WO2019107774A1 - Polypropylène et son procédé de préparation - Google Patents

Polypropylène et son procédé de préparation Download PDF

Info

Publication number
WO2019107774A1
WO2019107774A1 PCT/KR2018/013198 KR2018013198W WO2019107774A1 WO 2019107774 A1 WO2019107774 A1 WO 2019107774A1 KR 2018013198 W KR2018013198 W KR 2018013198W WO 2019107774 A1 WO2019107774 A1 WO 2019107774A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
molecular weight
catalyst composition
homopolypropylene
compound
Prior art date
Application number
PCT/KR2018/013198
Other languages
English (en)
Korean (ko)
Inventor
김석환
이현섭
채성민
김태진
홍대식
전상진
박희광
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 KR1020180132203A external-priority patent/KR102375854B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18883218.2A priority Critical patent/EP3647331A4/fr
Priority to CN201880046736.9A priority patent/CN110914316B/zh
Priority to US16/635,730 priority patent/US11248072B2/en
Priority to JP2020500899A priority patent/JP6893279B2/ja
Publication of WO2019107774A1 publication Critical patent/WO2019107774A1/fr
Priority to US17/546,307 priority patent/US11732069B2/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—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
    • C08F4/659—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

Definitions

  • the present invention relates to an injection-use polypropylene having a high ultrahigh molecular weight content and excellent rigidity, and a process for producing the polypropylene.
  • Polyolefins are becoming mainstream products using Ziegler-Natta catalysts, but the transition to polypropylene products (mPP) using metallocene catalysts with low odor and low dissolution characteristics is accelerating.
  • mPP polypropylene products
  • the olefin polymerization catalyst system can be classified into a Ziegler-Natta and metallocene catalyst system, and these two types of high-activity catalyst systems have been developed for each characteristic.
  • the Ziegler-Natta catalyst has been widely applied to commercial processes since its invention in the 1950s, but since it is a multi-site catalyst with multiple active sites, the polymer has a broad molecular weight distribution , There is a problem that the composition distribution of the comonomer is not uniform and there is a limit in securing desired physical properties.
  • the metallocene catalyst is composed of a combination of a main catalyst, which is a main component of the transition metal compound, and a cocatalyst, which is an organometallic compound mainly composed of aluminum.
  • a catalyst may be used as a homogeneous complex catalyst with a single active site catalyst 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • the molecular weight distribution is narrow according to the single active point characteristic and the polymer having a uniform composition distribution of the comonomer is obtained and the stereoregularity of the polymer is also controlled by changing the ligand structure of the catalyst and the polymerization conditions, Properties, molecular weight, crystallinity, and the like.
  • an object of the present invention is to provide injection-use polypropylene, specifically homopolypropylene, which has a high ultrahigh molecular weight content and a low low molecular weight content, thereby improving the injection rigidity of the product.
  • Another object of the present invention is to provide a process for producing the polypropylene for injection which is excellent in rigidity by polymerization under a low hydrogen addition polymerization condition using a specific metallocene catalyst having high hydrogen reactivity.
  • the present invention provides a homopolypropylene satisfying the following conditions:
  • the weight-average molecular weight measured by ash is not more than 150,000 (200,000 / 11101) ; A molecular weight distribution of 2.4 or less;
  • the present invention also relates to a process for the preparation of 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • the present invention provides a process for producing the homopolypropylene comprising:
  • each independently halogen or the same or different halogen is silicon or germanium
  • Each of 3 ⁇ 4 to 3 ⁇ 4 is independently the same as or different from each other, and is # alkylaryl.
  • the present invention by using a specific metallocene catalyst having a high hydrogen-reactive property and polymerizing under low hydrogen addition polymerization conditions, it is possible to provide an injection-molded polypropylene which has a narrow molecular weight distribution and has a high ultrahigh molecular weight content and a low low molecular weight content, Specifically, homopolypropylene can be produced. Therefore, the present invention is useful for providing a product having excellent physical properties.
  • homopolypropylene for injection and a method for producing the same according to a preferred embodiment of the present invention will be described in more detail. According to one embodiment of the invention, there is provided homopolypropylene satisfying the following conditions:
  • the integral value of the area where 1 ⁇ 1 ⁇ 2 is less than 4.5 is not more than 8% of the integral value of the X axis;
  • the integral value of the region where the room is 6 or more is 0.95% or more of the integral value of the X-axis
  • Residual stress ratio greater than 0.20% Residual stress ratio greater than 0.20%.
  • the present invention provides an injection-use polypropylene having a high ultrahigh molecular weight content and a low molecular weight content with improved injection rigidity, .
  • the present invention can easily produce a polypropylene having a molecular weight distribution of less than 200,000 as well as a polypropylene having a molecular weight of 200,000 or more while satisfying a narrow molecular weight distribution of 2.4 or less.
  • the low molecular weight polypropylene in the present invention may include polypropylene having Mw of less than 50,000, preferably 40,000 or less, and 30,000 or less.
  • the ultrahigh molecular weight polypropylene may include polypropylene having Mw of 500,000 or more, preferably Mw of 800,000 to 1,000,000 or more.
  • the meaning of the molecular weight may be based on a criterion (Log Mw 4, 5 or less, Log Mw 6.0 or more) which defines the GPC phase integral value. Therefore, the homopolypropylene of the present invention has a low molecular weight of 150,000 to 200,000 and a narrow molecular weight distribution, and can exhibit excellent rigidity upon injection. More preferably, the molecular weight distribution of the homopolypropylene may be 2.0 to 2.4, more specifically 2.2 to 2.4. In addition, the present invention provides a homopolypropylene having an increased content of an ultra high molecular region by an additional reaction between double bond chain ends of the polymer in order to increase injection rigidity.
  • the homopolypropylene of the present invention is characterized in that, in a GPC curve graph in which the X-axis is log Mw and the y-axis is dw / dlogMw, the integral value of the log Mw of 4.5 or less is 8% or less of the total value of the x-axis. Further, the homopolypropylene of the present invention is characterized in that, in a GPC curve graph in which the x-axis is log MW and the y-axis is dw / dlogMw, the integral value of the region having Log Mw of 6 or more is 0.95% or more of the integral value of the x- .
  • the logarithmic molecular weight and the mass fraction of homopolypropylene are measured by GPC and are plotted along the x and y axes.
  • Mw means a weight-average molecular weight.
  • the residual stress ratio of the homopolypropylene is increased to have a value of 0.20% or more. More preferably, the residual stress ratio may be not less than 0.25% and not more than 0.5%. The increase of the residual stress ratio leads to the improvement of the injection strength, but if the residual stress ratio is excessive, the workability may be lowered.
  • the residual stress ratio can be measured according to the following equation 1 by performing a stress relaxation test by applying a large strain to the homopolypropylene after confirming the injection processability through a rheological property test .
  • Residual stress ratio (RSi / RS 0) * 100
  • RSo is the homopolypropylene under 235 ° C
  • the residual stress ratio of the homopolypropylene according to the above-mentioned formula 1 is 0.20% or less, there is a problem that the effect of increasing the tensile strength is low. In addition, there is a problem that the workability is deteriorated even when the ratio is too high, so the upper limit value is preferably 0.5% or less.
  • RSo represents the residual stress immediately after the strain of 20 W is applied to the homopolypropylene under 235 ° C (for example, at a point of time less than 0.05 seconds). Then, Under the same conditions, within about 1.5 seconds (for example, at any point in time between 0.05 seconds and 2.00 seconds).
  • the to may be selected from 0.01 second, 0.015 second, or 0.02 second, or 0.025 second, or 0.03 second, or 0.035 second, or 0.04 second, or 0.045 second.
  • t 0 is 0.02 sec and 1.00 sec is in the above equation (2).
  • the homopolypropylene has a tensile strength at yield of 350 to 400 kg / cm, a flexural strength of 480 to 520 kg / cin, and a flexural modulus of 15500 to 16800 kg / cm < / RTI > This is much higher than the homo PP or metallocene catalyzed Homo PP applied to existing Ziegler-Natta catalysts.
  • the flexural strength and flexural modulus of the homopolypropylene refer to values measured by the ASTM D790 method well known in the art.
  • the tensile strength of the homopolypropylene refers to a value measured by the ASTM D638 method well known in the art.
  • a process for producing a propylene-based polymer composition comprising the steps of: continuously polymerizing a propylene monomer in the presence of a footwear composition comprising 0.1 to 5.0%
  • a method for producing homopolypropylene according to claim 1 can be provided.
  • M is a Group 4 transition metal
  • RTI ID 0.0 > 3 < / RTI > are each independently the same or different halogen,
  • A is silicon or germanium
  • R 2 are each independently the same as or different from each other, C, 20 alkyl or C 6-20 aryl,
  • Each of 3 ⁇ 4 to 3 ⁇ 4 is independently the same as or different from each other, and is C 740 alkylaryl.
  • a target MI product is prepared under a low hydrogen addition polymerization condition by applying the specific metallocene catalyst of the above formula (1) having high hydrogen reactivity.
  • the homopolypropylene having a high ultrahigh molecular weight content can be prepared by inducing the reaction of the main chain in the double bond chain end by progressing polymerization under a low hydrogen content condition.
  • the rheological properties and the injection properties of the homopolypropylene having a high ultrahigh molecular weight content were measured, and it was confirmed that the rigidity was improved. Further, the present invention can provide homopolypropylene with a low molecular weight content.
  • the term can be defined as follows. 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • Halogen O 131 can be fluorine 00, chlorine ((: 1), bromine () or iodine (I).
  • the 0 1-20 alkyl group may be a straight chain, branched chain or cyclic alkyl group, more preferably a straight chain or branched chain alkyl group.
  • the 0 1-20 alkyl group is a 0 1-15 straight-chain alkyl group; 0 1-10 straight chain alkyl group; 0 1-5 straight-chain alkyl group; 3 ⁇ 4- 2 ⁇ branched or cyclic alkyl group; 0 3 -15 branched or cyclic alkyl group; Or a 0 3 -10 branched or cyclic alkyl group.
  • the alkyl group having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, 11 -butyl group, Butyl group, a butyl group, an 11- pentyl group, - pentyl group or cyclic nucleus group and the like.
  • 0 6-20 Aryl can mean monocyclic, bicyclic or tricyclic aromatic hydrocarbons. Specifically, 0 6 -20 aryl may be phenyl, naphthyl or anthracenyl.
  • 0 7-40 alkylaryl may include substituents wherein at least one hydrogen of the aryl is substituted by 0 1-20 alkyl.
  • - 4- alkylaryl is methylphenyl, ethylphenyl, 11- propylphenyl, Propylphenyl , 11- butylphenyl, Butylphenyl or cyclohexylphenyl, and the like.
  • the catalyst composition used in the preparation of homopolypropylene according to one embodiment of the present invention includes the compound of Formula 1 as a single catalyst. Accordingly, the molecular weight distribution can be significantly narrowed as compared with the homopolypropylene produced in the past when two or more catalysts are used in combination.
  • substituent 3 ⁇ 4 and 3 ⁇ 4 of the show are the same with each other in terms of improving the loading efficiency by increasing the solubility, may be 0 1-10 alkyl group, more particularly 6 Straight or branched chain alkyl, 0 1-4 straight chain or branched chain alkyl groups, more particularly methyl, ethyl, or 1 6 -butyl, respectively.
  • both positions of the two indenyl groups, the ligands are specifically substituted with isopropyl and methyl groups, allowing the two indenyl groups to have higher hydrogen reactivity than the same catalyst, 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • each of the above-mentioned 3 ⁇ 4 and 3 ⁇ 4 may independently be a phenyl group substituted with 0 1-6 branched alkyl groups, more specifically substituted with 0 3-6 branched alkyl groups such as 1 61 1 -butylphenyl Lt; / RTI >
  • the substitution position of the alkyl group with respect to the phenyl group may be the 4th or the 3rd position bonded to the indenyl group and the 4th position corresponding to ? 3 positions.
  • each of 3 ⁇ 4 and 3 ⁇ 4 may independently be chloro.
  • Representative examples of the compound represented by the above formula (1) may be any one of the following structures:
  • the amount of hydrogen supplied using the compound of formula ( 1 ) may be set to 20 < 141 >
  • the present invention can easily produce polypropylene having a molecular weight distribution of less than or equal to 2.4, as well as polypropylene having a molecular weight of 200,000 or more, while improving injection rigidity.
  • the Hobo polypropylene of the present invention can be produced by a continuous polymerization process using a catalyst composition containing the compound represented by the above formula (1) and propylene with a low content of hydrogen in the presence of hydrogen gas. 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • the hydrogen gas is preferably used in an amount of about 200
  • the catalyst of the present invention has high hydrogen reactivity and thus exhibits sufficient catalytic activity, and the molecular weight distribution of the homopolypropylene to be produced can be narrowed, and a homo-propylene polymer having a high ultrahigh molecular weight content can be produced.
  • the homopolypropylene can be produced by a continuous polymerization process and is known to be a polymerization reaction of olefin monomers such as a continuous gas phase polymerization process, a solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process or an emulsion polymerization process Various polymerization processes can be employed.
  • a continuous gas phase polymerization process or a bulk-slurry polymerization process is preferred in terms of obtaining a uniform molecular weight distribution and commercial production of the product.
  • the homopolypropylene polymerization method of the present invention can be carried out according to a continuous slurry polymerization method using a prepolymerization reactor and a loop reactor.
  • Such a method of the present invention may employ a reaction apparatus in which a prepolymerization reactor and a loop reactor are continuously provided, and a catalyst composition containing 0.1 to 5.0% by weight of the compound of the formula (1).
  • the process for producing a homopolypropylene of the present invention comprises:
  • a compound of the formula I 0.1 to 5.0% by weight of a compound of the formula I and a propylene monomer in a prepolymerization reactor; Continuously moving the mixture of the catalyst composition and the propylene monomer introduced into the prepolymerization reactor into a loop reactor; And from 20 ⁇ 1 a loop reactor where the hydrogen added to the following can be included the step of polymerizing a propylene monomer.
  • a catalyst composition containing the compound of formula (1) is prepared, and then the prepolymer is added together with the propylene monomer to the prepolymerization reactor to carry out the prepolymerization in which the compound of the formula (1) is first contacted with the propylene monomer.
  • the polymerization proceeds in the reactor.
  • a device for introducing hydrogen into the loop reactor may be installed.
  • the catalyst composition containing the compound of formula (1) may be injected into the reactor in the form of a dispersion solution (mordant catalyst form) using a dispersant.
  • the catalyst composition upon introduction into the polymerization reactor, may be a dispersion solution further comprising a dispersant in the catalyst composition comprising 0.1 to 5% by weight of the compound of formula (1).
  • the dispersing agent may be a mixed solution of oil and grease. Mineral oil may be used as the oil.
  • the present invention (hereinafter, the first catalyst composition), the polymerization after preparing a catalyst composition comprising a catalyst (preferably a supported catalyst), the content of formula (I) from 0.1 to 5% by weight to a primary It may be used as a dispersing solution (hereinafter, referred to as a secondary catalyst composition) by mixing with oil / grease as a dispersant before the addition. Therefore, the catalyst composition fed into the prepolymerization reactor and the loop reactor may be a secondary catalyst composition.
  • the second catalyst composition may be a solution prepared so that the content of the first catalyst composition is 10 to 30% by weight relative to the weight of oil / grease.
  • the catalyst composition to be added to the polymerization reaction in the present invention is a catalyst composition comprising a mixture of an oil and a grease, in which the first catalyst composition containing the compound of Formula 1 is dispersed in an amount of 10 to 30% by weight or 10 to 20% To use. If the content of the first catalyst composition in the second catalyst composition is less than 10 wt%, the gas phase polymerization does not proceed smoothly. If the content of the first catalyst composition exceeds 30 wt%, the polymerization reaction is difficult to control.
  • the residence time of the catalyst composition and the propylene monomer is preferably maintained for 5 to 10 minutes.
  • the prepolymerisation reactor can be such that the temperature of 0 to 2, [20 °, a pressure from 10 to 30 1 3 ⁇ 4 £ / 11.
  • the residence time of the catalyst composition and the propylene monomer is preferably maintained at 50 to 120 minutes. 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • the polymerization reaction is carried out at a temperature of from about 40 to 110 X:
  • the polymerization time may be from 50 minutes to 120 minutes.
  • the catalyst may be used in a state of being dissolved or diluted in a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
  • a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
  • a solvent such as pentane, nucleic acid, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like.
  • the compound of Formula 1 may be used as a single component or in the form of a supported catalyst supported on a support.
  • a carrier containing a hydroxy group on its surface can be used, and preferably, a carrier having a hydroxyl group and a siloxane group having high reactivity and dried on the surface and having moisture removed can be used.
  • a carrier having a hydroxyl group and a siloxane group having high reactivity and dried on the surface and having moisture removed can be used.
  • the drying at high temperatures, silica, silica-alumina, and silica-like Marg, Echinacea can be used, and these are typically ⁇ 20, 3 ⁇ 4 ⁇ 3, 3 ⁇ 4 ssaet 4, and ⁇ control 03) the oxide of the second and so on, carbonates , Sulfate, and nitrate components.
  • the drying temperature of the carrier is preferably 200 to 800 ⁇ ,
  • the carrier is preferably from 300 to 400.
  • the amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.
  • the mass ratio of the compound of Formula 1 to the carrier is preferably 1: 1 to 1: 1000.
  • the carrier and the compound of formula (1) are contained at the above mass ratio, they exhibit appropriate supported catalyst activity, which is advantageous in terms of maintaining the activity of the catalyst and economical efficiency.
  • the content thereof may be carried in the range of 8 to 25 1111110 1, preferably 10 to 20 parts by weight per carrier weight, for example, for 1 silica.
  • the compound represented by the general formula (1) in addition to the carrier, may further include a cocatalyst in terms of improving the activity and the process stability.
  • the promoter may include at least one compound represented by the following general formula (2), (3) or (4).
  • the seedlings are neutral or cationic Lewis bases
  • the egg is a hydrogen atom; 2019/107774 1 »(: 1 ⁇ ⁇ 2018/013198
  • At least one hydrogen atom is independently selected from the group consisting of halogen, an aryl group substituted or unsubstituted with hydrocarbon, alkoxy or phenoxy of- 2 () , or an alkyl group of -20 .
  • Examples of the compound represented by the general formula (2) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like.
  • a more preferred compound is methylaluminoxane.
  • Examples of the compound represented by the formula (3) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro-aluminum, tri-isopropyl aluminum, tri-butyl aluminum, tri-cyclopentyl-aluminum, tri But are not limited to, pentylaluminum, triisopentylaluminum, triunfulylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-13-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, Triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylalumin
  • Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (I-tolyl) Boron, trimethylammoniumtetra ( 0,1) -dimethylphenyl) boron, tributylammoniumtetra (I ) -trifluoromethylphenyl) boron, trimethylammoniumtetra (I-
  • Tributylammonium tetrapentafluorophenylboron Diethylanilinium tetraphenylboron, diethylanilinium tetrapentafluorophenylboron, diethylanilinium tetrapentafluorophenylboron,
  • the method may include a step of supporting the carrier with a promoter compound, and a step of supporting the carrier with the compound represented by the formula (1) , Wherein the carrying order of the cocatalyst and the compound of formula (1) may be varied as needed.
  • hydrocarbon solvents such as pentane, nucleic acid, heptane and the like, or aromatic solvents such as benzene, toluene and the like may be used as a reaction solvent.
  • the metallocene supported catalyst of the present invention may be a carrier in which an alkylaluminoxane-based co-catalyst and a metallocene compound represented by the following general formula (1) are sequentially carried.
  • the reaction can proceed under an inert atmosphere.
  • preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention.
  • the following examples are provided only for the purpose of easier understanding of the present invention , and the present invention is not limited thereto.
  • Silica gel (SYLOPOL 952X, ca lc inated under 250 ° C, 100 g) was placed in a 2L reactor under Ar and methylaluminoxane (MAO) (766 mL) was slowly added at room temperature and stirred at 90 ° C for 15 hours . After the completion of the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 15 minutes and decant through cannula. Toluene (400 mL) was added to the reaction product, and the mixture was stirred for 1 minute and allowed to stand for 15 minutes to decant the solvent using a calla lantern.
  • MAO methylaluminoxane
  • each catalyst (700 y mol) shown in Table 1 was dissolved in toluene (400 mL), and then the catalyst-containing solution was transferred to the reactor using a calla liner. After stirring at 50 ° C for 5 hours, the solution was allowed to cool to room temperature and allowed to stand for 15 minutes to decant the solvent using a calla lol. Toluene (400 niL) was added, stirred for 1 minute, left for 15 minutes, and the solvent was removed using a cannula twice.
  • nucleic acid 400 mL was added in the same manner and stirred for 1 minute and allowed to stand for 15 minutes After using the cache neulra di cant and the solvent, dissolved in an antistatic agent (G 163.3 Mum ⁇ ) a nucleic acid (400: 1), was transferred using a cannula to the reactor. The mixture was stirred at room temperature for 20 minutes, and the reaction product was transferred to a glass filter to remove the solvent. Dried for 5 hours under vacuum, and vacuum-dried at 45 for 4 hours to obtain respective supported catalysts. Homopolypropylene manufacture (manufactured on a continuous pilot plant)
  • Each catalyst composition was mixed with oil / grease (oi 1 / grease) to prepare a 16 wt% mixture (mordant catalyst form). Then, the mixture and 20 kg / h of propylene were fed together in a pre-polymerizer reactor (reactor temperature: 20 ° C, pressure: 15 kgf ⁇ : m 2 ) And transferred to a loop reactor.
  • the polymer sample was pre-treated with PL-SP260 by dissolving in 1,2,4-trichlorobenzene containing 0.0125% of BHT at 160 ° C for 10 hours, and then, using PL-GPC220, And the number average molecular weight and the weight average molecular weight were measured.
  • the molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.
  • Residual stress ratio (Y) (RSi / RSo) * 100
  • RSo is the residual stress at 0.02 sec (t 0 ) after applying 200% deformation to the synthetic resin sample at 235 ° C
  • R 3 ⁇ 4 is 200% deformation of the synthetic resin sample at 235 ° C
  • the residual stress at (1.00 seconds).
  • Examples 1 to 3 of the present invention are inferior to low-molecular weight 1 to 4, low in low molecular weight, high in ultra high molecular weight, and excellent in injection properties.

Landscapes

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

Abstract

La présente invention concerne un polypropylène ayant une grande quantité de molécules de poids moléculaire élevé et une excellente rigidité, et son procédé de préparation.
PCT/KR2018/013198 2017-11-28 2018-11-01 Polypropylène et son procédé de préparation WO2019107774A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP18883218.2A EP3647331A4 (fr) 2017-11-28 2018-11-01 Polypropylène et son procédé de préparation
CN201880046736.9A CN110914316B (zh) 2017-11-28 2018-11-01 聚丙烯及其制备方法
US16/635,730 US11248072B2 (en) 2017-11-28 2018-11-01 Polypropylene and method for preparing the same
JP2020500899A JP6893279B2 (ja) 2017-11-28 2018-11-01 ポリプロピレンおよびその製造方法
US17/546,307 US11732069B2 (en) 2017-11-28 2021-12-09 Polypropylene and method for preparing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170160625 2017-11-28
KR10-2017-0160625 2017-11-28
KR10-2018-0132203 2018-10-31
KR1020180132203A KR102375854B1 (ko) 2017-11-28 2018-10-31 폴리프로필렌 및 그 제조방법

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US16/635,730 A-371-Of-International US11248072B2 (en) 2017-11-28 2018-11-01 Polypropylene and method for preparing the same
US17/546,307 Division US11732069B2 (en) 2017-11-28 2021-12-09 Polypropylene and method for preparing the same

Publications (1)

Publication Number Publication Date
WO2019107774A1 true WO2019107774A1 (fr) 2019-06-06

Family

ID=66665723

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/013198 WO2019107774A1 (fr) 2017-11-28 2018-11-01 Polypropylène et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2019107774A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060029247A (ko) * 2003-07-04 2006-04-05 바젤 폴리올레핀 게엠베하 올레핀 중합 방법
US20070015877A1 (en) * 1996-09-04 2007-01-18 Burkhardt Terry J Process of producing thermoplastic polymer blends
US20090137739A1 (en) * 2005-10-21 2009-05-28 Basell Polyolefine Gmbh Polypropylene for Injection Molding
US20090259009A1 (en) * 2005-10-21 2009-10-15 Basell Polyolefine Gmbh Propylene Polymers
KR20170108810A (ko) * 2016-03-18 2017-09-27 주식회사 엘지화학 폴리프로필렌

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070015877A1 (en) * 1996-09-04 2007-01-18 Burkhardt Terry J Process of producing thermoplastic polymer blends
KR20060029247A (ko) * 2003-07-04 2006-04-05 바젤 폴리올레핀 게엠베하 올레핀 중합 방법
US20090137739A1 (en) * 2005-10-21 2009-05-28 Basell Polyolefine Gmbh Polypropylene for Injection Molding
US20090259009A1 (en) * 2005-10-21 2009-10-15 Basell Polyolefine Gmbh Propylene Polymers
KR20170108810A (ko) * 2016-03-18 2017-09-27 주식회사 엘지화학 폴리프로필렌

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3647331A4 *

Similar Documents

Publication Publication Date Title
US6423795B1 (en) Tetramethylcyclopentadienyl titanium compounds for ethylene-α-olefin-copolymer production catalysts
US7569646B1 (en) Group IVB transition metal compounds
EP2563821B1 (fr) Catalyseurs
US6617466B1 (en) Monocylopentadienyl transition metal olefin polymerization catalysts
EP1874828B1 (fr) Catalyseurs pour polymerisation olefinique
EP3031832A1 (fr) Procédé de préparation de polyoléfine et polyoléfine ainsi préparée
US11732069B2 (en) Polypropylene and method for preparing the same
EP3441407B1 (fr) Résine à base d'un copolymère de propylène-diène présentant une remarquable tension de fusion
JP5848815B2 (ja) ビニル末端型ポリマーを製造するための新規な触媒およびその使用方法
KR101670468B1 (ko) 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀
WO2014052200A1 (fr) Polymères à terminaison vinyle et procédé de production associé
EP3246343A1 (fr) Procédé de préparation d'une polyoléfine
KR20200123449A (ko) C4-c12-알파 올레핀 공단량체 단위를 포함하는 프로필렌 공중합체의 제조 방법
USRE37788E1 (en) Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
JP2005504853A (ja) アルファ−オレフィンをベースとした枝分れポリマー
WO2019107774A1 (fr) Polypropylène et son procédé de préparation
EP3889191A1 (fr) Résine de polypropylène ayant d'excellentes caractéristiques à l'état fondu, et son procédé de préparation
EP4015542A1 (fr) Polyéthylène et son polyéthylène chloré
CN117377704A (zh) 共聚物
KR20210153556A (ko) 폴리에틸렌 및 이의 염소화 폴리에틸렌
WO2019124805A1 (fr) Polymère d'oléfine, son procédé de préparation et film l'utilisant
AU643237C (en) Monocyclopentadienyl transition metal olefin polymerization catalysts
KR20230102135A (ko) 신규한 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물 및 이를 이용한 에틸렌 및 α-올레핀의 공중합체의 제조방법
JP2004359851A (ja) プロピレン系重合体

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: 18883218

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020500899

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018883218

Country of ref document: EP

Effective date: 20200127

NENP Non-entry into the national phase

Ref country code: DE