WO2012070753A2 - 프로필렌 중합용 고체촉매 및 그 제조 방법 - Google Patents
프로필렌 중합용 고체촉매 및 그 제조 방법 Download PDFInfo
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- WO2012070753A2 WO2012070753A2 PCT/KR2011/006528 KR2011006528W WO2012070753A2 WO 2012070753 A2 WO2012070753 A2 WO 2012070753A2 KR 2011006528 W KR2011006528 W KR 2011006528W WO 2012070753 A2 WO2012070753 A2 WO 2012070753A2
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- WIPO (PCT)
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- hept
- dicarboxylic acid
- solid catalyst
- group
- ester
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
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- 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 solid catalyst for propylene polymerization and a method for manufacturing the same, and more particularly, to a propylene polymerization solid catalyst capable of polymerizing polypropylene having excellent stereoregularity with a high yield without containing environmentally harmful substances, and a preparation thereof. It is about a method.
- Polypropylene is a very industrially useful material, and it is widely applied in various applications, especially in materials related to automobiles and electronic products.
- the solid catalyst should be designed to exhibit high stereoregularity.
- 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.
- Korean Patent No. 0491387 describes a catalyst preparation method using a non-aromatic diether material, and Korean Patent No. 0572616 a non-aromatic material having both a ketone and an ether functional group as an internal electron donor.
- Korean Patent No. 0491387 describes a catalyst preparation method using a non-aromatic diether material
- Korean Patent No. 0572616 a non-aromatic material having both a ketone and an ether functional group as an internal electron donor.
- US Patent Publication No. 2009/0069515 A1 proposes a method for preparing a catalyst using non-aromatic diisobutyl-4-methyl-cyclohexane-1,2-dicarboxylate, but in terms of activity and stereoregularity. There is room for significant improvement in all, and no examples have used bicyclic compounds.
- the present invention has been made to solve the above problems, the problem to be solved of the present invention is a propylene polymerization capable of polymerizing polypropylene having excellent stereoregularity in a high yield without containing environmentally harmful substances. It is to provide a method for producing a solid catalyst for.
- the present invention provides a solid catalyst comprising titanium, magnesium, halogen and a bicycloalkenedicarboxylate-based internal electron donor represented by the general formula (II) or (III) .
- R 1 and R 2 are the same as or different from each other, and are a linear, branched or cyclic alkyl group, alkenyl group, aryl group, arylalkyl group or alkylaryl group having 1 to 20 carbon atoms;
- R 3 , R 4 , R 5 and R 6 are the same as or different from each other, and are hydrogen, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, alkenyl group, aryl group, arylalkyl group or alkylaryl group.
- the present invention also provides a process for preparing a solid catalyst comprising the following steps:
- step (1) One kind selected from bicycloalkenedicarboxylate-based internal electron donors represented by general formula (II) or (III) in the resultant of step (1) while the temperature is raised to a temperature of 60 to 150 ° C. Or reacting by adding two or more kinds; And
- step (3) reacting the result of step (2) with titanium halide at a temperature of 60 ⁇ 150 °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 aromatic hydrocarbons or halogenated hydrocarbons, 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 a mean particle size of 10 to 200 ⁇ m obtained by reacting metal magnesium with anhydrous alcohol in the presence of magnesium chloride, and the surface is smooth 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.
- 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 production 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 -20 ⁇ 50 °C.
- the amount of titanium halide used at this time is preferably 0.1 to 10 moles, more preferably 0.3 to 2 moles with respect to 1 mole of dialkoxymagnesium. If it is less than 0.1 mole, the reaction of dialkoxymagnesium 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.
- examples of the internal electron donor represented by the general formula (II) or the general formula (III) used in the step (2) are bicyclo [2.2.1] hept-2- En-2,3-dicarboxylic acid ethylhexyl ester, bicyclo [2.2.1] hept-2-ene-2,3-dicarboxylic acid octyl ester, bicyclo [2.2.1] hept-2-ene -2,3-dicarboxylic acid diisobutyl ester, bicyclo [2.2.1] hept-2-ene-2,3-dicarboxylic acid dibutyl ester, bicyclo [2.2.1] hept-2-ene- 2,3-dicarboxylic acid diisopropyl ester, bicyclo [2.2.1] hept-2-ene-2,3-dicarboxylic acid dipropyl ester, bicyclo [2.2.1] hept-2-ene-2 , 3-dicarboxylic
- hept-2,5-diene-2,3-dicarboxylic acid dibutyl ester 5,6-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxylic acid diisopropyl ester, 5,6-dimethylbicyclo [2.2.1] hept-2,5 -Diene-2,3-dicarboxylic acid dipropyl ester, 5,6-dimethylbicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxylic acid diethyl ester, 5,6-dimethyl Bicyclo [2.2.1] hept-2,5-diene-2,3-dicarboxylic acid dimethyl ester, and the like, and among these, one or two or more thereof may be mixed and used.
- Step (2) is carried out by slowly increasing the temperature of the resultant of step (1) to 60-150 ° C, preferably 80-130 ° C, and reacting for 1 to 3 hours by introducing an internal electron donor during the temperature rising process. If the temperature is less than 60 °C or the reaction time is less than 1 hour, the reaction is difficult to complete, if the temperature exceeds 150 °C or the reaction time exceeds 3 hours, the polymerization activity of the resulting catalyst by side reaction Or the stereoregularity of the polymer may be lowered.
- 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 60 ⁇ 150 °C, preferably 80 ⁇ 130 °C.
- titanium halide to be used include titanium halides of the general formula (I).
- the solid catalyst of the present invention prepared by the above method comprises magnesium, titanium, halogen and internal electron donor, and considering the catalytic activity, 5 to 40% by weight magnesium, 0.5 to 10% by weight titanium %, 50 to 85% by weight of halogen and 2.5 to 30% by weight of internal electron donor.
- the solid catalyst prepared by the method for preparing a catalyst of the present invention may be suitably used for a propylene polymerization or copolymerization method. Polymerizing propylene in the presence of a donor or copolymerizing propylene with other alphaolefins.
- 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 (IV):
- 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 (V) 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.
- polypropylene excellent in stereoregularity can be polymerized in a high yield without containing environmentally harmful substances.
- the temperature was lowered to 90 ° C. to stop stirring, the supernatant was removed, and further washed once with 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 2 hours.
- the slurry mixture was washed twice with 200 ml of toluene each time, and washed 5 times with 200 ml of each time with normal hexane 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 3.2% by weight and the content of the internal electron donor was 10.2% by weight.
- the resulting polymer was analyzed and shown in Table 1.
- catalytic activity and stereoregularity were determined by the following method.
- Example 1 In the preparation of the solid catalyst, bicyclo [2.2.1] hept-2 instead of 6.6 g of bicyclo [2.2.1] hept-2-ene-2,3-dicarboxylic acid dibutyl ester The catalyst was prepared using 6.5 g of, 5-diene-2,3-dicarboxylic acid dibutyl ester. The titanium content in the solid catalyst component was 3.0% by weight and the content of the internal electron donor was 9.4% 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, bicyclo [2.2.1] hept-2 instead of 6.6 g of bicyclo [2.2.1] hept-2-ene-2,3-dicarboxylic acid dibutyl ester The catalyst was prepared using 5.3 g of -ene-2,3-dicarboxylic acid diethyl ester. The content of titanium in the solid catalyst component was 2.9% by weight and the content of internal electron donor was 9.5% 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, bicyclo [2.2.1] hept-2 instead of 6.6 g of bicyclo [2.2.1] hept-2-ene-2,3-dicarboxylic acid dibutyl ester A catalyst was prepared using 5.3 g of, 5-diene-2,3-dicarboxylic acid diethyl ester. The titanium content in the solid catalyst component was 2.8 wt% and the content of internal electron donor was 9.3 wt%. 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.
- Examples 1 to 5 according to the present invention are excellent in both stereoregularity and activity using a bicycloalkenedicarboxylate-based internal electron donor, whereas Comparative Example 1 is very active It turns out that it is inferior and stereoregularity is inferior to an Example.
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Abstract
Description
Claims (4)
- 제 1항에 있어서, 상기 고체 촉매는 마그네슘 5~40중량%, 티타늄 0.5~10중량%, 할로겐 50~85중량% 및 내부전자공여체 2.5~30중량%를 포함하는 것을 특징으로 하는 프로필렌 중합용 고체촉매.
- 다음의 단계들을 포함하는 것을 특징으로 하는 프로필렌 중합용 고체촉매의 제조 방법:(1) 유기용매의 존재 하에서 디알콕시마그네슘과 티타늄할라이드를 반응시키는 단계;(2) 60~150℃의 온도로 승온시키면서, 상기 단계 (1)의 결과물에 하기 일반식(II) 또는 (III)으로 표시되는 비시클로알켄디카르복실레이트계 내부전자공여체 중에서 선택되는 1종 또는 2종 이상을 투입하여 반응시키는 단계,여기에서, R1 및 R2는 서로 동일하거나 상이하고, 탄소원자 1~20개의 선형, 가지형 또는 고리형 알킬기, 알케닐기, 아릴기, 아릴알킬기 또는 알킬아릴기이고; R3, R4, R5 및 R6은 서로 동일하거나 상이하고, 수소, 탄소원자 1~20개의 선형, 가지형 또는 고리형 알킬기, 알케닐기, 아릴기, 아릴알킬기 또는 알킬아릴기이다; 및(3) 60~150℃의 온도에서 상기 단계 (2)의 결과물과 티타늄할라이드를 반응시키고, 결과물을 세척하는 단계.
- 제 3항에 있어서, 상기 디알콕시마그네슘 1몰에 대하여 상기 내부전자공여체 0.1~1.0몰을 사용하는 것을 특징으로 하는 프로필렌 중합용 고체촉매의 제조방법.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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JP2013537593A JP5671625B2 (ja) | 2010-11-24 | 2011-09-02 | プロピレン重合用固体触媒およびその製造方法 |
EP11842944.8A EP2644628A4 (en) | 2010-11-24 | 2011-09-02 | SOLID CATALYST FOR POLYMERIZING PROPYLENE AND METHOD FOR THE PRODUCTION THEREOF |
US13/885,879 US9034781B2 (en) | 2010-01-13 | 2011-09-02 | Solid catalyst for the polymerization of propylene, and method for preparing same |
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KR1020100117370A KR101207628B1 (ko) | 2010-01-13 | 2010-11-24 | 프로필렌 중합용 고체촉매 및 그 제조 방법 |
KR10-2010-0117370 | 2010-11-24 |
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WO2012070753A2 true WO2012070753A2 (ko) | 2012-05-31 |
WO2012070753A3 WO2012070753A3 (ko) | 2012-07-19 |
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PCT/KR2011/006528 WO2012070753A2 (ko) | 2010-01-13 | 2011-09-02 | 프로필렌 중합용 고체촉매 및 그 제조 방법 |
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EP (1) | EP2644628A4 (ko) |
JP (1) | JP5671625B2 (ko) |
WO (1) | WO2012070753A2 (ko) |
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JP6054690B2 (ja) * | 2012-09-26 | 2016-12-27 | 東邦チタニウム株式会社 | オレフィン類重合用固体触媒成分、オレフィン類重合用触媒及びオレフィン類重合体の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4562173A (en) | 1984-08-24 | 1985-12-31 | Toho Titanium Co., Ltd. | Catalyst component for the polymerization of olefins and catalyst therefor |
US4981930A (en) | 1987-03-23 | 1991-01-01 | Idemitsu Petrochemical Company Limited | Method of production of polyolefins |
KR100491387B1 (ko) | 1996-02-27 | 2005-08-31 | 바셀 노쓰 아메리카 인코포레이티드 | 랜덤프로필렌공중합체의제조방법및그로부터수득된제품 |
KR100572616B1 (ko) | 2004-10-15 | 2006-04-24 | 삼성토탈 주식회사 | 올레핀 중합용 고체촉매 및 그 제조방법 |
US20090069510A1 (en) | 2007-09-11 | 2009-03-12 | Kansai Paint Co., Ltd. | Cationic electrodeposition paint compositions |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3932553A1 (de) * | 1989-09-29 | 1991-04-11 | Basf Ag | Katalysatorsysteme vom typ der ziegler-natta-katalysatoren |
FI90985C (fi) * | 1991-10-02 | 1994-04-25 | Neste Oy | Tehokkaan elektronidonorin sisältävä polymerointikatalyytin prokatalyyttikompositio |
JP2001114811A (ja) * | 1999-10-15 | 2001-04-24 | Idemitsu Petrochem Co Ltd | オレフィン重合用触媒及びオレフィン重合体の製造方法 |
DE60224205T2 (de) * | 2001-09-13 | 2008-12-11 | Basell Poliolefine Italia S.R.L. | Komponenten und katalysatoren für die polymerisation von olefinen |
KR100612108B1 (ko) * | 2004-10-29 | 2006-08-11 | 삼성토탈 주식회사 | 프로필렌 중합용 촉매 및 이를 이용한 프로필렌의 중합방법 |
KR100523474B1 (ko) * | 2005-03-29 | 2005-10-24 | 삼성토탈 주식회사 | 매우 높은 용융흐름성을 갖는 프로필렌 중합체의 제조방법 |
KR20100066612A (ko) * | 2008-12-10 | 2010-06-18 | 삼성토탈 주식회사 | 올레핀 중합 또는 공중합용 촉매, 이의 제조 방법 및 이를 이용한 올레핀의 중합 또는 공중합 방법 |
CN101824106B (zh) * | 2009-03-04 | 2012-05-30 | 中国石油天然气股份有限公司 | 烯烃聚合用催化组分及其催化剂 |
KR101207628B1 (ko) * | 2010-01-13 | 2012-12-03 | 삼성토탈 주식회사 | 프로필렌 중합용 고체촉매 및 그 제조 방법 |
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2011
- 2011-09-02 JP JP2013537593A patent/JP5671625B2/ja active Active
- 2011-09-02 WO PCT/KR2011/006528 patent/WO2012070753A2/ko active Application Filing
- 2011-09-02 EP EP11842944.8A patent/EP2644628A4/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4562173A (en) | 1984-08-24 | 1985-12-31 | Toho Titanium Co., Ltd. | Catalyst component for the polymerization of olefins and catalyst therefor |
US4981930A (en) | 1987-03-23 | 1991-01-01 | Idemitsu Petrochemical Company Limited | Method of production of polyolefins |
KR100491387B1 (ko) | 1996-02-27 | 2005-08-31 | 바셀 노쓰 아메리카 인코포레이티드 | 랜덤프로필렌공중합체의제조방법및그로부터수득된제품 |
KR100572616B1 (ko) | 2004-10-15 | 2006-04-24 | 삼성토탈 주식회사 | 올레핀 중합용 고체촉매 및 그 제조방법 |
US20090069510A1 (en) | 2007-09-11 | 2009-03-12 | Kansai Paint Co., Ltd. | Cationic electrodeposition paint compositions |
Non-Patent Citations (1)
Title |
---|
See also references of EP2644628A4 |
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JP5671625B2 (ja) | 2015-02-18 |
EP2644628A2 (en) | 2013-10-02 |
JP2014500346A (ja) | 2014-01-09 |
EP2644628A4 (en) | 2014-07-23 |
WO2012070753A3 (ko) | 2012-07-19 |
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