WO2015046995A1 - Polyoléfine - Google Patents

Polyoléfine Download PDF

Info

Publication number
WO2015046995A1
WO2015046995A1 PCT/KR2014/009119 KR2014009119W WO2015046995A1 WO 2015046995 A1 WO2015046995 A1 WO 2015046995A1 KR 2014009119 W KR2014009119 W KR 2014009119W WO 2015046995 A1 WO2015046995 A1 WO 2015046995A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
molecular weight
polyolefin
aryl
formula
Prior art date
Application number
PCT/KR2014/009119
Other languages
English (en)
Korean (ko)
Inventor
금돈호
이충훈
박상은
정승환
조윤희
도영실
박해웅
이영우
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020140129367A external-priority patent/KR101657680B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201480048452.5A priority Critical patent/CN105518034B/zh
Priority to EP14849825.6A priority patent/EP3037441B1/fr
Priority to JP2016545698A priority patent/JP6407291B2/ja
Priority to ES14849825T priority patent/ES2966662T3/es
Priority to US15/021,149 priority patent/US9701768B2/en
Publication of WO2015046995A1 publication Critical patent/WO2015046995A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • the present invention relates to polyolefins, and more particularly, to polyolefins having a narrow molecular weight distribution and exhibiting a characteristic comonomer distribution.
  • SUBSTITUTE SHEET (RULE 26) Compounds listed in the above figure have a phosphorus (1), ethylene or propylene (2), methylidene (3) and methylene ( 4 ) bridges instead of the CGC-structured silicon bridges, but ethylene polymerization or ethylene and alphalephine are introduced, respectively. When applied to the copolymerization did not show excellent results in terms of polymerization activity and co-polymerization performance compared to CGC.
  • the present invention uses a metallocene catalyst to control the distribution of comonomers according to the molecular weight.
  • the present invention controls the distribution of comonomers according to the molecular weight by using a metallocene catalyst.
  • Eggplant is to provide a polyolefin.
  • One aspect of the present invention for achieving the above object provides a polyolefin having a molecular weight distribution of 1.5 to 3, the branch gradient number (BGN) value of 0.01 to 1.0 calculated by the following formula (1):
  • the low molecular weight grain content means the grain content at the left boundary of 80%, except for the left and right ends 10% of the total area (branch content of 2 or more carbon atoms per 1,000 carbons, unit: 1,000 C).
  • the high molecular weight side branch content means the content of the branch at the right boundary.
  • the polyolefins of the present invention can be used in various fields, such as household articles, automobiles, shock absorbers, which alone or blended with other polymers, requiring high laminar strength and elasticity.
  • FIG. 1 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Example 1.
  • FIG. 2 is a graph showing the results of GPC-FTIR measurement of polyolefin of Example 2.
  • FIG. 3 is a graph showing the results of GPC-FTIR measurement of polyolefin of Comparative Example 1.
  • first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
  • the molecular weight distribution is 1.5 to 3, and the BGN (Branch gradient number) value calculated by the following Equation 1 provides 0.01 to 1.0 polyolefin.
  • Branch Gradient Number (BGN) High Molecular Weight Side Branch Content-Low Molecular Weight
  • BGN branch gradient number
  • SCB short carbon branch
  • LCB long carbon branch
  • the BGN (Branch gradient number) value is measured by using the GPC-FTIR equipment to measure the molecular weight, molecular weight distribution, and defect content at the same time continuously, and log-log (w / w) of the molecular weight (Molecular weight, Mw) as the x-axis.
  • the molecular weight distribution curve is plotted using the logarithmic molecular weight distribution (dwt / dlog Mw) as the y-axis, the low-molecular weight content of the low-molecular weight defect is determined at the left boundary of 80% except for the left and right ends 10% of the total area.
  • the content (unit: dog / 1,000C), and the high molecular weight side branch content means the value calculated according to the following formula 1 as the content of the defect at the right boundary of the middle 80%.
  • the content of the grains is to mean the content of two or more carbon atoms per 1,000 carbons.
  • the BGN value is positive, it means that the low content of grains is low in the low molecular weight region according to the molecular weight distribution curve for the logarithm of the molecular weight, and that the side branch content is relatively high in the high molecular weight region.
  • the value is negative (-), it means a structure that has a high content of grains in a low molecular weight region and a relatively low content of grains in a high molecular weight region.
  • the polyolefin of the present invention has a BGN value measured and calculated in the same manner as 0.01 to 1.0, or about 0.01 to about 0.9, or about 0.01 to about 0.5, or about 0.01 to about 0.2, or about 0.01 to about 0.1, or From about 0.03 to about 0.1. That is, the polyolefin of the present invention has a low branched content in the low molecular weight region, a relatively high branched content in the high molecular weight region, and the slope thereof is within the above-described range.
  • the physical properties of the polyolefin can be optimized to achieve high impact strength and good mechanical properties. This results in high layer strength and good mechanical properties when compounded with other polymers such as polypropylene resins. Can be achieved.
  • the polyolefin of the present invention may have a range of about 20 to about 120 carbon atoms, preferably about 50 to about 100 carbon atoms per 1,000 carbon atoms.
  • the polyolefins of the invention also have a range 3 ⁇ 4 ⁇ in which the molecular weight distribution (weight average molecular weight / number average molecular weight) is from about 1.0 to about 3.0, or from about 1.5 to about 3.0, or from about 1.5 to about 2.8, or from about 2.0 to about 18.
  • the polyolefin of the present invention may exhibit high layer strength by having a very narrow molecular weight distribution.
  • the polyolefin has a melt flow index (Ml) measured at 190 ° C. and a 2.16 kg load condition in accordance with ASTM D1238 of about 0.1 to about 2000 g / 10 min, preferably about 0.1 to about 1000 g / 10 min, Preferably about 0.1 to 500 g / 10min, but is not limited thereto.
  • Ml melt flow index
  • melt flow rate ratio (MFRR) of the polyolefin may be about 5 to about 15, preferably about 6 to about 13, but is not limited thereto.
  • density of the polyolefin can be about 0.85 to about 0.91 g cc, preferably about 0.86 to about 0.91 g / cc, more preferably about 0.86 to about 0.90 g / cc, but is not limited thereto. It is not.
  • the physical properties may be more optimized to achieve high laminar strength and good mechanical properties.
  • the polyolefin which concerns on this invention is a copolymer of ethylene which is an olefinic monomer, and an alpha olefin comonomer.
  • Alpha olefins having 3 or more carbon atoms may be used as the alpha olefin copolymer.
  • Alpha olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 4 -methylxopentene, 1'nucleene, 1-heptene, 1'octene, ⁇ decene, 1-undecene, 1-dodecene and 1- Tetradecene, 1-nuxadecene, 1-octadecene, or 1-eicosene.
  • Ateo a copolymer of said ethylene and alpha-olefin comonomer on, alpha eulre content of the pins co-monomer is from about 5 to about 70 parts by weight 0/0, preferably from about 5 to about 60 Increased 0 /., And more preferably About 10 to about 50 weight%.
  • the weight average molecular weight of the polyolefin according to the present invention may be about 10,000 to about 500,000 g / mol, preferably about 20,000 to about 200,000 g / m, but is not limited thereto.
  • the polyolefin according to the present invention has excellent layer strength when mixed with other polymers, and can be used in various fields such as household articles, automobiles, layer absorbers, and the like.
  • Polyolefins according to the present invention having the above characteristics can be obtained by copolymerization with ethylene and alpha olepin using a common metallocene compound including two metallocene compounds of different structures as catalysts,
  • the polyolefin may have a molecular weight distribution and a BGN value as described above. More specifically, the polyolefin of the present invention, the first metallocene compound represented by the formula (1); And in the presence of a common metallocene catalyst comprising a second metallocene compound represented by the formula (2), it can be obtained by combining the ethylene and alpha olepin comonomer.
  • R1 and R2 may be the same as or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid of a Group 4 metal substituted with hydrocarbyl; R 1 and R 2 or two R 2 may be connected to each other by an alkylidine including an alkyl having 1 to 20 carbon atoms or an aryl functional group having 6 to 20 carbon atoms to form a ring;
  • R3, 3 'and R3 may be the same or different from each other, and each independently Hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of said R3, R3 ', and R3 "may be linked to each other to form an aliphatic ring or an aromatic ring;
  • CY is a substituted or unsubstituted aliphatic or aromatic ring, and the substituents substituted in CY are halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an alkyl amido group having 1 to 20 carbon atoms; An aryl amido group having 6 to 20 carbon atoms, and when there are a plurality of substituents, two or more substituents in the substituents may be linked to each other to form an aliphatic or aromatic ring;
  • Ml is a Group 4 transition metal
  • Q1 and Q2 may be the same as or different from each other, and each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms.
  • M 2 is a Group 4 transition metal
  • Q3 and Q4 may be the same or different from each other, and each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Carbon number 1 Alkyl amido of from 20 to 20; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms;
  • R4 to R10 may be the same as or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Or alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms;
  • B is carbon, silicon, or germanium, and is a bridge that binds a cyclopentadienyl-based ligand and JR10 zy by a covalent bond;
  • J is a periodic table group 15 element or group 16 element
  • z is the oxidation number of the element J
  • y is the bond number of the J element
  • n is an integer of 0-10.
  • the polymerization reaction of the ethylene and alpha olefin comonomer may be made at about 130 to about 250 ° C, preferably about 140 to about 200 ° C.
  • the activity of the catalyst may be maintained even in a high temperature synthesis process of 130 ° C. or higher, so that the active point of the catalyst in the synthesis reaction of the polyolefin is 2 Make it ideal.
  • the metallocene catalyst for synthesizing the high-density pleurepine is generally not used in the solution polymerization step of applying a high reaction resistance due to its low activity in the high temperature region, but the second metallocene compound of Chemical Formula 2 is represented by Chemical Formula 1 When mixed with the first metallocene compound of the excellent catalytic activity can be exhibited even in a high temperature region of 130 ° C or more.
  • reaction reaction of the ethylene and alpha olefin comonomer may be carried out in a continuous solution polymerization process, bulk polymerization process, suspension polymerization process or emulsion polymerization process. It may proceed, but preferably by solution polymerization reaction in a single reactor.
  • polyolefin can be synthesized in a single reactor even though two different metallocene catalysts are used, and thus a simple manufacturing process can be configured to reduce process time and cost.
  • first metallocene compound of Formula 1 include, but are not limited to, the compound of Formula 3 or Formula 4.
  • R1, R2, Q1, Q2 and Ml are the same as defined in Formula 1, and R11 may be the same as or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or amido group; Two or more of the R 11 may be connected to each other to form an aliphatic ring or an aromatic ring.
  • R1, R2, Q1, Q2 and Ml are the same as defined in Formula 1, and R12 may be the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R 12 may be connected to each other to form an aliphatic ring or an aromatic ring.
  • R2 may be each independently hydrogen or methyl group
  • Q1 or Q2 may be the same or different from each other, and each independently may be a methyl group : dimethylamido group or chloride group.
  • Specific examples of the second metallocene compound of Chemical Formula 2 may include a compound of the following chemical formula, but are not limited thereto.
  • the common metallocene catalyst in the method for preparing the polyolefin, may further include a cocatalyst compound in addition to the first and second metallocene compounds described above.
  • the cocatalyst compound includes a Group 13 metal of the periodic table, and may be at least one selected from the group consisting of a compound of Formula 5, a compound of Formula 6, and a compound of Formula 7.
  • R13 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,
  • D is aluminum or boron
  • R14 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen
  • L is a neutral or cationic Lewis base
  • H is a hydrogen atom
  • Z is a Group 13 element
  • E may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
  • a compound represented by the above formula (V) may, for example, such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane may be.
  • MAO methyl aluminoxane
  • ethyl aluminoxane ethyl aluminoxane
  • isobutyl aluminoxane isobutyl aluminoxane
  • butyl aluminoxane may be.
  • alkyl metal compound represented by the formula (6) for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum,.
  • Examples of the compound represented by the formula (7) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P).
  • Tripropylammonium tetraphenylaluminum trimethylammonium tetra ( ⁇ -rylryl) aluminum, tripropylammonium tetra ( ⁇ -rylryl) aluminum, triethylammonium tetra ( ⁇ , ⁇ -dimethylphenyl) aluminum, tributylammonium Tetra ( ⁇ -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( ⁇ - trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, ⁇ , ⁇ -diethylanilinium tetraphenylaluminum, ⁇ , ⁇ - diethylanilinium tetraphenylaluminum, ⁇ , ⁇ - diethylanilinium tetrapentafluorophenylaluminum,
  • Triphenylphosphonium tetraphenylaluminum Trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra ( ⁇ -trifluoromethylphenyl) boron,
  • Triphenylcarbonium tetrapentafluorophenylboron and the like Triphenylcarbonium tetrapentafluorophenylboron and the like.
  • the content of the promoter is the amount of the first and second metallocene compound
  • the molar ratio of the Group 13 metals to Group 4 metals may be about 1 to about 10,000, preferably about 1 to about 1,000, more preferably about 1 to about 500. remind If the molar ratio is less than 1, the effect of the addition of the promoter is insignificant. If the molar ratio exceeds 10,000, the excess alkyl group, which does not participate in the reaction and the residual alkyl group, rather inhibits the catalytic reaction and may act as a catalyst poison. This may cause a problem that excess aluminum or boron will remain in the polymer.
  • a hydrocarbon solvent such as pentane, nucleic acid, heptane, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent, but is not necessarily limited thereto, and may be used in the art. Any solvent can be used.
  • the common metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for an olefin polymerization process, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof. It can be injected by dissolving or diluting with aromatic hydrocarbon solvents such as and toluene and benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene.
  • the solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.
  • a polyolefin satisfying the above-described physical properties may be manufactured. Copolymerization with alpha olefins when using a mixed metallocene catalyst is particularly induced by the second metallocene compound that makes the high molecular weight moiety, which enables the production of high performance polyolefins in which alpha olefin comonomers are concentrated on the high molecular weight chain side. do.
  • the polyolefin production can be carried out by solution polymerization, for example, can be carried out according to the conventional method while continuously supplying ethylene and alpha olefin comonomer at a constant ratio.
  • the alpha olephine comonomer is, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nucleene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1-octadecene or 1-eicosene may be used.
  • the present invention is not limited thereto.
  • the polymerization temperature when copolymerizing alpha olefin as a comonomer with the common metallocene catalyst may range from about 130 to about 250 ° C., preferably from about 140 to about 200 ° C.
  • the activity of the catalyst can be maintained even in a high temperature synthesis process of 130 ° C. or higher, so that the catalyst in the synthesis reaction of polyolefin Let the active point of be at least 2.
  • the metallocene catalyst for synthesizing high-density polyolefin is not generally used in the solution thickening step of applying a high reaction temperature because of its low activity in the high temperature region, but the second metallocene compound of Formula 2 is When mixed with the first metallocene compound, excellent catalytic activity may be exhibited even in a high temperature region of 130 ° C or higher.
  • the polymerization pressure is preferably performed at about 1 to about 150 bar, more preferably about 1 to about 120 bar, most preferably about 10 to about 120 bar.
  • the polymerization reaction of the ethylene and the alpha olefin pin comonomer can control the physical properties of the polyolefin prepared by adjusting the content of the second metallocene compound.
  • the common metallocene catalyst includes a second metallocene compound in a relatively low content. More specifically, the second metallocene compound is more than 0 mol% to less than about 50 mol%, preferably about 5 to about 30 mol%, based on the total amount of the first and second metallocene compounds, More preferably from about 5 to about 25 mol%.
  • the second metallocene compound is included in such a content ratio, it is possible to provide a polyolefin having a narrow molecular weight distribution but having a BGN value in the above-described range.
  • 1,2,3,4-tetrahydroquinoline 13.08 g, 98.24 mmol
  • diethyl ether 150 mL
  • the shield tank was immersed in a -78 ° C. low temperature bath made of dry ice and acetone and stirred for 30 minutes.
  • n-BuLi n-butyllithium, 39.3 mL, 2.5M, 98.24 mmol
  • the flask was stirred for 2 hours, the flask was cooled to room temperature while removing the generated butane gas.
  • the flask was again immersed in a -78 ° C low temperature bath to lower the silver and added CO 2 gas. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler to raise the temperature to room temperature while removing carbon dioxide gas. Thereafter, excess C0 2 gas and solvent were removed under vacuum. The flask was transferred to a dry box, pentane was added thereto, stirred vigorously, and filtered to obtain lithium carbamate of a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is 100%.
  • 6-t-buthoxyhexane was confirmed by ⁇ -NMR, and the Grignard reaction proceeded well from 6-t-butoxynucleic acid. .
  • 6-t-buthoxyhexyl magnesium chloride was synthesized.
  • the 2 L autoclave continuous process reactor was charged with nucleic acid solvent (5.38 kg / h) and 1-butene (0.82 kg / h), then the temperature at the top of the reactor was preheated to 160 ° C.
  • Triisobutylaluminum compound (0.05 mmol / min)
  • the first metallocene compound obtained above (0.45 ⁇ / ⁇ )
  • the crab 2 metallocene compound 0.05 ⁇ / min
  • dimethylanilinium tetrakis prenta Florophenyl
  • ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by copolymerization to obtain a copolymer.
  • the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured.
  • LG Chem's LLDPE (product name: SN318) prepared with a Ziegler-Natta catalyst was prepared. Comparative Example 2
  • BGN Branch gradient number: In the GPC-FTIR measurement result, the log value (log Mw) of the molecular weight (Mw) is the X-axis, and the molecular weight distribution (dwt / dlog Mw) is y for the log value.
  • the content of low molecular weight side branches is 80% at the left boundary, except for the left and right ends 10% of the total area.
  • the amount of grains was determined as the amount of grains at the right boundary of 80%, and the BGN value was obtained by calculating the value of the following formula (1). [Expression i] '
  • FIGS. 1 to 4 GPC-FTIR measurement results of the polyolefins of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIGS. 1 to 4, respectively.
  • the content of the carbon content of 2 or more carbon atoms at the left boundary point (point A) and the carbon content of 2 or more carbon atoms at the right boundary point (point B) in the middle 80% region of the molecular weight distribution curve area By measuring the content it can be seen that the BGN value calculated according to 1 has a positive value.
  • the polyolefin of Comparative Example 1 had a negative BGN value of ⁇ 0.14 and a molecular weight distribution exceeded 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne une polyoléfine présentant une distribution de poids moléculaire de 1,5 à 3,0, et une valeur de gradient de ramification (BGN) de 0,01 à 1,0. Selon la présente invention, il est possible de fournir une polyoléfine présentant d'excellentes propriétés physicomécaniques et de résistance aux chocs de par une distribution de poids moléculaire étroite et une distribution de comonomère inhérente.
PCT/KR2014/009119 2013-09-30 2014-09-29 Polyoléfine WO2015046995A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201480048452.5A CN105518034B (zh) 2013-09-30 2014-09-29 聚烯烃
EP14849825.6A EP3037441B1 (fr) 2013-09-30 2014-09-29 Polyoléfine
JP2016545698A JP6407291B2 (ja) 2013-09-30 2014-09-29 ポリオレフィン
ES14849825T ES2966662T3 (es) 2013-09-30 2014-09-29 Poliolefina
US15/021,149 US9701768B2 (en) 2013-09-30 2014-09-29 Polyolefin

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20130116760 2013-09-30
KR10-2013-0116760 2013-09-30
KR10-2014-0129367 2014-09-26
KR1020140129367A KR101657680B1 (ko) 2013-09-30 2014-09-26 폴리올레핀

Publications (1)

Publication Number Publication Date
WO2015046995A1 true WO2015046995A1 (fr) 2015-04-02

Family

ID=52743997

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/009119 WO2015046995A1 (fr) 2013-09-30 2014-09-29 Polyoléfine

Country Status (1)

Country Link
WO (1) WO2015046995A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019515097A (ja) * 2016-04-27 2019-06-06 ハンファ ケミカル コーポレーション 混成担持メタロセン触媒を用いた高密度エチレン系重合体及び製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547551A (en) * 1982-06-22 1985-10-15 Phillips Petroleum Company Ethylene polymer blends and process for forming film
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
KR960010734B1 (ko) * 1991-06-07 1996-08-07 후지쓰 가부시끼가이샤 메모리 셀 캐패시터를 구비한 반도체 메모리장치 및 그의 제조방법
JP2003507538A (ja) * 1999-08-19 2003-02-25 ボレアリス テクノロジー オイ 容器製造方法
KR20050088087A (ko) * 2002-11-27 2005-09-01 보레알리스 테크놀로지 오와이. 폴리에틸렌 조성물로서의 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4547551A (en) * 1982-06-22 1985-10-15 Phillips Petroleum Company Ethylene polymer blends and process for forming film
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
KR960010734B1 (ko) * 1991-06-07 1996-08-07 후지쓰 가부시끼가이샤 메모리 셀 캐패시터를 구비한 반도체 메모리장치 및 그의 제조방법
JP2003507538A (ja) * 1999-08-19 2003-02-25 ボレアリス テクノロジー オイ 容器製造方法
KR20050088087A (ko) * 2002-11-27 2005-09-01 보레알리스 테크놀로지 오와이. 폴리에틸렌 조성물로서의 용도

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEM. REV., vol. 103, 2003, pages 283

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019515097A (ja) * 2016-04-27 2019-06-06 ハンファ ケミカル コーポレーション 混成担持メタロセン触媒を用いた高密度エチレン系重合体及び製造方法

Similar Documents

Publication Publication Date Title
KR101726820B1 (ko) 가공성 및 환경 응력 균열 저항성이 우수한 에틸렌/1-헥센 또는 에틸렌/1-부텐 공중합체
KR101657680B1 (ko) 폴리올레핀
CN111108131A (zh) 基于烯烃的聚合物
KR102065164B1 (ko) 올레핀계 중합체
CN106795242B (zh) 基于烯烃的聚合物
KR102028063B1 (ko) 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀 중합체의 제조 방법
JP6440832B2 (ja) メタロセン化合物、メタロセン担持触媒およびこれを用いるポリオレフィンの製造方法
JP6499280B2 (ja) メタロセン担持触媒およびこれを用いるポリオレフィンの製造方法
US10669356B2 (en) Supported hybrid catalyst and method for preparing olefin polymer using the same
KR101049260B1 (ko) 새로운 포스트 메탈로센형 전이금속 화합물
KR101675509B1 (ko) 우수한 물성을 갖는 폴리올레핀
CN111491960B (zh) 基于烯烃的聚合物
WO2017111513A1 (fr) Catalyseur métallocène supporté et procédé de préparation d'une polyoléfine à l'aide de ce catalyseur
EP3330296B1 (fr) Procédé de préparation de catalyseur métallocène supporté
WO2015046995A1 (fr) Polyoléfine
CN113795524B (zh) 聚丙烯基复合材料
CN111491961B (zh) 基于烯烃的聚合物
KR102071588B1 (ko) 올레핀계 중합체
KR20210020424A (ko) 신규 전이금속 화합물 및 이를 이용한 폴리에틸렌의 제조방법
KR101579615B1 (ko) 폴리프로필렌계 수지 조성물 및 이로부터 제조되는 성형품
KR102034807B1 (ko) 신규한 전이금속 화합물
KR102034133B1 (ko) 신규한 전이금속 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
KR20170074678A (ko) 신규한 전이금속 화합물
RU2596186C2 (ru) Нанесенный на носитель неметаллоценовый катализатор, его получение и применение
KR20220062210A (ko) 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리에틸렌 공중합체의 제조 방법

Legal Events

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

Ref document number: 14849825

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016545698

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15021149

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2014849825

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE