WO2011071237A2 - 프로필렌 중합용 고체촉매의 제조 방법 - Google Patents

프로필렌 중합용 고체촉매의 제조 방법 Download PDF

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Publication number
WO2011071237A2
WO2011071237A2 PCT/KR2010/006720 KR2010006720W WO2011071237A2 WO 2011071237 A2 WO2011071237 A2 WO 2011071237A2 KR 2010006720 W KR2010006720 W KR 2010006720W WO 2011071237 A2 WO2011071237 A2 WO 2011071237A2
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Prior art keywords
diethyl
succinate
isobutyl
isopropyl
cyclohexyl
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PCT/KR2010/006720
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English (en)
French (fr)
Korean (ko)
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WO2011071237A3 (ko
Inventor
김상열
박준려
김은일
이진우
Original Assignee
삼성토탈 주식회사
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Priority to CN201080061607.0A priority Critical patent/CN102712705B/zh
Priority to EP10836133.8A priority patent/EP2511303B1/en
Priority to JP2012539796A priority patent/JP5554416B2/ja
Priority to US13/514,673 priority patent/US8664142B2/en
Publication of WO2011071237A2 publication Critical patent/WO2011071237A2/ko
Publication of WO2011071237A3 publication Critical patent/WO2011071237A3/ko
Priority to US14/016,537 priority patent/US9062135B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—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
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing a solid catalyst for propylene polymerization, and more particularly, a solid catalyst for propylene polymerization, which exhibits a high melt flow index and a wide molecular weight distribution and can polymerize polypropylene having excellent stereoregularity with a high yield. It relates to a method for producing.
  • Polypropylene is an industrially useful material, and has been widely applied to various applications, particularly for materials related to automobiles and electronic products. In order to expand the application of polypropylene, it is important to improve stereoregularity, widen the molecular weight distribution, and improve it to have high rigidity and excellent workability.
  • olefins such as propylene
  • a solid catalyst containing magnesium, titanium, an electron donor and a halogen as essential components is known, and olefins are polymerized or copolymerized with a catalyst system composed of the solid catalyst, an organoaluminum compound and an organosilicon compound.
  • Many methods to make it have been proposed. However, this method is not satisfactory enough to obtain high stereoregular polymers in high yield, and improvements are required in this respect.
  • the present invention has been made to solve the above problems, the problem to be solved of the present invention is to exhibit a high melt flow index and a wide molecular weight distribution and at the same time can be polymerized polypropylene excellent in stereoregularity with a high yield It is to provide a method for producing a solid catalyst for propylene polymerization.
  • the present invention provides a method for producing a solid catalyst comprising the following steps:
  • R 1 , R 2 , R 3 and R 4 are independently a linear, branched or cyclic alkyl group or hydrogen atom of 1 to 10 carbon atoms
  • R 1 and R 2 are independently 1 to 10 linear, branched or cyclic alkyl groups or hydrogen atoms, and R 3 and R 4 are independently 1 to 10 linear, branched or carbon atoms Cyclic alkyl group
  • R 1 , R 2 and R 4 are independently a linear, branched or cyclic alkyl group or hydrogen atom of 1 to 10 carbon atoms, and R 3 is a linear, branched or cyclic type of 1 to 10 carbon atoms Alkyl group);
  • step (3) reacting the result of step (2) with titanium halide at a temperature of 80 ⁇ 130 °C, washing the result.
  • organic solvent used in the step (1) there is no particular limitation on the kind, and C6-C12 aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, etc. may be used, and more preferably C7-C10 saturated aliphatic compounds. Or an aromatic hydrocarbon or a halogenated hydrocarbon, and specific examples thereof may be used alone or in combination of one or more selected from octane, nonane, decane, toluene and xylene, chlorobutane, chlorohexane, chloroheptane, and the like. have.
  • the dialkoxy magnesium used in the step (1) has an average particle diameter of 10 to 200 ⁇ m obtained by reacting metal magnesium with anhydrous alcohol in the presence of magnesium chloride, and the surface is spherical particles, the spherical particle shape of propylene It is preferable to maintain it as it is during the polymerization. If the average particle diameter is less than 10 mu m, the fine particles of the prepared catalyst increase, which is not preferable. If the average particle diameter exceeds 200 mu m, the apparent density tends to decrease, which is not preferable.
  • the use ratio of the organic solvent to the dialkoxy magnesium is preferably 1: 5 to 50, more preferably 1: 7 to 20, in terms of dialkoxy magnesium weight: organic solvent volume. If it is less than: 5, the viscosity of the slurry is rapidly increased to make it difficult to uniformly stir, and if it is more than 1:50, the apparent density of the resulting carrier decreases rapidly or the surface of the particles is rough, which is not preferable.
  • the titanium halide used in step (1) of the solid catalyst preparation process is preferably represented by the following general formula (I):
  • R is an alkyl group of 1 to 10 carbon atoms
  • X is a halogen element
  • a is for matching the valence of general formula, and is an integer of 0-3.
  • titanium halide it is preferable to use titanium tetrachloride.
  • step (1) of the solid catalyst preparation process is preferably carried out by slowly adding titanium halide in a state in which the dialkoxy magnesium is suspended in an organic solvent in the temperature range of 0 ⁇ 30 °C.
  • the amount of titanium halide to be used is preferably 0.1 to 10 moles, more preferably 0.3 to 2 moles per 1 mole of dialkoxy magnesium. If less than 0.1 mole, the reaction of dialkoxy magnesium to magnesium chloride is smooth. It is not preferable because it does not proceed, and exceeding 10 moles is not preferable because excessively many titanium components are present in the catalyst.
  • the internal electron donor used in the step (2) is an internal electron donor selected from the following general formula (II), and the internal electron donor selected from the general formula (III) or general formula (IV) Electron donors can be mixed and used.
  • R 1 , R 2 , R 3 and R 4 are independently a linear, branched or cyclic alkyl group or hydrogen atom of 1 to 10 carbon atoms
  • R 1 and R 2 are independently 1 to 10 linear, branched or cyclic alkyl groups or hydrogen atoms, and R 3 and R 4 are independently 1 to 10 linear, branched or carbon atoms Cyclic alkyl group
  • R 1 , R 2 and R 4 are independently a linear, branched or cyclic alkyl group or hydrogen atom of 1 to 10 carbon atoms, and R 3 is a linear, branched or cyclic type of 1 to 10 carbon atoms Alkyl group
  • Examples of the internal electron donor include diethyl-2,3-dimethylsuccinate, diethyl-2,3-diethylsuccinate, diethyl-2,3-dipropylsuccinate, diethyl-2,3- Diisopropylsuccinate, diethyl-2,3-dibutylsuccinate, diethyl-2,3-diisobutylsuccinate, diethyl-2,3-dipentylsuccinate, diethyl-2,3- Dihexylsuccinate, diethyl-2,3-dicyclopentylsuccinate, diethyl-2,3-dicyclohexylsuccinate, diethyl-2-cyclopentyl-3-methylsuccinate, diethyl-2- Cyclohexyl-3-methylsuccinate, diethyl-2-isopropyl-3-methylsuccinate, diethyl-2-isobutyl-3-methylsuccinate, die
  • the step (2) is preferably carried out by reacting for 1 to 3 hours by adding an internal electron donor during the temperature increase process while gradually increasing the temperature of the resultant of step (1) to 80 ⁇ 130 °C, the temperature is If the reaction time is less than 80 ° C. or less than 1 hour, the reaction is difficult to complete. If the temperature exceeds 130 ° C. or if the reaction time is more than 3 hours, the polymerization reaction of the resulting catalyst or the stereoregularity of the polymer may be lowered by side reactions. Can be.
  • the temperature and the number of the inputs are not particularly limited, and the total amount of the internal electron donor uses 0.1 to 1.0 mole based on 1 mole of dialkoxy magnesium used. It is preferable that outside the above range, the polymerization activity of the resulting catalyst or the stereoregularity of the polymer may be lowered.
  • Step (3) of the solid catalyst production process is a step of secondary reaction between the resultant of step (2) and titanium halide at a temperature of 80 ⁇ 130 °C.
  • titanium halide to be used include titanium halides of the general formula (I).
  • the solid catalyst prepared as described above comprises magnesium, titanium, halogen and internal electron donor, and considering the catalytic activity, 5 to 40 wt% magnesium, 0.5 to 10 wt% titanium, 50 to halogen It is preferred to comprise 85% by weight and 2.5-30% by weight of the internal electron donor.
  • the solid catalyst prepared by the catalyst preparation method of the present invention may be suitably used in the propylene polymerization or copolymerization method, and the propylene polymerization or copolymerization method using the solid catalyst prepared according to the present invention may be used for the solid catalyst, the cocatalyst and the external electron.
  • the solid catalyst may be prepolymerized with ethylene or alpha olefin before being used as a component of the polymerization reaction.
  • the prepolymerization reaction can be carried out in the presence of a hydrocarbon solvent (eg hexane), the catalyst component and an organoaluminum compound (eg triethylaluminum) at sufficiently low temperatures and ethylene or alphaolefin pressure conditions.
  • a hydrocarbon solvent eg hexane
  • an organoaluminum compound eg triethylaluminum
  • Prepolymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape.
  • the weight ratio of polymer / catalyst after prepolymerization is preferably about 0.1 to 20: 1.
  • an organometallic compound of Group II or Group III of the periodic table may be used as the cocatalyst component.
  • an alkylaluminum compound is used.
  • the alkylaluminum compound is represented by general formula (V):
  • R is a C1-C6 alkyl group.
  • alkyl aluminum compound examples include trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, triisobutyl aluminum, trioctyl aluminum and the like.
  • the ratio of the promoter component to the solid catalyst component is somewhat different depending on the polymerization method, but the molar ratio of metal atoms in the promoter component to titanium atoms in the solid catalyst component is preferably in the range of 1 to 1000, More preferably, it is good that it is the range of 10-300. If the molar ratio of the metal atom in the promoter component, for example, the aluminum atom, to the titanium atom in the solid catalyst component is out of the range of 1 to 1000, there is a problem that the polymerization activity is greatly reduced.
  • At least one of the alkoxysilane compounds represented by the following general formula (VI) may be used as the external electron donor:
  • R 1 , R 2 may be the same or different, a linear or branched or cyclic alkyl group having 1 to 12 carbon atoms, or an aryl group
  • R 3 is a linear or branched alkyl group having 1 to 6 carbon atoms
  • m and n are 0 or 1, respectively
  • m + n is 1 or 2, respectively.
  • the external electron donor include normal propyl trimethoxy silane, dinormal propyl dimethoxy silane, isopropyl trimethoxy silane, diisopropyl dimethoxy silane, normal butyl trimethoxy silane and di normal butyl dimethoxy Silane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, tertiarybutyltrimethoxysilane, dietarybutyldimethoxysilane, normalpentyltrimethoxysilane, dinormalpentyldimethoxysilane, cyclopentyltrimethoxy Silane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclohexyltrimethoxysilane, dicyclobut
  • the amount of the external electron donor to the solid catalyst varies slightly depending on the polymerization method, but the molar ratio of the silicon atom in the external electron donor to the titanium atom in the catalyst component is preferably in the range of 0.1 to 500, 1 to 100 It is more preferable that it is the range of. If the molar ratio of silicon atoms in the external electron donor to the titanium atoms in the solid catalyst component is less than 0.1, the stereoregularity of the resulting propylene polymer is significantly lowered, and if it exceeds 500, the polymerization activity of the catalyst is significantly lowered. There is this.
  • the temperature of the polymerization reaction is 20 to 120 ° C. If the temperature of the polymerization reaction is less than 20 ° C, the reaction does not proceed sufficiently, and if it exceeds 120 ° C, It is not preferable because the deterioration is severe and adversely affects the polymer physical properties.
  • solid catalyst prepared by the method of the present invention it is possible to polymerize polypropylene having high melt flowability and wide molecular weight distribution and excellent stereoregularity with high yield without containing environmentally harmful substances.
  • the resulting polymer was analyzed and shown in Table 1.
  • catalytic activity was determined by the following method.
  • Example 1 In the preparation of the solid catalyst, 2.9 g of diethyl-2,3-diisopropylidene succinate and 2.9 g of diethyl-2,3-diisopropyl succinate were used instead of di- A catalyst was prepared using a mixture of 2.3 g of ethyl-2,3-diisopropylidene succinate and 3.5 g of diethyl-2,3-diisopropylsuccinate. The titanium content in the solid catalyst component was 3.2% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.
  • Example 1 In the preparation of the solid catalyst, 2.9 g of diethyl-2,3-diisopropylidene succinate and 2.9 g of diethyl-2,3-diisopropyl succinate were used instead of di- A catalyst was prepared using a mixture of 1.4 g of ethyl-2,3-diisopropylidene succinate and 4.3 g of diethyl-2,3-diisopropylsuccinate. The titanium content in the solid catalyst component was 3.1% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.
  • Example 1 In the preparation of the solid catalyst, 2.9 g of diethyl-2,3-diisopropylidene succinate and 2.9 g of diethyl-2,3-diisopropyl succinate were used instead of di- A catalyst was prepared using a mixture of 2.9 g of ethyl-2-isopropylidene-3-isopropylsuccinate and 2.9 g of diethyl-2,3-diisopropylsuccinate. The titanium content in the solid catalyst component was 3.1% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.
  • the temperature was lowered to 90 ° C. to stop stirring, the supernatant was removed, and further washed once using the same method using 200 ml of toluene.
  • 150 ml of toluene and 50 ml of titanium tetrachloride were added thereto, and the temperature was raised to 110 ° C. and maintained for 1 hour.
  • the slurry mixture was washed twice with 200 ml of toluene ⁇ each time, and washed 5 times with 200 ml of hexane each time at 40 ° C. to obtain a pale yellow solid catalyst component.
  • the titanium content in the solid catalyst component obtained by drying for 18 hours in flowing nitrogen was 3.3% by weight.
  • Example 1 In the preparation of the solid catalyst, 2.9 g of diethyl-2,3-diisopropylidene succinate and 2.9 g of diethyl-2,3-diisopropyl succinate were used instead of di- The catalyst was prepared using 5.8 g of ethyl-2,3-diisopropylsuccinate. The titanium content in the solid catalyst component was 2.8% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.
  • Example 1 In the preparation of the solid catalyst, 2.9 g of diethyl-2,3-diisopropylidene succinate and 2.9 g of diethyl-2,3-diisopropyl succinate were used instead of di- The catalyst was prepared using 4.8 g of ethyl-2-cyclohexylsuccinate. The titanium content in the solid catalyst component was 3.8% by weight. Next, polypropylene polymerization was carried out in the same manner as in Example 1, and the results are shown in Table 1.
  • Examples 1 to 4 according to the present invention show excellent melt flow index and broad molecular weight distribution while having high activity and stereoregularity, whereas Comparative Examples 1 and 3 have very low activity.
  • Narrow molecular weight distribution, comparative example 2 shows that the melt flow index was inferior while the molecular weight distribution was narrower compared with Examples 1 to 4.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
PCT/KR2010/006720 2009-12-08 2010-10-01 프로필렌 중합용 고체촉매의 제조 방법 WO2011071237A2 (ko)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201080061607.0A CN102712705B (zh) 2009-12-08 2010-10-01 丙烯聚合用固体催化剂的制备方法
EP10836133.8A EP2511303B1 (en) 2009-12-08 2010-10-01 Manufacturing method of solid catalyst for propylene polymerization
JP2012539796A JP5554416B2 (ja) 2009-12-08 2010-10-01 プロピレン重合用固体触媒の製造方法
US13/514,673 US8664142B2 (en) 2009-12-08 2010-10-01 Manufacturing method of solid catalyst for propylene polymerization
US14/016,537 US9062135B2 (en) 2009-12-08 2013-09-03 Manufacturing method of solid catalyst for propylene polymerization

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090121300A KR101114073B1 (ko) 2009-12-08 2009-12-08 프로필렌 중합용 고체촉매의 제조 방법
KR10-2009-0121300 2009-12-08

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US13/514,673 A-371-Of-International US8664142B2 (en) 2009-12-08 2010-10-01 Manufacturing method of solid catalyst for propylene polymerization
US14/016,537 Division US9062135B2 (en) 2009-12-08 2013-09-03 Manufacturing method of solid catalyst for propylene polymerization

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WO2011071237A3 WO2011071237A3 (ko) 2011-08-25

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US (2) US8664142B2 (ja)
EP (1) EP2511303B1 (ja)
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CN106317268A (zh) * 2015-06-19 2017-01-11 中国石油天然气股份有限公司 一种用于合成高流动聚丙烯的催化剂及其制备方法与应用
US9777084B2 (en) 2016-02-19 2017-10-03 Formosa Plastics Corporation, Usa Catalyst system for olefin polymerization and method for producing olefin polymer
US11427660B2 (en) 2016-08-17 2022-08-30 Formosa Plastics Corporation, Usa Organosilicon compounds as electron donors for olefin polymerization catalysts and methods of making and using same
US9815920B1 (en) 2016-10-14 2017-11-14 Formosa Plastics Corporation, Usa Olefin polymerization catalyst components and process for the production of olefin polymers therewith
US10124324B1 (en) 2017-05-09 2018-11-13 Formosa Plastics Corporation, Usa Olefin polymerization catalyst components and process for the production of olefin polymers therewith
US10822438B2 (en) 2017-05-09 2020-11-03 Formosa Plastics Corporation Catalyst system for enhanced stereo-specificity of olefin polymerization and method for producing olefin polymer
JP7429097B2 (ja) * 2019-06-07 2024-02-07 サンアロマー株式会社 ポリプロピレン系樹脂組成物の製造方法及びシート成形体の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125504A1 (ja) * 2012-02-20 2013-08-29 サンアロマー株式会社 シート成形用ポリプロピレン系樹脂組成物
JPWO2013125504A1 (ja) * 2012-02-20 2015-07-30 サンアロマー株式会社 シート成形用ポリプロピレン系樹脂組成物

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EP2511303B1 (en) 2014-10-15
EP2511303A4 (en) 2013-11-06
JP5554416B2 (ja) 2014-07-23
US20140005038A1 (en) 2014-01-02
WO2011071237A3 (ko) 2011-08-25
KR20110064618A (ko) 2011-06-15
CN102712705A (zh) 2012-10-03
CN102712705B (zh) 2014-03-12
JP2013510941A (ja) 2013-03-28
EP2511303A2 (en) 2012-10-17
US9062135B2 (en) 2015-06-23
US20120264593A1 (en) 2012-10-18
KR101114073B1 (ko) 2012-02-22

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