titanium (Ti).
  • B 2 may be a radical containing carbon (C), germanium (Ge), or silicon (Si), preferably a radical containing carbon (C) or silicon (Si), and the carbon (C) or silicon (Si) may be substituted with one or more of C 1-6 alkyl and C 2-12 alkoxyalkyl. More specifically, B 2 may be dimethylsilyl, diethylsilyl, methyl (tert-butoxyhexyl) silyl, dimethylmethylene, cyclohexylene).
  • J is NR f
  • R f may be C 1-6 alkyl, C 6-12 aryl, C 2-6 alkenyl, or C 2-12 alkoxyalkyl, preferably methyl, ethyl, propyl , Isopropyl, n-butyl, tert-butyl, butenyl, phenyl, or tert-butoxyhexyl.
  • Cp 5 may be cyclopentadienyl, indenyl, or fluorenyl.
  • R e may be hydrogen, C 1-6 alkyl, C 7-12 arylalkyl, C 2-12 alkoxyalkyl, C 6-12 aryl, or C 2-10 alkenyl, preferably hydrogen, methyl, Ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, butenyl, phenyl, phenyl substituted methyl, phenyl substituted butyl, or tert-butoxyhexyl.
  • Z 3 may be each a halogen atom, preferably chlorine (Cl).
  • the compound represented by Formula 3 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
  • M 4 may be zirconium (Zr) or hafnium (Hf), preferably zirconium (Zr).
  • Q may be silicon (Si).
  • R 1 to R 17 may each be hydrogen, C 1-8 alkyl, C 2-8 alkenyl, or C 6-12 aryl, preferably methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, or phenyl, but is not limited thereto.
  • L is more preferably C 4-8 linear or branched alkylene, but is not limited thereto.
  • the alkylene group may be unsubstituted or substituted with C 1-20 alkyl, C 2-20 alkenyl, or C 6-20 aryl.
  • L may be hexylene.
  • D may be -O-.
  • A may be hydrogen, C 1-6 alkyl, C 1-6 alkoxy, C 2-12 alkoxyalkyl, or C 5-12 heteroaryl, but is not limited thereto.
  • A is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-butoxymethyl group, 1-ethoxyethyl group, 1-methyl-1 -Methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group.
  • X 1 and X 2 may be each halogen, preferably chlorine (Cl).
  • the compound represented by Formula 4 may be, for example, a compound represented by the following structural formula, but is not limited thereto.
  • the polyethylene according to the present invention at least one first metallocene compound represented by Formula 1; And in the presence of one or more of the second metallocene compound selected from the compounds represented by Formulas 2 to 4, it can be prepared by polymerizing ethylene.
  • the polyethylene may be prepared in the presence of a catalyst in which at least one second metallocene compound represented by Formula 2 is mixed with one or more first metallocene compounds represented by Formula 1, or In addition to at least one first metallocene compound represented by Formula 1, at least one second metallocene compound represented by Formula 4 may be prepared in the presence of a hybrid supported catalyst.
  • polyethylene, under the metallocene catalyst as described above may be prepared while introducing hydrogen gas.
  • the hydrogen gas may be added in an amount of about 60 ppm to about 150 ppm, or about 65 ppm to about 135 ppm, based on the weight of ethylene. Specifically, based on 15 kg / hr of ethylene, hydrogen gas may be added in a content of about 0.1 g / h to about 0.2 g / hr.
  • the metallocene catalyst used in the present invention may be supported on a carrier together with a cocatalyst compound.
  • the supported metallocene catalyst may induce the formation of a long chain branch (LCB) in the polyethylene produced.
  • LCB long chain branch
  • the cocatalyst supported on the carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes the olefin under a general metallocene catalyst. If it can be used when it is not particularly limited.
  • the cocatalyst is not particularly limited as long as it is an organometallic compound containing a Group 13 metal and can be used when polymerizing ethylene under a general metallocene catalyst.
  • the cocatalyst may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 5 to 7:
  • Each R 18 is independently halogen, C 1-20 alkyl, or C 1-20 haloalkyl,
  • c is an integer of 2 or more
  • D is aluminum or boron
  • Each R 19 is 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+
  • Each E is 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 Substituted with one or more substituents selected from the group consisting of C 6-20 aryloxy.
  • the compound represented by Chemical Formula 5 may be, for example, an alkyl aluminoxane such as modified methyl aluminoxane (MMAO), methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane or the like.
  • MMAO modified methyl aluminoxane
  • MAO methyl aluminoxane
  • ethyl aluminoxane isobutyl aluminoxane
  • butyl aluminoxane or the like.
  • the alkyl metal compound represented by the formula (6) is, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro Aluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, 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 (7) 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, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o, p-dimethylphenyl) boron, trimethyl ammonium tetra (o, p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluoropheny
  • the amount of the supported promoter 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, and preferably has a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface.
  • Carriers can be used.
  • silica, silica-alumina, silica-magnesia, etc., dried at high temperature may 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. If the drying temperature of the carrier is less than 200 °C water is too much to react with the surface of the water and the promoter reacts, if it exceeds 800 °C the surface area is reduced as the pores of the carrier surface is combined, and also a lot of hydroxyl groups on the surface It is not preferable because it disappears and only siloxane groups remain and the reaction site with the promoter decreases.
  • the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 mmol / g to 10 mmol / g, more preferably 0.5 mmol / g to 5 mmol / g.
  • the amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than 0.1 mmol / g, the reaction site with the promoter is small, and if the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. not.
  • the mass ratio of the total transition metal to the carrier included 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 can be exhibited.
  • the mass ratio of cocatalyst compound to carrier may be from 1: 1 to 1: 100.
  • 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 ethylene polymerization reaction may be performed using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor.
  • 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 or about 80 ° C to about 150 ° C.
  • the polymerization pressure is from about 1 kgf / cm 2 to about 100 kgf / cm 2 , preferably from about 1 kgf / cm 2 to about 50 kgf / cm 2 , more preferably from 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, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, such as dichloromethane and chlorobenzene.
  • the solution may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom.
  • the solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.
  • the reaction with chlorine may be carried out by dispersing the prepared polyethylene with water, an emulsifier and a dispersant, and then adding a catalyst and chlorine.
  • polyether or polyalkylene oxide may be used as the emulsifier.
  • the dispersant may be a polymer salt or an organic acid polymer salt, and the organic acid may be methacrylic acid or acrylic acid.
  • the catalyst may be used a chlorination catalyst used in the art, for example benzoyl peroxide may be used.
  • the chlorine may be used alone, but may be mixed with an inert gas.
  • the reaction is preferably performed at about 60 ° C. to about 150 ° C. or about 100 ° C. to about 140 ° C., and the reaction time is preferably about 10 minutes to about 10 hours or about 30 minutes to about 8 hours.
  • the chlorinated polyethylene produced by the above reaction can be further subjected to a neutralization process, a washing process and / or a drying process, and thus can be obtained in powder form.
  • the method for producing a molded article from the chlorinated polyethylene according to the present invention can be applied to conventional methods in the art.
  • the molded article may be manufactured by roll-milling the chlorinated polyethylene and extruding it.
  • t-butyl-O- (CH 2 ) 6 -C 5 H 5 was dissolved in tetrahydrofuran (THF) at -78 degrees Celsius (° C), and n-butyllithium (n-BuLi) was slowly added, followed by room temperature. After heating up, the mixture was reacted for 8 hours. The solution was added slowly to the suspension solution of ZrCl 4 (THF) 2 (170 g, 4.50 mmol) / THF (30 mL) at ⁇ 78 ° C. and further reacted at room temperature for 6 hours. . All volatiles were removed by vacuum drying and hexane was added to the resulting oily liquid to filter.
  • THF tetrahydrofuran
  • the supported catalyst prepared in Preparation Example 4 was added to a 220 L reactor of the pilot plant in a single slurry polymerization process to prepare a high density polyethylene according to the conventional method. 15 kg / hr of ethylene and 0.1 g / hr of hydrogen were continuously reacted in the form of a hexane slurry at a reactor temperature of 82 ° C., followed by a solvent removal and a drying process to prepare a high density polyethylene in powder form.
  • Example 2 It was prepared in the same manner as in Example 1 except that the ethylene content was 20 kg / hr and the hydrogen content was 1.0 g / hr to prepare a high density polyethylene in powder form.
  • the density (g / cm 3 ) of polyethylene was measured by the method of the American Society for Testing and Materials, ASTM D 1505.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Agilent), and the weight average molecular weight was divided by the number average molecular weight (PDI). ) was calculated.
  • the calibration curves formed using polystyrene standard specimens were used to derive the values of Mw and Mn.
  • the weight average molecular weight of the polystyrene standard specimens 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 species of / mol were used.
  • the melting point and melting temperature (Tm) of polyethylene were measured by using a differential scanning calorimeter (DSC, apparatus name: Q20, manufacturer: TA instruments). Specifically, the polymer was heated to a temperature of 190 ° C., held at that temperature for 5 minutes, then lowered to 50 ° C., and then increased again to melt the top of the DSC (Differential Scanning Calorimeter, manufactured by TA instruments) curve. Measured by (Tm). At this time, the rate of rise and fall of the temperature is 10 °C / min, the melting temperature (Tm) was used to measure the result of the interval of the second temperature rises and falls.
  • DSC differential scanning calorimeter
  • DSC Different Scanning Calorimeter
  • DMA Dynamic Instruments Analyzer
  • Endothermic Initiation Temperature The endothermic initiation temperature was measured as the temperature at which the onset of the melting peak occurred in the section in which the second temperature of the DSC analysis result as described above rises.
  • Chlorinated polyethylene was prepared using the polyethylenes prepared in Examples and Comparative Examples.
  • Example 1 5000 L of water and 550 kg of the high density polyethylene prepared in Example 1 were added to the reactor, followed by sodium polymethacrylate as a dispersant, oxypropylene and oxyethylene copolyether as an emulsifier, and benzoyl peroxide as a catalyst. Chlorinated by injecting gaseous chlorine for 3 hours at 132 °C. The chlorinated reactant was added to NaOH, neutralized for 4 hours, washed again with running water for 4 hours, and finally dried at 120 ° C. to prepare chlorinated polyethylene in powder form.
  • polyethylene produced in Examples 2 to 3 and Comparative Examples 1 to 3 also prepared chlorinated polyethylene in powder form, respectively, in the same manner as above.
  • Examples 1 to 3 compared with Comparative Example 1, the time required for the chlorination process is greatly shortened to about 65% to about 80%, CPE daily output is significantly increased to about 120% to about 167% excellent effect It can be seen that.
  • Comparative Examples 2 to 5 compared with Comparative Example 1, while the time required for the chlorination process is increased to about 103% to about 124%, the CPE daily production was also confirmed to decrease to about 81% to about 97% could.
  • FIGS. 2 and 3 SEM images were analyzed to compare the morphology of chlorinated polyethylene after completion of the chlorination process using polyethylene according to Example 1 and Comparative Example 1, and the results are shown in FIGS. 2 and 3, respectively.
  • Figure 2 in the case of Example 1 it can be seen that most have an irregular shape and the surface is rough.
  • Figure 3 in the case of Comparative Example 1 it was confirmed that it has a recessed form and the surface is smooth. This is because in Example 1, there was little structural change in the surface and inside of the particles during the chlorination process. Meanwhile, in Comparative Example 1, the pores are blocked by the surface melting during the chlorination process, and the surface becomes smooth, and the water trapped inside the particles is removed in the drying process to have a recessed shape.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Un polyéthylène, selon la présente invention, présente une répartition de taille de particules étroite et réduit au minimum la variation de structure cristalline, et par conséquent, en faisant réagir celui-ci avec du chlore, un polyéthylène chloré présentant une excellente productivité de chloration et une excellente stabilité thermique peut être produit.
PCT/KR2019/011171 2018-08-30 2019-08-30 Polyéthylène et polyéthylène chloré associé WO2020046051A1 (fr)

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EP19853688.0A EP3770185A4 (fr) 2018-08-30 2019-08-30 Polyéthylène et polyéthylène chloré associé
US17/052,726 US11702488B2 (en) 2018-08-30 2019-08-30 Polyethylene and chlorinated polyethylene thereof
CN201980030726.0A CN112105653B (zh) 2018-08-30 2019-08-30 聚乙烯及其氯化聚乙烯

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JP2022547499A (ja) * 2020-06-10 2022-11-14 エルジー・ケム・リミテッド ポリエチレンおよびその塩素化ポリエチレン

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JPH0762020A (ja) * 1993-08-23 1995-03-07 Tokuyama Sekisui Ind Corp 塩素化塩化ビニル樹脂の製造方法
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
KR200312308Y1 (ko) 2003-02-06 2003-05-09 주식회사 제일 유브이 유턴형 컨베이어 자외선 경화기
KR20160045434A (ko) * 2014-10-17 2016-04-27 주식회사 엘지화학 폴리에틸렌 및 이의 염소화 폴리에틸렌
KR20160121940A (ko) * 2015-04-13 2016-10-21 주식회사 엘지화학 내환경 응력 균열성이 우수한 에틸렌/알파-올레핀 공중합체
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JPH0762020A (ja) * 1993-08-23 1995-03-07 Tokuyama Sekisui Ind Corp 塩素化塩化ビニル樹脂の製造方法
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
KR200312308Y1 (ko) 2003-02-06 2003-05-09 주식회사 제일 유브이 유턴형 컨베이어 자외선 경화기
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JP2022547499A (ja) * 2020-06-10 2022-11-14 エルジー・ケム・リミテッド ポリエチレンおよびその塩素化ポリエチレン
JP7366483B2 (ja) 2020-06-10 2023-10-23 エルジー・ケム・リミテッド ポリエチレンおよびその塩素化ポリエチレン

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