WO2019139355A1 - Procédé pour la préparation d'une polyoléfine à l'aide d'un catalyseur métallocène hybride supporté - Google Patents

Procédé pour la préparation d'une polyoléfine à l'aide d'un catalyseur métallocène hybride supporté Download PDF

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WO2019139355A1
WO2019139355A1 PCT/KR2019/000354 KR2019000354W WO2019139355A1 WO 2019139355 A1 WO2019139355 A1 WO 2019139355A1 KR 2019000354 W KR2019000354 W KR 2019000354W WO 2019139355 A1 WO2019139355 A1 WO 2019139355A1
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substituted
unsubstituted
group
borate
polyolefin
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PCT/KR2019/000354
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English (en)
Korean (ko)
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홍복기
박진영
이시정
최이영
유성훈
박성현
한창완
김선미
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주식회사 엘지화학
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Priority claimed from KR1020190002462A external-priority patent/KR102363189B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/957,925 priority Critical patent/US11560441B2/en
Priority to EP19738286.4A priority patent/EP3715384A4/fr
Priority to CN201980006507.9A priority patent/CN111491952B/zh
Publication of WO2019139355A1 publication Critical patent/WO2019139355A1/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
    • 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
    • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • 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
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a method for producing a polyolefin using a hybrid supported metallocene catalyst.
  • Olefin polymerization catalysts can be categorized into Ziegler-Natta and metallocene catalysts, and these two highly active catalysts have been developed to suit their respective characteristics.
  • Ziegler-Natta catalysts have been widely applied to existing commercial processes since the invention in the 50s, but multi-active catalysts with multiple active sites
  • the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a metallocene compound and a cocatalyst composed of an organometallic compound composed of aluminum as the main component. , Copolymerization properties, molecular weight, crystallinity, etc. can be changed.
  • U. S. Patent No. 5,032, 562 describes a method for preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • chlorinated polyolefins such as Chlorinated Polyethylene (CPE) are widely used for the purpose of impact modifiers for pipes and window profiles through compounding with PVC.
  • CPE Chlorinated Polyethylene
  • polyethylene is reacted with chlorine in suspension. Or by reacting polyethylene with chlorine in aqueous HC1 solution.
  • excellent impact strength is required, and the strength of the compound varies depending on the physical properties of the chlorinated polyolefin.
  • the present invention is to provide a method for producing a polyolefin showing a narrow molecular weight distribution more easily and effectively in order to improve the impact strength of the shock compound.
  • the present invention is to provide a method for producing a chlorinated polyolefin to further perform a chlorination reaction after producing the polyolefin by the above method.
  • the present invention is to provide a composition comprising a chlorinated polyolefin and a vinyl chloride polymer ( ⁇ rule) produced by the above method.
  • the present invention to metallocene supported catalyst to the the metallocene compound to the second metal at least one represented by the first sensor 25, the compound and the formula 2 as a first metal at least one represented by the general formula (1) supported on a support metal, and a co-catalyst
  • a method for producing a polyolefin comprising the step of polymerizing an olefinic monomer while introducing the promoter at 70 to 140 /.
  • 01 to 020 alkyl substituted or unsubstituted 02 to 020 and alkenyl, substituted or unsubstituted alkylaryl of 07 to 040, substituted or unsubstituted arylalkyl of 07 to 040, optionally substituted 06 to 020 Aryl, substituted or unsubstituted 01 to 020 alkylidene, substituted or unsubstituted amino group, substituted or unsubstituted alkylalkoxy of 0,2 to 020, or substituted to unsubstituted arylalkoxy;
  • ⁇ are each independently of each other substituted or unsubstituted alkyl, substituted or unsubstituted 01 to (: 10 alkoxy, substituted or unsubstituted 02 to 020 alkoxyalkyl, or substituted or unsubstituted 06 To 020 aryl;
  • the show is one or more of carbon, germanium, or silicon atom-containing radicals or a combination thereof;
  • X 1 and X 2 are the same as or different from each other, and each independently a halogen atom, a substituted or unsubstituted alkyl of Cl to 020, a substituted or unsubstituted 02 to (alkenyl of 10; 0 to 0 unsubstituted) 040 alkylaryl, substituted or unsubstituted arylalkyl of 07 to 040, substituted or unsubstituted aryl of 06 to 020, substituted or unsubstituted alkylidene of 01 to 020, substituted or unsubstituted amino group, 02 to 020 Alkylalkoxy, or substituted or unsubstituted 07 to 040 arylalkoxy;
  • To Figure 17 are the same as or different from each other, and each independently hydrogen, a halogen atom, substituted or unsubstituted alkyl of 01 to 020, substituted or unsubstituted C2 to 020 alkenyl, substituted or unsubstituted 01 to ⁇ 20 Alkylsilyl, substituted or unsubstituted 01 to £ 20 silylalkyl, substituted or unsubstituted 01 to 020 alkoxysilyl, substituted or unsubstituted 01 to (10: alkoxy, substituted or unsubstituted 02 to 020 of 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • At least one is represented by the following formula (3), I? At least one of 9 to 7 is represented by the following formula (3),
  • the present invention also provides a polyolefin prepared according to the method as described above.
  • the present invention also provides a method for producing a chlorinated polyolefin comprising treating the polyolefin with chlorine (, # 10 116) to chlorinate it.
  • the present invention also provides a chlorinated polyolefin prepared according to the method as described above.
  • the present invention is the chlorinated polyolefin and chlorinated polyolefin and 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • a metallocene supported catalyst having at least one first metallocene compound represented by Formula 1 and at least one second metallocene compound represented by Formula 2 supported on a carrier, And in the presence of a cocatalyst, a method for producing a polyolefin comprising the step of polymerizing the olefin monomer 30 while the cocatalyst is added to 70 to 140 (/) can be provided.
  • the polymerization reaction is one or more first metallocene compound represented by the formula (1) and at least one second metallocene compound represented by the formula (2) is supported on the carrier It is carried out in the presence of a metallocene supported catalyst.
  • 0 1 , 0 2 are each independently substituted or unsubstituted ci to
  • the show is one or more of carbon, germanium, or silicon atom-containing radicals or a combination of sons;
  • X 1 and X 2 are the same as or different from each other, and are each independently a halogen atom, substituted or unsubstituted alkyl of 01 to 020, substituted or unsubstituted 02 to (: 10 alkenyl, substituted or unsubstituted to 040 Alkylaryl, substituted or unsubstituted arylalkyl of 07 to 040, substituted or unsubstituted aryl of 06 to 020, substituted or unsubstituted alkylidene of Cl to 020, substituted or unsubstituted amino group, 02 to 020 Alkylalkoxy, or substituted or unsubstituted 07 to 040 arylalkoxy; 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • To 7 are the same as or different from each other, and each independently hydrogen, a halogen atom, substituted or unsubstituted alkyl of 01 to 020, substituted or unsubstituted alkenyl of 02 to 020, substituted or unsubstituted Cl to 020 alkyl Silyl, substituted or unsubstituted 01-020 silylalkyl, substituted or unsubstituted 01-020 alkoxysilyl, substituted or unsubstituted 01-(: 10 alkoxy, substituted or unsubstituted 02-020 alkoxyalkyl Substituted or unsubstituted 06 to 020 aryl, substituted or unsubstituted 06 to (: 10 aryloxy, substituted or unsubstituted 07 to 040 alkylaryl, substituted or unsubstituted arylalkyl 07 to 040, Substituted or unsubstituted arylalkeny
  • 1 / is 01 to (: 10 alkylene
  • I) 1 is 06 to 020 aryl, 04 to 020 cycloalkyl, or 02 to
  • the alkyl group of 01 to 020 includes a linear, branched, and cyclic alkyl group, and specifically, methyl group (3 ⁇ 43 ⁇ 4, 111 1 ⁇ 1), ethyl group (, 11 group), propyl group (, mae), isopropyl group.
  • 11-butyl group (11-811, 11- & 71), ⁇ ; -butyl group ( ⁇ , 1 61 1; ⁇ 3 ⁇ 4 ⁇ 7 1)), pentyl group (L, near), nuclear group (3 ⁇ 4, 3 ⁇ 4 One), 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the alkylene group of Cl to 020 includes a linear or branched alkylene group, and specifically, may include methylten group, ethylene group, propylene group, butylten group, pentylene group, and nucleosilten group. no.
  • the cycloalkyl group of 04 to 020 refers to a cyclic alkyl group among the alkyl groups described above, and specifically, but not limited to a cyclobutyl group, a cyclopentyl group, a cyclonuxyl group, and the like.
  • the alkenyl group of 02 to 020 includes a straight or branched alkenyl group, and specifically, may include an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like, but is not limited thereto.
  • the aryl groups of 06 to 020 include monocyclic or condensed aryl groups, and specifically include phenyl groups, biphenyl groups, naphthyl groups, phenanthrenyl groups, and fluorenyl groups, but are not limited thereto.
  • Examples of 01 to 020 alkoxy groups include, but are not limited to, methoxy, ethoxy, phenyloxy and cyclonucleooxy groups.
  • the alkoxyalkyl group of 02 to 020 is a functional group in which at least one hydrogen of an alkyl group is substituted with an alkoxy group, and specifically, a methoxymethyl group, a methoxyethyl group , an ethoxymethyl group, a ⁇ 30 -propoxymethyl group, Foxy ethyl group , Alkoxyalkyl groups such as-!;-Butoxymethyl group,!:-Butoxyethyl group, and 1 61 1; -butoxy nuclear group; Or an aryloxyalkyl group such as a phenoxynucleosil group, but is not limited thereto. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the alkyl silyl group of 01 to 020 or the alkoxysilyl group of 01 to 020 is a functional group in which 1 to 3 hydrogens of 3 ⁇ 4 are substituted with 1 to 3 alkyl groups or alkoxy groups as described above, and specifically methylsilyl group, dimethyl Alkylsilyl groups such as silyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group or dimethylpropylsilyl group; Alkoxy silyl groups, such as a methoxy silyl group, a dimethoxy silyl group, a trimethoxy silyl group, or a dimethoxy ethoxy silyl group; And alkoxyalkylsilyl groups such as methoxydimethylsilyl group, diethoxymethylsilyl group or dimethoxypropylsilyl group, but are not limited thereto.
  • the silylalkyl group of Cl to 020 is 1 of
  • the halogen 0 13 1 0 yo 611 ) may be fluorine), chlorine band), bromine (a) or iodine (I).
  • the sulfonate group may be an alkyl group of 01 to 020 in the structure of -0- ' 2- .
  • the 01 to 020 sulfonate group may include a methanesulfonate group or a phenylsulfonate group, but is not limited thereto.
  • a hydroxyl group optionally within the range to be exerted; halogen; Alkyl or alkenyl, aryl, alkoxy groups; An alkyl group or alkenyl group, an aryl group, an alkoxy group containing at least one hetero atom of the group 14 to 16 hetero atoms; Silyl groups; Alkylsilyl group or alkoxysilyl group; Phosphine groups; Phosphide groups; Sulfonate groups; And it may be substituted with one or more substituents selected from the group consisting of sulfone groups.
  • the Group 4 transition metals include titanium (), zirconium ( ⁇ ), and hafnium 0, but are not limited thereto.
  • an olefin polymer prepared using a grouping medium having a transition metal compound containing a cyclopentyl radical as ligands has shown a problem of controlling molecular weight distribution.
  • polyolefins prepared using a catalyst supported with a transition metal compound having a cyclopentyl radical as a ligand have a problem that it is difficult to produce chlorinated polyolefins having a high elongation when chlorinated by a wide molecular weight distribution.
  • an olefin is used by using a hybrid supported catalyst including a metallocene compound of Formula 1 and Chemical Formula 2 as described above.
  • the first metallocene compound contains a long chain branch and is easy to prepare a low molecular weight olefin polymer, and the second metallocene compound is less than that of the first metallocene compound. It is easy to prepare olefin polymers of relatively high molecular weight, including positive long chain branches. In particular, there are many long chain branches in the polymer, and when the molecular weight is large, the melt strength increases. However, in the case of the first metallocene compound, there are limitations in improving the low molecular weight compared to the long chain branches. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • a first metallocene compound containing a relatively large long chain branch and producing a polymer having a low molecular weight and a second metallocene compound producing a polymer having a relatively low long chain branch and a high molecular weight By using a hybrid supported catalyst, molecular weight distribution can be effectively controlled while maintaining excellent high molecular weight.
  • the long-chain branching present in the polymer is located at a relatively low molecular weight side, thereby improving molecular weight distribution.
  • the first metallocene compound represented by Chemical Formula 1 has a structure including a ligand of indenyl series, and when the catalyst of such a structure is polymerized, there is a small amount of long chain branching, and molecular weight distribution words, ⁇ ! ), Melt Flow Index 6 ⁇ ⁇ 1? 6 yo, 1 13 ⁇ 4) relatively narrow polymer can be obtained.
  • Chemical Formula 1 is or;
  • the hybrid supported catalyst can provide an olefin polymer having excellent processability.
  • Specific examples of the metallocene compound of Formula 1 may include bis (3- (6- 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the ligand compound may be prepared by various synthesis processes, and then a metal precursor compound may be added to perform metallization (0 ⁇ 1 011) , but the present invention is not limited thereto. You can refer to it.
  • the second metallocene compound represented by the formula (2) includes a specific substituent cyclopentylmethyl group in the ligand, the ligand has a structure that is crosslinked by such. When the catalyst of this structure is polymerized, there is a small amount of long chain branching, and the molecular weight distribution 1) 1 ,
  • a narrow polymer can be obtained.
  • the molecular weight of the olefin polymer prepared by adjusting the degree of steric hindrance effect according to the type of substituted functional group of the ligand can be easily adjusted.
  • Chemical Formula 2 is, ⁇ or; The show is carbon, germanium, or silicon; 0 1 , ⁇ are each independently alkyl of 01 to 020, or alkoxyalkyl of 02 to 20; Or I? 7 is represented by the following formula (3), yo 10 or Figure 16 is represented by the following formula (3), I?
  • the remainder of 1 to 7 is hydrogen, halogen, or alkyl of 01 to 020; X 1 and X 2 may each independently be a halogen atom.
  • the catalyst can provide an olefin polymer having excellent processability.
  • Is C1 to C10 alkylene and D 2 is C6 to C20 aryl or C4 to C20 cycloalkyl.
  • D 2 is C6 to C20 aryl or C4 to C20 cycloalkyl.
  • A is silicon;
  • Q 1 , Q 2 are each independently methyl, ethyl, propyl, or tert-butoxynucleus;
  • R 2 or R 7 is represented by the following Chemical Formula 3b,
  • R 10 or R 16 is represented by the following Chemical Formula 3b, and the remaining of R 1 to R 17 are hydrogen;
  • X 1 and X 2 may be each independently a halogen atom.
  • R 2 and R 16 are represented by the following formula (3b), R 1 , R 3 to R 15 , and R 17 may be hydrogen.
  • the second metallocene compound represented by Formula 2 may be synthesized by applying known reactions. Specifically, after preparing the ligand compound through a variety of synthetic processes may be prepared by adding a metal precursor compound to perform a metal ray ( 111 31 13 011) , but is not limited to this, a more detailed synthesis method is See also. As such, the hybrid supported metallocene catalyst may include the first and second metallocene compounds, and may effectively produce a polyolefin having excellent processability and high molecular weight of a linear polymer with a wide molecular weight distribution. .
  • the mixed molar ratio of the first metallocene compound and the second metallocene compound may be about 1: 1 to 1: 3 or about 1: 1 to 1: 2.
  • the mixed molar ratio of the first metallocene compound and the second metallocene compound may be 1: 1 or more in terms of molecular weight control, and may be 1: 3 or less for high activity.
  • the method for producing a polyolefin according to the present invention by using a hybrid supported catalyst containing a specific metallocene compound as described above by optimizing the amount of cocatalyst to perform the olefin polymerization process, polyolefin showing a narrow molecular weight distribution To improve the chlorinated polyolefin and impact strength Can be manufactured effectively.
  • the polymerization reaction to prepare a polyolefin in the present invention should be carried out under a promoter in order to prevent the catalyst activity lowered by water in the polymerization solvent, the promoter is about 70 00 / ⁇ to about 140 00 / ⁇ 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the cocatalyst may be introduced at about 80 / dl to about 135 00 / ⁇ , or about 90 (/ to about 130 / dl, or about 90 (/ addition to about 110 /).
  • the input amount of the promoter gas should be about 70 cc / hx or more in terms of complete moisture removal in the polymerization solvent, and in the case of excessive injection, about 140 00 in terms of preventing the activity deterioration due to the reaction with the catalyst. Should be less than / ⁇
  • 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 olefins under a general metallocene catalyst.
  • the polymerization reaction may be carried out by homopolymerization with one olefin monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
  • the polymerization reaction may be carried out in a slurry phase polymerization in a hydrocarbon solvent (for example, an aliphatic hydrocarbon solvent such as nucleic acid, butane, pentane, etc.).
  • a hydrocarbon solvent for example, an aliphatic hydrocarbon solvent such as nucleic acid, butane, pentane, etc.
  • the first and second metallocene compounds according to the present invention exhibit excellent solubility in aliphatic hydrocarbon solvents, they are stably supplied to the dissolution and reaction system, and the polymerization reaction can be effectively progressed.
  • the polyolefin and the manufacturing method according to an embodiment of the present invention In the polymerization reactor, for example, the polymerization may proceed in the presence of an inert gas such as nitrogen.
  • a hydrogen gas may be used for controlling the molecular weight and the molecular weight distribution of the polyolefin.
  • the polymerization reaction pressure is about 6.8 1 3 ⁇ 4 / 11 2 to about 8.7 1 3 ⁇ 4 / 11 2 , or about 7.0 1 3 ⁇ 4 / (pe 2 to about 8.5 1 3 ⁇ 4 / (L 2 , or about 8.0 1 3 ⁇ 4 / ( ® 2 to about 8.5 1 3 ⁇ 4 / 011 2 ).
  • the polymerization pressure is blocked by high molecular weight and overproduction 0 31 to 3 ⁇ 4 )
  • It may be about 8.7 1 3 ⁇ 4 / 2 or less under the polymerization conditions in consideration of the reduction of ethylene source unit.
  • an organic solvent may be further used in the polymerization reaction as a reaction medium or a diluent. Such an organic solvent may be used in an amount such that slurry phase polymerization may be appropriately performed in consideration of the content of the olefin monomer.
  • the cocatalyst compound may include at least one of an aluminum-containing first cocatalyst of Formula 4 and a borate-based second cocatalyst of Formula 5 below.
  • ,,, and are the same as or different from each other, and are each independently hydrogen, halogen, a hydrocarbyl group of Cl to 020, or a hydrocarbyl group of 01 to 020 substituted with halogen;
  • 01 is an integer of 2 or more
  • Is a monovalent polyvalent ion 6 is boron in the +3 oxidation state, and are each independently a hydride group, a dialkyl amido group, a halide group, an alkoxide group, an aryl oxide group, a hydrocarbyl group, and a haloka. It is selected from the group consisting of a bil group and a halo-substituted hydrocarbyl group, which has up to 20 carbons, but is a halide group at less than one position.
  • the first cocatalyst of Chemical Formula 4 may be an alkylaluminoxane compound or a trialkylaluminum compound in which a repeating unit is bonded in a linear, circular or reticulated form.
  • the alkyl group bonded to aluminum in the first cocatalyst compound may be one having 1 to 20 carbon atoms or 1 to 10 carbon atoms, respectively.
  • a first catalyst examples include alkyl aluminoxane compounds such as methyl aluminoxane ([]), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane; Or trialkylaluminum compounds such as trimethylaluminum, triethylaluminum 03 ⁇ 40, triisobutylaluminum, trinuxylaluminum, trioctylaluminum or isoprenylaluminum.
  • alkyl aluminoxane compounds such as methyl aluminoxane ([]), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane
  • trialkylaluminum compounds such as trimethylaluminum, triethylaluminum 03 ⁇ 40, triisobutylaluminum, trinuxylaluminum, trioctyla
  • the second cocatalyst of Formula 5 may be a borate compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt.
  • a second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • Borate compounds in the form of trisubstituted ammonium salts such as tetrafluorophenyl) borate; Borate type in the form of dialkyl ammonium salt, such as dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, ditetedecyl ammonium tetrakis (pentafluorophenyl) borate, or dicyclonucleosilammonium tetrakis (pentafluorophenyl) borate Compound; Or triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate or tri (2,6-, 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the first and second metallocene compounds in the hybrid supported metallocene catalyst may be stably supported on the carrier by having the above-described structural characteristics.
  • a carrier containing a hydroxyl group or a siloxane group may be used.
  • the carrier may be a carrier containing a highly reactive hydroxyl group or siloxane group by drying at high temperature to remove moisture on the surface.
  • the carrier may be silica, alumina, magnesia or mixtures thereof, and silica may be more preferable.
  • the carrier may be dried at a high temperature, for example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, which are typically 3 ⁇ 40, 3 ⁇ 4 (: 0 3, 6 3804 and 3 ⁇ 43 ⁇ 40). 3) atda can include an oxide, carbonate, sulfate, nitrate component of 2, and so on.
  • the drying temperature of the carrier is about 200 To about 800 ° C., and from about 300 0 to about 600 Further preferred, about 300 X: to about 400 X: most preferred.
  • the drying temperature of the carrier is about 200 If the water content is less than the water, the surface water and the cocatalyst react with each other. If the water content exceeds 800 ° C , the pores on the surface of the carrier are combined to reduce the surface area. The reaction site with the promoter decreases, which is undesirable.
  • the amount of hydroxy groups on the surface of the carrier is from about 0.1 1 to about 101 / to
  • 1 01 / yaw is preferred, and more preferably from about 0.5 ⁇ / dragon to about 5 11 ⁇ 101 / sugar.
  • the amount of hydroxy groups on the surface of the carrier may be determined by the method and conditions for the preparation or drying conditions, such as temperature, time, vacuum or spray drying. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • a promoter may be further supported on a carrier to activate the metallocene compound.
  • the cocatalyst supported on the carrier is not particularly limited as long as it is an organometallic compound including a Group 13 metal, and can be used when polymerizing olefins under a general metallocene catalyst. Specific examples of such promoters are as described above.
  • the mass ratio of the total transition metal to the carrier included in the first metallocene compound and the second metallocene compound may be 1:10 to 1: 1000.
  • the mass ratio of the promoter catalyst to the carrier used in the hybrid supported metallocene catalyst may be 1: 1 to 1: 100.
  • the mass ratio includes a promoter and a carrier, the active and polymer microstructures can be optimized.
  • the hybrid supported metallocene catalyst of the embodiment the step of supporting the promoter on the carrier; Supporting the first and second metallocene compounds on the carrier on which the promoter is supported; It can be prepared by a manufacturing method comprising a.
  • the first and second metallocene compounds may be supported one by one in sequence, or two may be supported together.
  • the shape of the hybrid supported metallocene catalyst may be improved by first supporting the second metallocene catalyst having a relatively poor shape ( 1110 to 1 1010 ), and thus the second metallocene. After supporting the catalyst, the first metallocene catalyst can be supported in order.
  • the supporting conditions are not particularly limited and may be performed in a range well known to those skilled in the art. For example, it is possible to proceed by using a high-temperature support and a low-temperature support as appropriate, for example, the support temperature is possible in the range of about -30 3 ⁇ 4 to 150 X :, preferably at room temperature (about 25 V)
  • the reacted supported catalyst can be used as it is by removing the reaction solvent by filtration or distillation under reduced pressure, or, if necessary, by using a Soxhlet filter with an aromatic hydrocarbon such as toluene.
  • the preparation of the supported catalyst may be performed under a solvent or a solventless.
  • the solvents that can be used include aliphatic hydrocarbon solvents such as nucleic acids or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, ethers such as diethyl ether or tetrahydrofuran 03 ⁇ 4.
  • aliphatic hydrocarbon solvents such as nucleic acids or pentane
  • aromatic hydrocarbon solvents such as toluene or benzene
  • hydrocarbon solvents substituted with chlorine atoms such as dichloromethane
  • ethers such as diethyl ether or tetrahydrofuran 03 ⁇ 4.
  • Most organic solvents, such as a solvent, acetone, and ethyl acetate, are mentioned, and nucleic acid, heptane, toluene, or dichloromethane are preferable.
  • the hybrid supported metallocene catalyst of the embodiment can be used in the polymerization of the
  • the hybrid supported metallocene catalyst may be prepared by using a prepolymerized catalyst by contact reaction with an olefinic monomer.
  • the catalyst may be used separately, such as ethylene, propylene, 1-butene, 1-nuxene, 1-octene, and the like. It can also be prepared and used as a prepolymerized catalyst by contacting with an olefinic monomer. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the olefinic monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.
  • Specific examples of the olefin monomers include ethylene, propylene, 1-butene,
  • the metallocene supported catalyst is an aliphatic hydrocarbon solvent of 05 to (: 12, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, chloro It may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as benzene and injected into the reaction system.
  • 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.
  • the polymerization reaction is carried out by supporting at least one first metallocene compound represented by Formula 1 and at least one second metallocene compound represented by Formula 2 on a carrier.
  • other additives such as molecular weight modifiers may be carried out.
  • the polyolefin obtained according to the above-described method for producing an embodiment is characterized by having a relatively narrow molecular weight distribution.
  • melt index of the polyolefin (3 ⁇ 40 5.0, conditional drawing, 190 ° 0,
  • the polyolefin Sean and a density of about 0.94 ⁇ / 0111 3 or more or about 0.94 to about 0.96 ⁇ ⁇ 3 L 3 days.
  • the content of the crystal structure of the polyolefin is high and dense, which is characterized by a hard change of the crystal structure during the chlorination process.
  • the density of the polyolefin can be measured by the method based on Show ⁇ 3 ⁇ 41 0-792. Since the polyolefin has a relatively narrow molecular weight distribution, it shows excellent chlorine distribution uniformity in polyethylene during chlorination (1 01 ⁇ 11 ) 11 , and can significantly improve elongation, compatibility with chlorinated polyolefin, and impact reinforcement performance. have.
  • the polyolefin is characterized by having a relatively narrow molecular weight distribution, the molecular weight distribution) may be about 2.3 to about 5.0. Also,
  • the molecular weight distribution may be obtained by gel permeation chromatography (GPC, gel permeat ion chromatography, manufactured by Water) to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyolefin.
  • the weight average molecular weight can be measured and divided by the number average molecular weight.
  • GPC gel permeation chromatography
  • a Waters PL-GPC220 device may be used, and a Polymer Laboratores PLgel MIX-B 300 mm length column may be used.
  • the measurement temperature is 160 ° C
  • 1,2,4-trichlorobenzene (1,2, 4-Tr i chlorobenzene) can be used as a solvent
  • the flow rate can be applied at 1 mL / min.
  • the polyethylene sample was pretreated by dissolving in trichlorobenzene (1,2,4-Tr chlorobenzene) containing 0.0125% of BHT using GPC analysis device (PL-GP220) for 160 ° C for 10 hours, and 10 mg / It may be prepared at a concentration of 10 mL and then supplied in an amount of 200 y L.
  • the test curves formed using polystyrene standard specimens can be 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 / mo 1, 30000 g / mol, 70000 g / mol, 200000 g / mol, 700000 g / mol, 2000000 g / mol, 4000000 g / mol, 10000000
  • the polyolefin produced by the polymerization reaction as described above may be a homopolymer of an olefin that does not contain a separate copolymer, for example, an ethylene homopolymer.
  • the polyolefin is, for example, an ethylene homopolymer, preferably a high density polyethylene
  • the above-described physical properties may be more suitably satisfied.
  • high density polyethylene has excellent softening point, hardness, strength and electrical insulation, and is used for various containers, packaging films, fibers, pipes, packings, and insulating materials.
  • the metallocene supported on which at least one first metallocene compound represented by Formula 1 and at least one second metallocene compound represented by Formula 2 is supported on a carrier Polymerizing an olefinic monomer in the presence of a catalyst and a cocatalyst, while introducing the cocatalyst at 70 to 140 (/ 1 11 .; And chlorinating the polyolefin with chlorine (h).
  • And ⁇ are the same or different from each other, and are each independently selected from the group consisting of indenyl and 4, 5, 6, 7-tetrahydro-1 -indenyl radicals, which can be substituted with 01 to 020 hydrocarbons And;
  • ⁇ And are the same as or different from each other, and are each independently hydrogen, substituted or unsubstituted Cl to 020 alkyl, substituted or unsubstituted 01 to (10: alkoxy, substituted or unsubstituted alkoxyalkyl to 02 to 020, Substituted or unsubstituted aryl of 06 to 020, substituted or unsubstituted 06 to (: 10 aryloxy, substituted or unsubstituted 02 to 020 alkenyl, substituted or unsubstituted alkylaryl of 07 to 040, substitution Optionally substituted 07 to 040 arylalkyl, optionally substituted 08 to 40 arylalkenyl, or optionally substituted 02 to (10) alkynyl;
  • the show is one or more of carbon, germanium, or silicon atom-containing radicals or a combination thereof;
  • X 1 and are the same as or different from each other, and each independently a halogen atom, substituted or unsubstituted alkyl of 01 to 020, substituted or unsubstituted 02 to (alkyl of 10, substituted or unsubstituted to 040 alkyl) Aryl, substituted or unsubstituted to arylalkyl of 04 to 04, substituted or unsubstituted aryl of 06 to 02o, substituted or unsubstituted alkylidene of Cl to 020, substituted or unsubstituted amino group, 02 to 020 alkyl Alkoxy, or substituted or unsubstituted 07 to 04 arylalkoxy;
  • To 7 are the same as or different from each other , and each independently hydrogen, a halogen atom, substituted or unsubstituted alkyl of Cl to 020, substituted or unsubstituted alkenyl of 02 to 020, substituted or unsubstituted 01 to 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • At least one is represented by the following formula (3)
  • At least one of ⁇ to 7 is represented by the formula (3)
  • I) 1 is 06 to 020 aryl, 04 to 020 cycloalkyl, or C 2 to 020 alkoxyalkyl.
  • Specific reaction conditions of the step of polymerizing the olefin monomer to prepare the polyolefin, and specific examples of the first and second metallocene compounds, the carrier, the cocatalyst, and the hybrid supported catalyst including the same are as described above.
  • Chlorinated polyolefin ( ⁇ 101 ⁇ 11 6 (1 1301 016 11) can be produced by treating polyolefin with chlorine (# 10 11 ⁇ 2) to chlorinate it.
  • Such chlorinated polyolefins can generally be prepared by an aqueous phase method in which polyolefins are reacted with chlorine in suspension, or by an acid phase method in which polyethylene is reacted with chlorine in a ⁇ 1 (: 1 aqueous solution).
  • aqueous phase method in which polyolefins are reacted with chlorine in suspension
  • acid phase method in which polyethylene is reacted with chlorine in a ⁇ 1 (: 1 aqueous solution).
  • the aqueous phase method is a method of chlorination using, for example, an emulsifier and a dispersant together with water
  • the acidic method is, for example, chlorination of an acid aqueous solution such as an aqueous solution of hydrochloric acid (HC1) using an emulsifier and a dispersant. It is a way.
  • the chlorination reaction may be performed by dispersing polyethylene with water, an emulsifier and a dispersant, and then reacting with a catalyst and chlorine.
  • the emulsifier is for example polyether or polyalkylene oxide.
  • the dispersant is for example a polymer salt or an organic acid polymer salt.
  • the organic acid may be, for example, methacrylic acid, acrylic acid, or the like.
  • the catalyst is, for example, a chlorination catalyst, and in another example, a peroxide or an organic peroxide.
  • the chlorine may be used alone or in admixture with an inert gas, for example.
  • the final chlorination reaction temperature is about 60 To about 150 ° 0, about 70X: to about 145 ° 0, about 90X: to about 140X :, or about 130 To about 137 I :.
  • the chlorination reaction time is for example about 10 minutes to about 10 hours, about 1 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the time is about 6 hours, or about 2 hours to about 4 hours.
  • the chlorination reaction is another example of 100 parts by weight of polyethylene, about 0.01 parts by weight to about 1.0 parts by weight, or about 0.05 parts by weight to about 0.5 parts by weight, and about 0.1 parts by weight to about 10 parts by weight, or about 0.5 parts by weight of the dispersant.
  • the dispersant After dispersing about 5.0 parts by weight in water, about 0.01 parts by weight to about 1.0 parts by weight or about 0.05 parts by weight to about 0.5 parts by weight of chlorine and about 80 parts by weight to about 200 parts by weight or about 100 parts by weight to about 150 parts by weight can be added to react.
  • the chlorinated polyethylene produced by the reaction or chlorination process may be obtained as a powdered chlorinated polyethylene through further neutralization (washing) and washing (drying), for example.
  • the neutralization process may be a process of neutralizing the reactant, which has undergone chlorination, at about 70 ° C. to about 90 V or about 75 ° C. to about 80 ° C. as a basic solution for about 4 hours to about 8 hours.
  • the chlorinated polyolefin obtained according to the manufacturing method of the above-described embodiment has excellent chlorine distribution uniformity in the chlorinated polyolefin due to the narrow molecular weight distribution, and has high elongation and excellent compatibility with PVC. It is done.
  • the chlorinated polyolefin may have an elongation of at least 900% or from 900% to 1500%, or at least 950% or at 950% to 1400%, or at least 1200% or at 1200 to 1300%.
  • elongation (%) of chlorinated polyolefin can be measured by the method based on ASTMD-2240.
  • the chlorinated polyolefin may have a chlorine content of 20 to 45 wt%, 31 to 40 wt%, or 33 to 38 wt%.
  • the chlorine content of the chlorinated polyolefin is combustion ion chromatography (Combust ion IC, Ion 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the combustion ion chromatography method uses a combustion IC (ICS-5000 / AQF-2100H) device equipped with an IonPac AS18 (4 x 250 mm) column, internal device temperature (Inlet temperature) 900 ° C, external Out let temperature Can be measured under flow conditions of 1 mL / min using K0H (30.5 mM) as eluent at a combustion temperature of 1000 ° C.
  • the chlorinated polyolefin may be, for example, a random chlorinated polyolefin such as random chlorinated polyethylene.
  • the chlorinated polyolefin prepared according to the present invention is excellent in chemical resistance, weather resistance, flame retardancy, processability and impact strength reinforcing effect, and is widely used as an impact modifier of PVC pipe and window profile. III.
  • PVC composition ICS-5000 / AQF-2100H
  • a PVC composition comprising chlorinated polyolefin and vinyl chloride polymer (PVC) prepared by the method as described above.
  • the PVC composition may include about 1% to about 40% by weight of chlorinated polyolefin and about 60% to about 99% by weight of vinyl chloride polymer (PVC) prepared by the method described above.
  • the chlorinated polyolefin may be, for example, about 1% to about 15%, or about 5% to about 10% by weight.
  • the vinyl chloride polymer (PVC) may be, for example, about 85% to about 99% by weight, or about 90% to about 95% by weight. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the PVC composition of the present disclosure may comprise about 1% to about 20% by weight of chlorinated polyethylene of the present disclosure, about 70% to about 90% by weight of vinyl chloride polymer (PVC), about 1% to about Ti0 2. 10% by weight, about 1% to about 10% by weight of CaC0 3 and about 1% to about 10% by weight composite stearate (Ca, Zn-stearate).
  • PVC vinyl chloride polymer
  • the PVC composition may have a plasticization time of about 170 seconds or less, about 150 seconds or less, or about 150 seconds to about 100 seconds.
  • the PVC composition has a Charpy impact strength of about 10.9 kJ / m 2 measured at a low temperature of ⁇ 10 ° C., when combined with vinyl chloride polymer (PVC), for example, under 160 ° C. to 190 ° C. conditions. Or about 10.9 kJ / m 2 to about 17 kJ / m 2 , or about 11.1 kJ / m 2 or more or about 11.1 kJ / m 2 to about 16.5 kJ / m 2 , or about 13.8 kJ / m 2 or more or about 13.8 kJ / m 2 to about 16.1 kJ / m 2 . Within this range, the physical property balance and productivity are excellent.
  • the Charpy impact strength (-10 ° C, kJ / m 2 ) of the PVC composition can be measured by the method according to ASTM D-256.
  • the polyolefin having a narrow molecular weight distribution can be very effectively by introducing the content of the promoter in an optimum range in the presence of a hybrid supported metallocene catalyst containing two or more metallocene compounds having a specific chemical structure. It can manufacture.
  • the polyolefin according to the production method of the present invention is excellent in the chlorine distribution uniformity in polyethylene during chlorination (chlor inat ion), it is possible to significantly improve the elongation of the chlorinated polyolefin and compatibility with PVC and impact reinforcement performance, As a result, it has excellent chemical resistance, weather resistance, flame retardancy, processability and impact strength reinforcing effect. It can be suitably applied as impact modifier of window profile.
  • T-Buty- 0- (CH 2) 6 -C 9 H 7 was dissolved in THF at 78 ° C., and normal butyllium (n_BuLi) was slowly added, and the reaction mixture was heated to room temperature for 8 hours.
  • the solution was again synthesized as described above in a suspension solution of ZrCl 4 ( THF) 2 ( 1.70 g, 4.50 mmol) / THF (30 mL) at -78 ° C as li thium sal t) The solution was slowly added and reacted for about 6 hours at room temperature. All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of a hexane solvent.
  • T-ButW-0- (CH 2) 6 _Cl is prepared by the method presented in Tetrahedron Lett. 2951 (1988 ) using 6- chlorohexanol, and 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • the nucleic acid was removed at 70 ° C to obtain a pale yellow liquid.
  • the obtained liquid was identified to be the desired methyl (6-t-butoxy hexyl) di chi orosi lane ⁇ compound through 1 H-NMR. 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • Dilithium salt (di 1 i thium sal ts) slurry solution was slowly added to a slurry solution of ZrCl 4 ( THF) 2 (2.26 g, 6 mmol) / nucleic acid (20 mL) and further reacted at room temperature for 8 hours. The precipitate was filtered and washed several times with nucleic acid to give (tert-Bu-0- (CH 2) 6) MeSi (9-C 13 H 9) 2 ZrCl 2 compound as a red solid (4.3 g, yield 94.5%). . 0 606): 1.15 (911, £), 1.26 (3 ⁇ £), 1.58 (2 «0 ,
  • the dried silica 10 sugar was put in a glass reactor at room temperature, and 100 kPa of toluene was further added and stirred. After sufficiently dispersing the silica, 100.6% methylaluminoxane (()) / toluene solution was added to 60.6 and the temperature was increased to 80 ° (1! After lowering to, toluene was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by depressurizing.Toluene 100 1 was added again, the first metallocene compound according to Synthesis Example 1 0.25 was the reaction for 1 hour by introducing, as by dissolving in the out fall of toluene.
  • the dried silica 10 urine was put into a glass reactor at room temperature, and 100 kPa of toluene was further added and stirred. After sufficiently dispersing the silica, 60.6 was added to 10% methylaluminoxane ( ⁇ / toluene solution) and the reaction mixture was slowly reacted by raising the temperature to 80 ° (: lowering the temperature to 200 ° C for 16 hours.
  • the reactor was maintained at 82 ° C, pressure was maintained at 7.0 kg / cm 2 to 7.5 kg / cm 2 , and the polymerization was carried out for about 4 hours.
  • the polymerization product was then made into final polyethylene via a solvent removal plant and a dryer.
  • the polyethylene produced was mixed with 1000 ppm of calcium stearate (manufactured by Dubon Industries) and 2000 ppm of heat stabilizer 21B (manufactured by Songwon Industries) and then made into pellets.
  • Example 2 Preparation of Polyolefin
  • polyethylene was prepared in the same manner as in Example 1, except that triethylaluminum (TEAL) was adjusted at a flow rate of 110 cc / hr and 90 cc / hr, respectively.
  • TEAL triethylaluminum
  • polyethylene was prepared in the same manner as in Example 1, except that the polymerization process was performed using the hybrid supported metallocene catalyst according to Preparation Example 3 (precursors of Synthesis Examples 2 and 2). Prepared. Comparative Example 4: Preparation of Polyolefin
  • MIs . o and MFRRC 21.6 / 5) Melt Index (MI 5. o) for polyethylene was measured according to ASTM D1238 (Condition E, 190 ° C, 5.0 kg load) specification. In addition, the melt flow rate ratio (MFRR, 21.6 / 5) for polyethylene was calculated by dividing MFR 21.6 by MFR 5 and MFR 21.6 measured under a temperature of 190 ° C and a load of 21.6 kg according to ISO 1133. And MFR 5 according to ISO 1133 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • Elongation (%) of CPE The elongation (%) of chlorinated polyethylene was measured by the method according to ASTM D-2240.
  • Sharpy impact strength (-10 C kJ / m ! ) Of PVC compound: Sharpy impact strength (-10 ° C, kJ / m 2 ) was measured by the method according to ASTM D-256.
  • Examples 1 to 4 implement a high elongation after chlorination based on the narrow molecular weight distribution of high density polyethylene 2019/139355 1 »(: 1 ⁇ 1 ⁇ 2019/000354
  • Examples 3 and 4 exhibited a melt flow index (MFRR) of 10 or less through the reduction of TEAL input in the polymerization process, not only a narrow molecular weight distribution, but also excellent elongation characteristics of more than 1200%, respectively. It can be seen that the impact strength is improved to 13.8 kJ / m 2 and 16 kJ / m 2 .
  • Comparative Examples 1 to 5 have shown a problem that the elongation of the chlorinated polyethylene is lowered and the impact strength of the PVC compound is lowered due to the wider molecular weight distribution of the high density polyethylene.
  • Comparative Examples 1 to 5 show a high melt flow index (MFRR) of 13.8 to 14.5, and the elongation and impact strength inferior to the wider molecular weight distribution were shown.
  • Comparative Example 2 was found to have a lower molecular weight distribution effect in spite of the TEAL input control in the process, thereby lowering the impact strength of the final PVC compound.

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Abstract

La présente invention concerne un procédé pour la préparation d'une polyoléfine à l'aide d'un catalyseur métallocène hybride supporté. Selon la présente invention, une polyoléfine ayant une étroite distribution de la masse moléculaire peut être préparée très efficacement par l'injection d'une certaine quantité d'un cocatalyseur dans la plage optimale en présence d'un catalyseur métallocène hybride supporté comprenant deux ou plus de deux types de composés métallocènes ayant des structures chimiques particulières. En particulier, une polyoléfine préparée selon le procédé de préparation selon la présente invention présente une excellente homogénéité de la distribution de chlore à l'intérieur d'une polyoléfine pendant la chloration et permet d'améliorer remarquablement l'allongement, la compatibilité avec le PVC, les performances de modification de la résistance au choc et similaires d'une polyoléfine chlorée, ce qui permet d'obtenir une excellente résistance aux produits chimiques, une excellente résistance aux intempéries, un caractère ignifuge, une aptitude à la transformation, un effet de modification de la résistance au choc et similaires, et peut ainsi être appliquée de manière appropriée à un modificateur de la résistance au choc d'un tuyau en PVC, d'un profilé de fenêtre et similaires.
PCT/KR2019/000354 2018-01-11 2019-01-09 Procédé pour la préparation d'une polyoléfine à l'aide d'un catalyseur métallocène hybride supporté WO2019139355A1 (fr)

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US16/957,925 US11560441B2 (en) 2018-01-11 2019-01-09 Method for preparing polyolefin using supported hybrid metallocene catalyst
EP19738286.4A EP3715384A4 (fr) 2018-01-11 2019-01-09 Procédé pour la préparation d'une polyoléfine à l'aide d'un catalyseur métallocène hybride supporté
CN201980006507.9A CN111491952B (zh) 2018-01-11 2019-01-09 使用负载型混杂茂金属催化剂制备聚烯烃的方法

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US20210230323A1 (en) * 2018-12-10 2021-07-29 Lg Chem, Ltd. Polyethylene and Chlorinated Polyethylene Thereof
CN115260365A (zh) * 2021-04-29 2022-11-01 中国石油化工股份有限公司 支化烯烃聚合物及其制备方法和应用

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CN115260365B (zh) * 2021-04-29 2023-07-21 中国石油化工股份有限公司 支化烯烃聚合物及其制备方法和应用

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