WO2008117916A1 - Preparation method of a solid titanium catalyst for olefin polymerization - Google Patents
Preparation method of a solid titanium catalyst for olefin polymerization Download PDFInfo
- Publication number
- WO2008117916A1 WO2008117916A1 PCT/KR2007/005464 KR2007005464W WO2008117916A1 WO 2008117916 A1 WO2008117916 A1 WO 2008117916A1 KR 2007005464 W KR2007005464 W KR 2007005464W WO 2008117916 A1 WO2008117916 A1 WO 2008117916A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- preparation
- halide compound
- magnesium
- solid titanium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 239000010936 titanium Substances 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000007787 solid Substances 0.000 title claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 35
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- -1 magnesium halide compound Chemical class 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 19
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 4
- 150000001298 alcohols Chemical class 0.000 claims abstract description 3
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 15
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- OLSMQDUPRYIMTC-UHFFFAOYSA-L magnesium;ethanol;dichloride Chemical compound [Mg+2].[Cl-].[Cl-].CCO OLSMQDUPRYIMTC-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—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
-
- 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
- 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
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a preparation method of a solid titanium catalyst for olefin polymerization, more specifically, to a preparation method of a solid titanium catalyst for olefin polymerization which has a uniform spherical shape, excellent catalyst activity and hydrogen reactivity, and high stereoregularity. Further, polymers prepared by using the catalyst have a small amount of xylene solubles.
- Titanium-based catalysts for olefin polymerization which contains magnesium and methods for preparing such catalysts, particularly, methods for preparing a catalyst using a magnesium compound solution for adjusting the particle shape and size of the catalyst have been reported many in this field of art.
- Tetrahydrofuran which is a cyclic ether, has been variously used as a solvent for magnesium chloride compound (for example, US patent No. 4,482,687), an additive of a cocatalyst (US patent No. 4,158,642), and a solvent (US patent No. 4,477,639).
- the present invention has been designed to resolve the problems of prior art as mentioned above. Therefore, the objects of the present invention is to provide a preparation method of a solid titanium catalyst for olefin polymerization which has a uniform spherical shape, excellent catalyst activity and hydrogen reactivity, and high stereoregularity, and can produce polymers having a small amount of xylene solubles.
- a preparation method of a solid titanium catalyst for olefin polymerization according to the present invention characteristically comprises the steps of:
- Examples of the magnesium halide compound used in the step (1) include halogenated magnesium, alkyl magnesium halide, alkoxymagnesium halide and ary- loxymagnesium halide.
- the magnesium halide compound may be used as a mixture of two or more species, and also effectively used as a complex compound with other metals.
- the cyclic ethers used in the step (1) is preferably a cyclic ether having 3-6 carbon atoms in the ring and derivatives thereof; more preferably tetrahydrofuran and 2-methyl tetrahydrofuran; and most preferably tetrahydrofuran.
- the alcohol used in the step (1) is preferably a monohydric alcohol or a polyhydric alcohol of C 1-20, and more preferably an alcohol of C2-12.
- the amount of said oxygen-containing solvent of the step (1) is 1-15 mol per 1 mol of magnesium atoms in the magnesium halide compound, preferably about 2-10 mol.
- the amount is less than 1 mol, the magnesium halide compound hardly dissolves, whereas when it is above 15 mol, the amount of the magnesium halide compound used is excessive large, as well as controls of particles is hardly achieved.
- the ratio of the amount of a cyclic ether and an alcohol in the oxygen-containing solvent is preferably 0.5-3.5 mol of an alcohol per 1 mol of a cyclic ether, however, it can be suitably adjusted, depending on the desired particle properties and dimensions of the resulted catalyst.
- the dissolving temperature in the step (1) is, although it may vary according to the species and amount of a cyclic ether and an alcohol used therein, preferably 20-200 0 C, and more preferably about 50-150 0 C.
- a hydrocarbon solvent may be additionally used as a diluent.
- a hydrocarbon solvent aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcy- clohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethyl benzene; and halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene may be mentioned.
- a titanium halide compound represented as the following general formula (I) is primarily added to the magnesium compound solution obtained from the step (1) at -10-30 0 C in a way of preventing particle generation, at a molar ratio of the oxygen-containing solvent: the titanium halide compound being 1:3.0-10, and then particles are precipitated by raising the temperature or aging. Thereafter, a titanium halide compound represented as the following general formula (I) is secondly added to the resulted magnesium compound solution for further reaction, at a molar ratio of the oxygen-containing solvent: the titanium halide compound being 1:0.3-7.0, thereby obtaining a carrier:
- R is a Cl-10 alkyl group
- X is a halogen atom
- a is an integer of 0-3, which is to meet the atomic valence of the formula.
- the step (3) is a step of impregnating titanium within the carrier by reacting the carrier obtained from the step (2) with the titanium halide compound and an electron donor, i.e. phthalic acid dialkylester having C9-13 alkyl groups.
- the reaction may be completed through a single reaction, however it is preferred to accomplish the reaction through twice or three times or more of reactions.
- the carrier obtained from the step (2) is reacted with the titanium halide compound or a suitable electron donor, and slurry remained after separating the liquid portion from the mixture is reacted again with the titanium halide compound and phthalic acid dialkylester as an electron donor. Subsequently, solids are separated from the resulted mixture, and then again reacted with the titanium halide compound or an appropriate electron donor.
- dialkyl phthalates such as diisononylphthalate, diisode- cylphthalate, di-tert-decylphthalate or the like and derivatives thereof may be mentioned.
- the molar ratio of the phthalic acid dialkylester electron donor used in the step (3) and the magnesium halide compound of the step (1) is 1:0.08-2.5.
- the step (4) is a step of washing the catalyst prepared from the step (3) with a hydrocarbon solvent at a high temperature, through which a highly stereoregular catalyst is completed.
- Examples of the hydrocarbon solvent used in the step (4) may include: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethyl benzene; and halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene.
- aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene
- alicyclic hydrocarbons such as cyclohexane and methylcyclohexane
- aromatic hydrocarbons such as benzene, toluene, xylene and ethyl benzene
- the washing temperature in the step (4) is 40-200 0 C, and preferably 50-150 0 C.
- a solid complex titanium catalyst prepared through the foregoing steps (I)- (4), may be used in polymerization of propylene; copolymerization of olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene or the like; and copoly- merization of conjugated or non-conjugated dienes such as polyunsaturated compounds.
- Step 1 preparation of a magnesium compound solution
- Step 2 preparation of a carrier
- Step 3 preparation of a catalyst
- Each particle size distribution of the resulted carrier and the catalyst was determined by using a laser particle size analyzer (Mastersizer X, Malvern Instruments), and the composition of the catalyst was analyzed by ICP.
- the catalyst as prepared above was determined to have about 25D of an average particle size, and 1.8 wt% of titanium.
- a catalyst was prepared by the same process as in Example 1, except that 0.09 mol of diisodecylphthalate per mol of MgCl instead of diisononylphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.09 mol of di-tert-decylphthalate per mol of MgCl instead of diisononylphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 3,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
- a catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 5,000ml of hydrogen was used in the polymerization process.
- the results were shown in Table 1.
- a catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 7,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diisodecylphthalate per mol of MgCl instead of diisononylphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1. [69] Example 11
- a catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diisodecylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 3,000ml of hydrogen was used in the polymerization process.
- the results were shown in Table 1.
- a catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 5,000ml of hydrogen was used in the polymerization process.
- the results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst was prepared by the same process as in Example 1, except that 0.09 mol of diethylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- Comparative Example 7 A catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diethylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- Comparative Example 8 A catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diethylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
- a catalyst obtained by a preparation method of a solid titanium catalyst for olefin polymerization according to the present invention has a uniform spherical shape, excellent catalyst activity and hydrogen reactivity, and high stereoregularity. Further, polymers prepared by using the catalyst have a small amount of xylene solubles, thereby increasing the productivity of a polymerization process.
Abstract
A preparation method of a solid titanium catalyst for olefin polymerization characteristically comprises the steps of: (1) obtaining a magnesium compound solution by dissolving a magnesium halide compound in an oxygen-containing solvent that is a mixed solvent of a cyclic ether and at least one of alcohols; (2) preparing a carrier by primarily reacting the obtained magnesium compound solution with a titanium halide compound at -10-30°C, then raising a temperature or aging so as to obtain particles, and secondly reacting the particles with a titanium halide compound; (3) preparing a catalyst by reacting the carrier with a titanium halide compound and an electron donor of phthalic acid dialkylester having a C9-13 alkyl group; and (4) washing the prepared catalyst with a hydrocarbon solvent at 40-200°C.
Description
Description
PREPARATION METHOD OF A SOLID TITANIUM CATALYST FOR OLEFIN POLYMERIZATION
Technical Field
[1] The present invention relates to a preparation method of a solid titanium catalyst for olefin polymerization, more specifically, to a preparation method of a solid titanium catalyst for olefin polymerization which has a uniform spherical shape, excellent catalyst activity and hydrogen reactivity, and high stereoregularity. Further, polymers prepared by using the catalyst have a small amount of xylene solubles. Background Art
[2] So far, many catalysts for olefin polymerization and polymerization methods using the same have been reported. However, efforts have been made to improve the physical properties of polymers obtained by using such designed catalysts so as to increase the productivity and product quality, in order to raise the commercial significance of a catalyst. Further, there still have been demands for improvement in the activity and stereospecificity of a catalyst per se.
[3] Titanium-based catalysts for olefin polymerization which contains magnesium, and methods for preparing such catalysts, particularly, methods for preparing a catalyst using a magnesium compound solution for adjusting the particle shape and size of the catalyst have been reported many in this field of art.
[4] For obtaining such magnesium compound solution, there are methods of reacting a magnesium compound with an electron donor such as an alcohol, amine, ether, ester, carboxylic acid and the like, in the presence of a hydrocarbon solvent. Examples of a method using an alcohol are described in US patent Nos. 4,330,649 and 5,106,807, and Japanese laid-open patent publication Sho58-83006. Moreover, US patent Nos. 4,315,874, 4,399,054 and 4,071,674 also report methods of preparing a magnesium solution.
[5] Tetrahydrofuran, which is a cyclic ether, has been variously used as a solvent for magnesium chloride compound (for example, US patent No. 4,482,687), an additive of a cocatalyst (US patent No. 4,158,642), and a solvent (US patent No. 4,477,639).
[6] US patent Nos. 4,347,158, 4,422,957, 4,425,257, 4,618,661 and 4,680,381 suggest a method for preparing a catalyst by adding a Lewis acid compound such as aluminum chloride to a support, magnesium chloride, and then milling the mixture.
[7] However, although the above-mentioned patents have been improved in terms of a catalyst activity, there are still problems such that the shape, size and size distribution of a catalyst are irregular, and the stereoregularity should be further improved.
[8] US patent No. 5,360,776 discloses a catalyst obtained by reacting a magnesium chloride-ethanol complex carrier with dialkyl phthalate having 10 carbon atoms as an electron donor. It insists that thus obtained catalyst shows higher activity, however any mention regarding stereoregularity as well as hydrogen reactivity are not found. There are many cases that the hydrogen reactivity is mostly often a major requisite of a catalyst at the time of producing a certain polypropylene product through a polymerization process. Therefore, it can be said that a catalyst having such characteristic is preferred.
Disclosure of Invention Technical Problem
[9] As described above, improvement of the commercial value of a catalyst for alpha- olefin polymerization is focused on efforts for improving product quality by preparing a catalyst having high polymerization activity and stereoregularity; efforts for increasing the productivity by regulating the shape and size of a catalyst; and efforts for reducing production cost by improving the production yield and activity of a catalyst in catalyst production. Such efforts are being made in this field of art, and improvement in such efforts, as an important factor to a catalyst economy, is in demand. Technical Solution
[10] The present invention has been designed to resolve the problems of prior art as mentioned above. Therefore, the objects of the present invention is to provide a preparation method of a solid titanium catalyst for olefin polymerization which has a uniform spherical shape, excellent catalyst activity and hydrogen reactivity, and high stereoregularity, and can produce polymers having a small amount of xylene solubles.
[11] A preparation method of a solid titanium catalyst for olefin polymerization according to the present invention characteristically comprises the steps of:
[12] (1) obtaining a magnesium compound solution by dissolving a magnesium halide compound in an oxygen-containing solvent that is a mixed solvent of a cyclic ether and at least one of alcohols;
[13] (2) preparing a carrier by primarily reacting the obtained magnesium compound solution with a titanium halide compound at -10-300C, then raising a temperature or aging so as to obtain particles, and secondly reacting the particles with a titanium halide compound;
[14] (3) preparing a catalyst by reacting the carrier with a titanium halide compound and phthalic acid dialkylester having a C9-13 alkyl group as an electron donor; and
[15] (4) washing the prepared catalyst with a hydrocarbon solvent at 40-2000C.
[16] Examples of the magnesium halide compound used in the step (1) include halogenated magnesium, alkyl magnesium halide, alkoxymagnesium halide and ary-
loxymagnesium halide. The magnesium halide compound may be used as a mixture of two or more species, and also effectively used as a complex compound with other metals.
[17] The cyclic ethers used in the step (1) is preferably a cyclic ether having 3-6 carbon atoms in the ring and derivatives thereof; more preferably tetrahydrofuran and 2-methyl tetrahydrofuran; and most preferably tetrahydrofuran.
[18] The alcohol used in the step (1) is preferably a monohydric alcohol or a polyhydric alcohol of C 1-20, and more preferably an alcohol of C2-12.
[19] The amount of said oxygen-containing solvent of the step (1) is 1-15 mol per 1 mol of magnesium atoms in the magnesium halide compound, preferably about 2-10 mol. When the amount is less than 1 mol, the magnesium halide compound hardly dissolves, whereas when it is above 15 mol, the amount of the magnesium halide compound used is excessive large, as well as controls of particles is hardly achieved.
[20] The ratio of the amount of a cyclic ether and an alcohol in the oxygen-containing solvent, is preferably 0.5-3.5 mol of an alcohol per 1 mol of a cyclic ether, however, it can be suitably adjusted, depending on the desired particle properties and dimensions of the resulted catalyst.
[21] The dissolving temperature in the step (1) is, although it may vary according to the species and amount of a cyclic ether and an alcohol used therein, preferably 20-2000C, and more preferably about 50-1500C.
[22] In the step (1), a hydrocarbon solvent may be additionally used as a diluent. As a hydrocarbon solvent, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcy- clohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethyl benzene; and halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene may be mentioned.
[23] In the step (2), a titanium halide compound represented as the following general formula (I) is primarily added to the magnesium compound solution obtained from the step (1) at -10-300C in a way of preventing particle generation, at a molar ratio of the oxygen-containing solvent: the titanium halide compound being 1:3.0-10, and then particles are precipitated by raising the temperature or aging. Thereafter, a titanium halide compound represented as the following general formula (I) is secondly added to the resulted magnesium compound solution for further reaction, at a molar ratio of the oxygen-containing solvent: the titanium halide compound being 1:0.3-7.0, thereby obtaining a carrier:
[24] Ti(OR) a X (4-a) (I)
[25] wherein, R is a Cl-10 alkyl group; X is a halogen atom; and a is an integer of 0-3, which is to meet the atomic valence of the formula.
[26] When primarily adding the titanium halide compound to the magnesium compound solution in the step (2), conditions such as a temperature at the time of addition and a molar ratio between the oxygen-containing solvent and the titanium halide compound may be suitably adjusted to prevent precipitates from being generated, which is important to control the morphology of the resulting carrier. After the generation of carrier particles, the second addition of the titanium halide compound may be conducted for further reaction, thereby increasing the production yield of a catalyst.
[27] The step (3) is a step of impregnating titanium within the carrier by reacting the carrier obtained from the step (2) with the titanium halide compound and an electron donor, i.e. phthalic acid dialkylester having C9-13 alkyl groups. The reaction may be completed through a single reaction, however it is preferred to accomplish the reaction through twice or three times or more of reactions.
[28] Preferably, in the step (3), the carrier obtained from the step (2) is reacted with the titanium halide compound or a suitable electron donor, and slurry remained after separating the liquid portion from the mixture is reacted again with the titanium halide compound and phthalic acid dialkylester as an electron donor. Subsequently, solids are separated from the resulted mixture, and then again reacted with the titanium halide compound or an appropriate electron donor.
[29] As for an electron donor, i.e. phthalic acid dialkylester having C9-13 alkyl groups used in the step (3), dialkyl phthalates such as diisononylphthalate, diisode- cylphthalate, di-tert-decylphthalate or the like and derivatives thereof may be mentioned.
[30] The molar ratio of the phthalic acid dialkylester electron donor used in the step (3) and the magnesium halide compound of the step (1) (the magnesium halide compound: phthalic acid dialkylester) is 1:0.08-2.5.
[31] The step (4) is a step of washing the catalyst prepared from the step (3) with a hydrocarbon solvent at a high temperature, through which a highly stereoregular catalyst is completed.
[32] Examples of the hydrocarbon solvent used in the step (4) may include: aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethyl benzene; and halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride and chlorobenzene.
[33] In order to further increase the stereoregularity of a solid complex titanium catalyst, the washing temperature in the step (4) is 40-2000C, and preferably 50-1500C.
[34] A solid complex titanium catalyst prepared through the foregoing steps (I)- (4), may be used in polymerization of propylene; copolymerization of olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene or the like; and copoly-
merization of conjugated or non-conjugated dienes such as polyunsaturated compounds.
Mode for the Invention
[35] The present invention will be understood fully by the following examples, however it should be noted that such examples are only to illustrate the present invention, and they are not to limit the scope of the right sought to be protected by the present invention.
[36] Examples
[37] Example 1
[38] Preparation of a solid titanium catalyst
[39] Step 1 : preparation of a magnesium compound solution
[40] To a 1OL volume reactor equipped with a mechanical stirrer, of which atmosphere was substituted with nitrogen, 300g of MgCl , 4.5kg of toluene, 350g of tetrahydrofuran and 60Og of butanol were added, and the temperature was raised to 11O0C, while stirring at 550rpm. It was maintained for 3 hours, thereby obtaining a uniform solution.
[41] Step 2: preparation of a carrier
[42] The solution obtained from the step 1 was cooled to 2O0C, and thereto 70Og of TiCl
4 was added. Then, the temperature of the reactor was elevated to 6O0C over 1 hour, and when reached to 6O0C, 28Og of TiCl was added thereto over 40 minutes and allowed to react for 30 minutes. After the reaction, it was allowed to stand for 30 minutes so as to precipitate carriers and then the upper portion of the solution was removed. The slurry remained in the reactor was subjected to, after addition of 2kg of toluene, stirring, standing, removal of the supernatant, and the above procedure was repeated 3 times for washing.
[43] Step 3: preparation of a catalyst
[44] To the carrier prepared in the above step 2, 2.0kg of toluene and 2.0kg of TiCl 4 were added, and then the temperature of the reactor was elevated to 11O0C over 1 hour. The mixture was aged for 1 hour, and stood still for 15 minutes so that solids can be precipitated, and then the supernatant was removed. To the remained slurry, 2.0kg of toluene, 2.0kg of TiCl and diisononylphthalate at the amount of 0.09 mol per mol of MgCl used in the step 1 were added. The temperature of the reactor was elevated to 1130C and maintained for 1 hour for allowing a reaction. After the reaction, the resultant was stood still for 30 minutes and then the supernatant was separated. Then, 2.0kg of toluene and 2.0kg of TiCl were added thereto again, and it was allowed to
4 react at 1000C for 30 minutes. After the reaction, it was stirred for 30 minutes and stood still, and then the supernatant was removed therefrom.
[45] Step 4: washing
[46] To the catalyst slurry separated from the step 3, 2.0kg of hexane was added, and the temperature of the reactor was maintained at 4O0C for 30 minutes while stirring. Then, stirring was stopped, and the mixture was maintained still for 30 minutes. The supernatant was removed. The remained catalyst slurry was washed 6 times again in the same way with the addition of hexane, thereby producing the final solid titanium catalyst.
[47] Each particle size distribution of the resulted carrier and the catalyst was determined by using a laser particle size analyzer (Mastersizer X, Malvern Instruments), and the composition of the catalyst was analyzed by ICP.
[48] The catalyst as prepared above was determined to have about 25D of an average particle size, and 1.8 wt% of titanium.
[49] Polymerization
[50] Polymerization of propylene was carried out in order to evaluate the performance of the resulted catalyst. In a glove box under a nitrogen atmosphere, about 7mg of the prepared catalyst were weighed and placed into a glass bulb. The glass bulb was sealed and installed in a 4L autoclave in a way that the bulb breaks simultaneously with the operation of a stirrer so as to start the reaction. The reactor was purged with nitrogen for about 1 hour so that the atmosphere of the reactor was changed to dry nitrogen. Thereto, triethyl aluminum (molar ratio of Al/Ti=850) and dicy- clopentyldimethoxysilane (molar ratio of Si/Al=0.1) as an external electron donor were added, and the reactor was tightly closed. After injecting 1,000ml of hydrogen and 2,400ml of liquid propylene by using a syringe pump into the reactor, the glass bulb was broken by beginning stirring so as to initiate a polymerization reaction and at the same time the temperature of the reactor was raised to 7O0C over 20 minutes. The polymerization was carried out for 1 hour. After 1 hour, unreacted propylene was vented out into air, and the temperature of the reactor was cooled down to room temperature. The produced polymers were dried in a vacuum oven at 5O0C and weighed. Thus prepared polypropylene powder was analyzed for xylene solubles and MI (melt index), which are routinely practiced in this field of art. The results were represented in Table 1 shown below.
[51] Example 2
[52] A catalyst was prepared by the same process as in Example 1, except that 0.09 mol of diisodecylphthalate per mol of MgCl instead of diisononylphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[53] Example 3
[54] A catalyst was prepared by the same process as in Example 1, except that 0.09 mol
of di-tert-decylphthalate per mol of MgCl instead of diisononylphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[55] Example 4
[56] A catalyst was prepared by the same process as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[57] Example 5
[58] A catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 3,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
[59] Example 6
[60] A catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 5,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
[61] Example 7
[62] A catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.11 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 7,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
[63] Example 8
[64] A catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[65] Example 9
[66] A catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diisononylphthalate per mol of MgCl was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[67] Example 10
[68] A catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diisodecylphthalate per mol of MgCl instead of diisononylphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[69] Example 11
[70] A catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diisodecylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[71] Comparative Example 1
[72] A catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[73] Comparative Example 2
[74] A catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 3,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
[75] Comparative Example 3
[76] A catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 5,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
[77] Comparative Example 4
[78] A catalyst preparation and polymerization were carried out by the same processes as in Example 1, except that 0.15 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1, and 7,000ml of hydrogen was used in the polymerization process. The results were shown in Table 1.
[79] Comparative Example 5
[80] A catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diisobutylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[81] Comparative Example 6
[82] A catalyst was prepared by the same process as in Example 1, except that 0.09 mol of diethylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[83] Comparative Example 7 [84] A catalyst was prepared by the same process as in Example 1, except that 0.15 mol of diethylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[85] Comparative Example 8 [86] A catalyst was prepared by the same process as in Example 1, except that 0.20 mol of diethylphthalate per mol of MgCl instead of diisononyphthalate was used in the step 3 of the preparation of a solid titanium catalyst in Example 1. The results were shown in Table 1.
[87] [88] Table 1
[89] (1) DINP: diisononyl phthalate [90] (2) DIDP: diisodecyl phthalate [91] (3) DTDP: di-tert-decyl phthalate [92] (4) DIBP: diisobutyl phthalate [93] (5) DEP: diethyl phthalate [94]
Industrial Applicability
[95] A catalyst obtained by a preparation method of a solid titanium catalyst for olefin polymerization according to the present invention has a uniform spherical shape, excellent catalyst activity and hydrogen reactivity, and high stereoregularity. Further, polymers prepared by using the catalyst have a small amount of xylene solubles, thereby increasing the productivity of a polymerization process.
[96]
Claims
(1) obtaining a magnesium compound solution by dissolving a magnesium halide compound in an oxygen-containing solvent that is a mixed solvent of a cyclic ether and at least one of alcohols;
(2) preparing a carrier by primarily reacting the obtained magnesium compound solution with a titanium halide compound at -10-300C, then raising a temperature or aging so as to obtain particles, and secondly reacting the particles with a titanium halide compound;
(3) preparing a catalyst by reacting the carrier with a titanium halide compound and phthalic acid dialkylester having C9-13 alkyl groups as an electron donor; and
(4) washing the prepared catalyst with a hydrocarbon solvent at 40-2000C. [2] The preparation method of a solid titanium catalyst for olefin polymerization according to claim 1, wherein the amount of oxygen-containing solvent in the step (1) is 1-15 mol per 1 mol of magnesium atoms contained in the magnesium halide compound.
[3] The preparation method of a solid titanium catalyst for olefin polymerization according to claim 1, wherein the titanium halide compound in the step (2) is a compound of a general formula (I): Ti(OR) X (I) a (4-a) wherein R is a Cl-10 alkyl group; X is a halogen atom, and; a is an integer of 0-3.
[4] The preparation method of a solid titanium catalyst for olefin polymerization according to claim 1, wherein the electron donor, phthalic acid dialkylester having C9-13 alkyl groups in the step (3) is diisononylphthalate, diisode- cylphthalate or di-tert-decylphthalate.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07833772A EP2129694A4 (en) | 2007-03-28 | 2007-10-31 | Preparation method of a solid titanium catalyst for olefin polymerization |
US12/530,280 US20100105543A1 (en) | 2007-03-28 | 2007-10-31 | Preparation method of a solid titanium catalyst for olefin polymerization |
JP2009553503A JP2010534724A (en) | 2007-03-28 | 2007-10-31 | Method for producing solid titanium catalyst for olefin polymerization |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020070030326A KR100878429B1 (en) | 2007-03-28 | 2007-03-28 | A preparation method of a solid titanium catalyst for olefin polymerization |
KR10-2007-0030326 | 2007-03-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008117916A1 true WO2008117916A1 (en) | 2008-10-02 |
Family
ID=39788639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2007/005464 WO2008117916A1 (en) | 2007-03-28 | 2007-10-31 | Preparation method of a solid titanium catalyst for olefin polymerization |
Country Status (6)
Country | Link |
---|---|
US (1) | US20100105543A1 (en) |
EP (1) | EP2129694A4 (en) |
JP (1) | JP2010534724A (en) |
KR (1) | KR100878429B1 (en) |
CN (1) | CN101663333A (en) |
WO (1) | WO2008117916A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034025A (en) * | 1997-05-09 | 2000-03-07 | Samsung General Chemicals, Co., Ltd. | Catalyst for polymerization and copolymerization of olefins |
US6111038A (en) * | 1995-10-11 | 2000-08-29 | Mitsui Chemicals | Process for preparing solid titanium catalyst component for olefin polymerization and process for preparing polyolefin |
KR20050087573A (en) * | 2004-02-27 | 2005-08-31 | 삼성토탈 주식회사 | Method for the preparation of a solid titanium catalyst for olefin polymerization |
KR20050087574A (en) * | 2004-02-27 | 2005-08-31 | 삼성토탈 주식회사 | Method for the preparation of a solid titanium catalyst for olefin polymerization |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
US4158642A (en) * | 1977-04-25 | 1979-06-19 | Exxon Research & Engineering Co. | Trialkyl aluminum cocatalyst |
IT1098272B (en) * | 1978-08-22 | 1985-09-07 | Montedison Spa | COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
JPS6037804B2 (en) * | 1979-04-11 | 1985-08-28 | 三井化学株式会社 | Method for manufacturing carrier for olefin polymerization catalyst |
JPS56811A (en) * | 1979-06-18 | 1981-01-07 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer or copolymer |
US4482687A (en) * | 1979-10-26 | 1984-11-13 | Union Carbide Corporation | Preparation of low-density ethylene copolymers in fluid bed reactor |
US4618661A (en) * | 1980-05-02 | 1986-10-21 | Phillips Petroleum Company | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
US4422957A (en) * | 1980-05-02 | 1983-12-27 | Phillips Petroleum Company | Methods of producing polyolefins using supported high efficiency polyolefin catalyst components |
US4347158A (en) * | 1980-05-02 | 1982-08-31 | Dart Industries, Inc. | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
US4425257A (en) * | 1980-05-02 | 1984-01-10 | Phillips Petroleum Company | Supported high efficiency polyolefin catalyst component and methods of making and using the same |
JPS5869225A (en) * | 1981-10-20 | 1983-04-25 | Kanegafuchi Chem Ind Co Ltd | Isolation of polymer |
JPS5883006A (en) * | 1981-11-13 | 1983-05-18 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
US4477639A (en) * | 1983-05-27 | 1984-10-16 | Shell Oil Company | Olefin polymerization catalyst component and composition and method of preparation |
IT1241062B (en) * | 1990-01-10 | 1993-12-29 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
FI86548C (en) * | 1990-11-07 | 1992-09-10 | Neste Oy | Improved stereoselective catalyst for polymerization of olefins |
FI88047C (en) * | 1991-05-09 | 1993-03-25 | Neste Oy | Catalyst-based catalyst for polymerization of olivines |
GB2321462B (en) * | 1997-01-25 | 1999-03-03 | Samsung General Chemicals Co | An improved process for polymerization and copolymerization of olefins |
KR100530797B1 (en) * | 2004-01-28 | 2005-11-23 | 삼성토탈 주식회사 | Method for preparation of a solid titanium catalyst for olefin polymerization |
KR100604962B1 (en) * | 2004-02-27 | 2006-07-26 | 삼성토탈 주식회사 | Method for the preparation of a solid titanium catalyst for olefin polymerization |
KR100723365B1 (en) * | 2005-09-30 | 2007-05-30 | 삼성토탈 주식회사 | Method for producing propylene polymer using alkoxysilane compound containing trialkylsilyl group in molecular structure |
-
2007
- 2007-03-28 KR KR1020070030326A patent/KR100878429B1/en not_active IP Right Cessation
- 2007-10-31 JP JP2009553503A patent/JP2010534724A/en not_active Withdrawn
- 2007-10-31 US US12/530,280 patent/US20100105543A1/en not_active Abandoned
- 2007-10-31 WO PCT/KR2007/005464 patent/WO2008117916A1/en active Application Filing
- 2007-10-31 EP EP07833772A patent/EP2129694A4/en active Pending
- 2007-10-31 CN CN200780052352A patent/CN101663333A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6111038A (en) * | 1995-10-11 | 2000-08-29 | Mitsui Chemicals | Process for preparing solid titanium catalyst component for olefin polymerization and process for preparing polyolefin |
US6034025A (en) * | 1997-05-09 | 2000-03-07 | Samsung General Chemicals, Co., Ltd. | Catalyst for polymerization and copolymerization of olefins |
KR20050087573A (en) * | 2004-02-27 | 2005-08-31 | 삼성토탈 주식회사 | Method for the preparation of a solid titanium catalyst for olefin polymerization |
KR20050087574A (en) * | 2004-02-27 | 2005-08-31 | 삼성토탈 주식회사 | Method for the preparation of a solid titanium catalyst for olefin polymerization |
Non-Patent Citations (1)
Title |
---|
See also references of EP2129694A4 * |
Also Published As
Publication number | Publication date |
---|---|
KR100878429B1 (en) | 2009-01-13 |
EP2129694A1 (en) | 2009-12-09 |
KR20080088017A (en) | 2008-10-02 |
US20100105543A1 (en) | 2010-04-29 |
EP2129694A4 (en) | 2011-05-04 |
CN101663333A (en) | 2010-03-03 |
JP2010534724A (en) | 2010-11-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1992019659A1 (en) | A large-pore polyolefin, a method for its production and a procatalyst containing a transesterification product of a lower alcohol and a phthalic acid ester | |
EP2516479A2 (en) | New internal and external donor compounds for olefin polymerization catalysts | |
WO2013082631A1 (en) | Internal electron donor for olefin polymerization catalysts, method of making and using the same | |
AU9262498A (en) | Components and catalysts for the polymerization of olefins | |
US7566676B2 (en) | Preparation method of solid titanium catalyst for olefin polymerization | |
US20100240846A1 (en) | Catalyst component for the polymerization of olefins based on 1,3-diethers | |
EP2029277B1 (en) | Catalyst component for the polymerization of olefins | |
WO2004072122A2 (en) | The preparation of a magnesium halide support for olefin polymerization and a catalyst composition using the same | |
US20070298964A1 (en) | Preparation Method Of Solid Titanium Catalyst For Olefin Polymerization | |
WO2008117916A1 (en) | Preparation method of a solid titanium catalyst for olefin polymerization | |
EP2578604A1 (en) | Production method for a spherical carrier for an olefin polymerization catalyst, and a solid catalyst using the same and propylene polymers | |
KR100554269B1 (en) | A method for the preparation of a solid catalyst for alpha olefin polymerization | |
CN112759604B (en) | Magnesium halide adduct and preparation method thereof, catalyst component for olefin polymerization, catalyst and olefin polymerization method | |
KR100546506B1 (en) | A method for the preparation of a solid titanium catalyst for olefin polymerization | |
KR102467581B1 (en) | Catalyst COMPOSITION for Polymerization of oleFin, METHOD OF PRODUCING THE SAME, AND METHOD OF PRODUCING POLYOLEFIN USING THE SAME METHOD | |
KR100869442B1 (en) | Olefin polymerization or copolymerization method | |
KR100827192B1 (en) | A preparation method of a solid titanium catalyst for olefin polymerization | |
KR100554268B1 (en) | A method for the preparation of a solid catalyst for alpha olefin polymerization | |
KR102160452B1 (en) | Method for manufacturing catalyst composition for polymerization of olefin, catalyst composition for polymerization of olefin manufactured by the method and process for polymerization of olefin using the same | |
WO2012118510A1 (en) | Internal and external donor compounds for olefin polymerization catalysts iii | |
KR100870818B1 (en) | Olefin polymerization or copolymerization method | |
KR100573920B1 (en) | Method for the preparation of a solid titanium catalyst for olefin polymerization |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780052352.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07833772 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007833772 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009553503 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |