CN115975080A - Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method - Google Patents
Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method Download PDFInfo
- Publication number
- CN115975080A CN115975080A CN202111200521.8A CN202111200521A CN115975080A CN 115975080 A CN115975080 A CN 115975080A CN 202111200521 A CN202111200521 A CN 202111200521A CN 115975080 A CN115975080 A CN 115975080A
- Authority
- CN
- China
- Prior art keywords
- titanium
- magnesium
- compound
- catalyst component
- ethylene polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000005977 Ethylene Substances 0.000 title claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 22
- -1 alcohol compound Chemical class 0.000 claims abstract description 18
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 13
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 229910052749 magnesium Inorganic materials 0.000 claims description 25
- 239000011777 magnesium Substances 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QMJUEAKSVSCCQL-UHFFFAOYSA-N benzyl phosphite Chemical compound [O-]P([O-])OCC1=CC=CC=C1 QMJUEAKSVSCCQL-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000004438 haloalkoxy group Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002680 magnesium Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- UZFAAQNJTDECPW-UHFFFAOYSA-N CC(C)C[AlH]CC(C)C.Cl Chemical compound CC(C)C[AlH]CC(C)C.Cl UZFAAQNJTDECPW-UHFFFAOYSA-N 0.000 description 1
- MVJSLTMEEOSFIE-UHFFFAOYSA-N CC[AlH]CC.Cl Chemical compound CC[AlH]CC.Cl MVJSLTMEEOSFIE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention belongs to the technical field of ethylene polymerization, and discloses a magnesium-titanium-containing catalyst component for ethylene polymerization, a catalyst and an ethylene polymerization reaction method, wherein the preparation method of the magnesium-titanium-containing catalyst component comprises the following steps: 1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at the reaction temperature of 95-110 ℃ to obtain a uniform solution; 2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, washing and drying to obtain the magnesium-titanium-containing catalyst component. The bulk density and particle sphericity of the polymer prepared by the catalyst are obviously higher.
Description
Technical Field
The invention belongs to the technical field of ethylene polymerization, and particularly relates to a magnesium-titanium-containing catalyst component and a catalyst for ethylene polymerization, and an ethylene polymerization reaction method.
Background
In the polymerization of olefins, particularly in the polymerization of ethylene or the copolymerization of ethylene and α -olefins, catalyst components based on magnesium, titanium, halogen and an electron donor are mostly used.
In fact, the above catalyst components are mainly composed of magnesium chloride, titanium chloride and electron donors. The early catalyst component is prepared by mixing and grinding magnesium chloride, titanium tetrachloride and electron donor, and the catalyst has low activity, the prepared polymer has wide particle size distribution, and more coarse powder and fine powder, and is basically eliminated at present.
One is to load the catalyst component on a porous spherical silica gel in a fixed form, for example, patent document CN1158136 discloses a main catalyst for producing ethylene high polymer, which comprises an inorganic carrier (preferably active silica carrier), a chlorine compound supported on the carrier, a magnesium compound supported on the carrier, a titanium compound supported on the carrier. The main catalyst is characterized in that: the catalyst has spherical particle shape, good fluidity and good hydrogen regulation sensitivity, the polymerization activity is reduced less along with the increase of the addition amount of the chain transfer agent (hydrogen), and the catalyst is more suitable for producing the polyethylene resin with wide molecular weight distribution.
The other method is to dissolve a magnesium compound into a uniform solution, and then react the magnesium compound with a titanium compound to precipitate magnesium chloride particles and simultaneously load titanium chloride and an electron donor, as disclosed in patent documents CN85100997, CN1112373C, CN1229092A, CN1958620 and the like. The method generally dissolves a magnesium compound in a polar solvent, and the magnesium compound and titanium tetrachloride contact and react through a dissolving solution to separate out catalyst component particles containing titanium magnesium and electron donors.
Patent document CN85100997 is prepared by dissolving a magnesium halide in an organic epoxy compound or an organic phosphorus compound to form a homogeneous solution, and reacting the solution with at least one precipitation aid, and a halide of titanium transition metal or a derivative thereof. Because the organic epoxy compound and the organic phosphorus compound which do not contain active hydrogen are used as solvents, the magnesium chloride is slowly dissolved, and the reaction with titanium tetrachloride is convenient to control, the particle shape of the precipitated particles is good and is similar to a sphere, the particle shape of the prepared polymer is good, the stacking density is high, but the activity of the prepared catalyst component is low, and the ash content in the product is particularly high when the catalyst is applied to industrial production.
Patent document CN1112373C is prepared by dissolving magnesium chloride in isooctanol using decane as a dispersant, adding silane as a precipitating agent, and precipitating catalyst component particles by reaction with titanium tetrachloride. The solvent used in the system is isooctanol, the raw material is simple, the activity of the catalyst component is higher during the ethylene polymerization, the hydrogen regulation performance is better, but the preparation method of the catalyst component uses more titanium tetrachloride, and the particle shape of the catalyst component is similar to a sphere and is not regular.
Patent document CN1229092a discloses a catalyst for ethylene polymerization or copolymerization, which is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound, and then adding a low carbon alcohol as an electron donor activator to form a uniform solution, and then reacting the uniform solution with at least one anhydride auxiliary precipitator and halides of transition metal titanium and derivatives thereof.
In patent document CN1958620, the catalyst is prepared by dissolving magnesium halide in organic epoxy compound, organic phosphorus compound and a lower alcohol to form a homogeneous solution, and reacting with at least one silane compound and halide of transition metal titanium and its derivatives, and the activity of the catalyst is higher when the catalyst is used for slurry polymerization of ethylene, but the particle morphology and particle size distribution of the catalyst component prepared by the method still need to be improved.
Disclosure of Invention
In view of the above circumstances, it is an object of the present invention to provide a magnesium-titanium-containing catalyst component for ethylene polymerization, a catalyst and an ethylene polymerization process, wherein the polymer obtained by using the catalyst of the present invention has a high bulk density and a high degree of particle sphericity, and the surface of the polymer is relatively smooth.
The first aspect of the present invention provides a magnesium-containing titanium catalyst component for ethylene polymerization, which is prepared by a method comprising:
1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at the reaction temperature of 95-110 ℃ to obtain a uniform solution;
2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, washing and drying to obtain the magnesium-titanium-containing catalyst component.
In a second aspect of the present invention, there is provided a catalyst for ethylene polymerization, which comprises the above magnesium-titanium-containing catalyst component, and an organoaluminum compound.
A third aspect of the present invention provides an ethylene polymerization process comprising: ethylene or ethylene and an alpha-olefin are reacted in the presence of the catalyst described above.
The invention dissolves the magnesium compound in a solvent system containing an organic phosphorus compound, an organic alcohol compound and a diluent, controls the temperature during dissolution, obtains the catalyst with normal activity, prepares the polymer with equivalent molecular weight, obviously improves the bulk density and the particle sphericity of the polymer, and has smoother surface and less protrusions. The catalyst component of the invention has simple preparation materials and can still obtain the catalyst with better performance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an electron micrograph of the polymer obtained in example 1.
FIG. 2 is an electron micrograph of a polymer obtained in comparative example.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a magnesium-containing titanium catalyst component for ethylene polymerization, the magnesium-containing titanium catalyst component being prepared by a process comprising:
1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at the reaction temperature of 95-110 ℃ to obtain a uniform solution;
2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, washing and drying to obtain the magnesium-titanium-containing catalyst component.
In the present invention, the magnesium compound may be a magnesium-containing compound known to those skilled in the art, such as a magnesium halide, a magnesium alcoholate, a magnesium haloalcoholate, or the like. Preferably, the magnesium compound is a magnesium dihalide or a derivative of the formula magnesium dihalide in which one halogen atom is replaced by a hydrocarbyl or halohydrocarbyloxy group.
According to the invention, the organophosphorus compound can be chosen from hydrocarbyl or halogenated hydrocarbyl esters of orthophosphoric acid, hydrocarbyl or halogenated hydrocarbyl esters of phosphorous acid. For example, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, and the like.
According to the present invention, the organic alcohol compound may be selected from linear alcohols or isomeric alcohols having 1 to 8 carbon atoms. Specific examples of organic alcohol compounds include, but are not limited to: at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol, and isooctanol. Preferably a linear alcohol or an isomeric alcohol of 3 to 8 carbon atoms.
In the present invention, the diluent may be benzene, toluene, xylene, chlorobenzene, or derivatives thereof.
According to the invention, the titanium compound has the general formula Ti (OR) aXb, where R is C 1 -C 14 X is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, and a + b =3 or 4.
Specifically, the titanium compound may be at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, and titanium trichloride. The titanium compound is preferably titanium tetrachloride, titanium trichloroethoxy or titanium trichloride.
According to the present invention, the organophosphorus compound is contained in an amount of 0.01 to 10 mol, preferably 0.02 to 4 mol, per mol of the magnesium compound; the amount of the organic alcohol compound is 0.01 to 15 mol, preferably 0.05 to 10 mol; the dosage of the diluent is 0.2-5L; the titanium compound is used in an amount of 0.2 to 30 moles, preferably 1 to 20 moles.
Preferably, in the step 1), the stirring speed is 350-500rpm, and the reaction time is 0.5-1.5h.
Preferably, in the step 2), the temperature of the uniform solution is reduced to-30 ℃ to 5 ℃, and the temperature of the uniform solution is increased to 60 ℃ to 110 ℃.
According to a second aspect of the present invention, there is provided a catalyst for ethylene polymerization, which comprises the above magnesium-titanium-containing catalyst component, and an organoaluminum compound.
In the present invention, the organoaluminum compound may have the general formula AlR 1 n X 3-n In the formula, R 1 A hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, an aralkyl group or an aryl group, which is hydrogen; x is halogen, preferably chlorine or bromine; n is a number which is more than 0 and less than or equal to 3.
Specifically, the organoaluminum compound may be trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride or ethylaluminum dichloride, and preferably triethylaluminum or triisobutylaluminum.
The molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-containing titanium catalyst component is 5-5000: 1, preferably 20-500: 1.
According to a third aspect of the present invention, there is provided an ethylene polymerization process comprising: ethylene or ethylene and an alpha-olefin are reacted in the presence of the catalyst described above.
The ethylene polymerization reaction of the present invention is carried out in a slurry state, and the solvent may be a straight or branched alkane such as hexane, heptane, octane, decane or derivatives thereof.
The reaction conditions include: the pressure of the reaction is 0.05-10Mpa, preferably 0.1-5Mpa; the reaction temperature is 30-120 ℃, preferably 40-90 ℃, when the temperature is too high, the ethylene molecules are easy to generate free radical polymerization, the molecular weight of the prepared polyethylene is not high, and when the temperature is too low, the activity of the catalyst is low or the catalyst is not polymerized; the reaction time is 1.5-10h, preferably 1.5-2.5h.
The present invention is further illustrated by the following examples. But is not limited by these examples.
In the following examples and comparative examples:
the particle size distribution of the catalyst components: mastersizer 2000 instrument, malvern, uk;
polymer apparent Bulk Density (BD): measured with reference to ASTM D1895-96;
polymer molecular weight (Mw): a viscosity method;
sphericity of the polymer: a camsize particle analyzer;
description of the drawings: when the sphericity is 1, the particles are spherical, and the smaller the sphericity is, the more irregular the particle shape is.
Examples 1-4 are intended to illustrate the magnesium and titanium containing catalyst component and catalyst of the present invention and the polymerization of ethylene.
Example 1
Adding 4.8 g of magnesium chloride, 110 ml of toluene, 5.0 ml of tributyl phosphate and 11.6 ml of n-butyl alcohol into a reaction kettle, reacting for 1 hour under the conditions of stirring speed of 450rpm and temperature of 103 ℃, cooling to-10 ℃, dropwise adding 36 ml of titanium tetrachloride, heating to 80 ℃ within 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing 4 times with organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Ethylene polymerization: and (2) alternately filling nitrogen into a 2-cubic-liter polymerization kettle and vacuumizing for three times, adding 1-cubic-liter n-hexane, 2mmol of triethyl aluminum and 2 mg of magnesium-titanium-containing catalyst component, heating to 60 ℃, adding ethylene to maintain the kettle pressure at 0.7MPa, and reacting for 2 hours at 60 ℃. The activity of the catalyst is calculated, and the bulk density and sphericity of the polymer are determined. The photograph of the polymer is shown in FIG. 1.
Example 2
Adding 4.8 g of magnesium chloride, 100 ml of toluene, 6.0 ml of tributyl phosphate and 8.4 ml of n-propanol into a reaction kettle, reacting for 1 hour under the conditions of stirring speed of 450rpm and temperature of 103 ℃, cooling to-10 ℃, dropwise adding 36 ml of titanium tetrachloride, heating to 80 ℃ within 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing 4 times with an organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Ethylene polymerization: the same as in example 1.
Example 3
Adding 4.8 g of magnesium chloride, 90 ml of toluene, 6.0 ml of tributyl phosphate and 9.2 ml of n-butyl alcohol into a reaction kettle, reacting for 1 hour under the conditions of stirring speed of 450rpm and temperature of 103 ℃, cooling to-10 ℃, dropwise adding 40 ml of titanium tetrachloride, heating to 80 ℃ within 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing for 4 times with organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Ethylene polymerization: the same as in example 1.
Example 4
The preparation of the magnesium-containing titanium catalyst component differs from example 1 in that titanium tetrachloride is added dropwise by cooling to-20 ℃.
Ethylene polymerization: the same as in example 1.
Comparative example 1
Adding 4.8 g of magnesium chloride, 55 ml of toluene, 3.0 ml of epoxy chloropropane, 3.6 ml of tributyl phosphate and 7.6 ml of ethanol into a reaction kettle, reacting for 1 hour under the conditions of stirring speed of 450rpm and temperature of 55 ℃, adding 0.8 g of phthalic anhydride, keeping the temperature of 55 ℃ constant for 1 hour, cooling to-30 ℃, dropwise adding 40 ml of titanium tetrachloride, heating to 80 ℃ within 4 hours, keeping the temperature constant for 1.0 hour, washing twice with 120 ml of toluene at 60 ℃, washing 4 times with an organic solvent hexane, and drying to obtain the catalyst component. The photograph of the polymer is shown in FIG. 2.
Ethylene polymerization: the catalyst component was added in an amount of 10 mg as in example 1.
Comparative example 2
Adding 4.8 g of magnesium chloride, 110 ml of toluene, 5.0 ml of tributyl phosphate and 11.6 ml of n-butyl alcohol into a reaction kettle, and reacting for 1 hour under the conditions of stirring speed of 450rpm and temperature of 55 ℃, wherein the dissolution is incomplete and the system is turbid. Cooling to-10 ℃, dropwise adding 36 ml of titanium tetrachloride, heating to 80 ℃ within 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing 4 times with organic solvent hexane, and drying to obtain the magnesium-titanium-containing catalyst component.
Ethylene polymerization: the catalyst component was added in an amount of 10 mg as in example 1.
The catalyst activities and polymer properties of the respective examples and comparative examples are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the activity of the catalyst of the present invention was normal, the molecular weight of the polymer produced was comparable, and the bulk density and particle sphericity of the polymer were significantly higher, as compared with the comparative catalyst. Comparing FIGS. 1 and 2, it can be seen that the polymer prepared with the catalyst component of the present invention has a smoother surface and less protrusions.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A magnesium-containing titanium catalyst component for ethylene polymerization, characterized in that the magnesium-containing titanium catalyst component is prepared by a method comprising:
1) Mixing a magnesium compound, an organic phosphorus compound, an organic alcohol compound and a diluent, and stirring for reaction at the reaction temperature of 95-110 ℃ to obtain a uniform solution;
2) And cooling the uniform solution to below 0 ℃, carrying out contact reaction with a titanium compound, heating to separate out solid particles, washing and drying to obtain the magnesium-titanium-containing catalyst component.
2. The magnesium-containing titanium catalyst component for ethylene polymerization as claimed in claim 1, wherein the magnesium compound is magnesium dihalide or a derivative of magnesium dihalide in which one halogen atom in the molecular formula is substituted by a hydrocarbon group or a haloalkyloxy group.
3. The magnesium-titanium-containing catalyst component for ethylene polymerization of claim 1, wherein said organophosphorus compound is selected from a hydrocarbyl or halohydrocarbyl ester of orthophosphoric acid, a hydrocarbyl or halohydrocarbyl ester of phosphorous acid; preferred are trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite.
4. The magnesium-containing titanium catalyst component for ethylene polymerization according to claim 1, wherein the organic alcohol compound is selected from a linear alcohol or an isomeric alcohol having a carbon number of 1 to 8; preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol and isooctanol.
5. The magnesium-containing titanium catalyst component for ethylene polymerization as claimed in claim 1, wherein the diluent is benzene, toluene, xylene, chlorobenzene or derivatives thereof.
6. The magnesium-containing titanium catalyst component for ethylene polymerization as claimed in claim 1, wherein the titanium compound has a general formula of Ti (OR) a X b Wherein R is C 1 -C 14 X is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, a + b =3 or 4;
the titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium and titanium trichloride, and more preferably titanium tetrachloride, trichloromonoethoxytitanium or titanium trichloride.
7. The magnesium-containing titanium catalyst component for ethylene polymerization according to claim 1, wherein the organophosphorus compound is contained in an amount of 0.01 to 10 mol, preferably 0.02 to 4 mol, per mol of the magnesium compound; the amount of the organic alcohol compound is 0.01 to 15 mol, preferably 0.05 to 10 mol; the dosage of the diluent is 0.2-5L; the titanium compound is used in an amount of 0.2 to 30 moles, preferably 1 to 20 moles.
8. The magnesium-titanium-containing catalyst component for ethylene polymerization according to claim 1, wherein in the step 1), the rotation speed of stirring is 350 to 500rpm, and the reaction time is 0.5 to 1.5 hours;
in the step 2), the temperature of the uniform solution is reduced to-30 ℃ to 5 ℃, and the temperature is increased to 60-110 ℃.
9. A catalyst for ethylene polymerization, characterized in that it comprises the magnesium-titanium-containing catalyst component according to any one of claims 1 to 8, and an organoaluminum compound;
preferably, the organoaluminum compound has the formula AlR 1 n X 3-n In the formula, R 1 Is hydrogen, alkyl, aralkyl or aryl with 1-20 carbon atoms; x is chlorine or bromine; n is a number of more than 0 and less than or equal to 3; the organoaluminum compound is preferably trimethylaluminumTriethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, more preferably triethylaluminum and triisobutylaluminum;
the molar ratio of aluminum in the organoaluminum compound to titanium in the magnesium-containing titanium catalyst component is 5-5000: 1, preferably 20-500: 1.
10. An ethylene polymerization process, comprising: reacting ethylene or ethylene and an alpha-olefin in the presence of the catalyst of claim 9;
the reaction conditions include: the pressure of the reaction is 0.05-10Mpa, preferably 0.1-5Mpa; the reaction temperature is 30-120 ℃, and preferably 40-90 ℃; the reaction time is 1.5-10h, preferably 1.5-2.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111200521.8A CN115975080B (en) | 2021-10-14 | 2021-10-14 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111200521.8A CN115975080B (en) | 2021-10-14 | 2021-10-14 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115975080A true CN115975080A (en) | 2023-04-18 |
| CN115975080B CN115975080B (en) | 2024-09-17 |
Family
ID=85974553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111200521.8A Active CN115975080B (en) | 2021-10-14 | 2021-10-14 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975080B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1523044A (en) * | 2003-02-17 | 2004-08-25 | 中国石油化工股份有限公司 | Catalyst component for polymerizing ethylene and catalyst thereof |
| CN1752115A (en) * | 2004-09-23 | 2006-03-29 | 中国石油化工股份有限公司 | Catalyst used for ethylene polymerization or copolymerization and its preparation method |
| CN101353385A (en) * | 2008-09-27 | 2009-01-28 | 北京化工大学 | Catalyst for ethylene polymerization or copolymerization and its preparation method |
| CN101775086A (en) * | 2009-01-09 | 2010-07-14 | 中国石油天然气股份有限公司 | Preparation method of ethylene homopolymerization and copolymerization |
| CN103059171A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization |
| CN106589175A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst component for alkene polymerization, catalyst, and preparation method thereof |
| CN107936147A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Granular pattern catalytic component and its preparation method and application |
| CN108084305A (en) * | 2016-11-22 | 2018-05-29 | 中国石油天然气股份有限公司 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
| CN112625154A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Titanium catalyst component for olefin polymerization, preparation method thereof, catalyst containing titanium catalyst component and application of catalyst |
-
2021
- 2021-10-14 CN CN202111200521.8A patent/CN115975080B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1523044A (en) * | 2003-02-17 | 2004-08-25 | 中国石油化工股份有限公司 | Catalyst component for polymerizing ethylene and catalyst thereof |
| CN1752115A (en) * | 2004-09-23 | 2006-03-29 | 中国石油化工股份有限公司 | Catalyst used for ethylene polymerization or copolymerization and its preparation method |
| CN101353385A (en) * | 2008-09-27 | 2009-01-28 | 北京化工大学 | Catalyst for ethylene polymerization or copolymerization and its preparation method |
| CN101775086A (en) * | 2009-01-09 | 2010-07-14 | 中国石油天然气股份有限公司 | Preparation method of ethylene homopolymerization and copolymerization |
| CN103059171A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization |
| CN106589175A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst component for alkene polymerization, catalyst, and preparation method thereof |
| CN107936147A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Granular pattern catalytic component and its preparation method and application |
| CN108084305A (en) * | 2016-11-22 | 2018-05-29 | 中国石油天然气股份有限公司 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
| CN112625154A (en) * | 2019-10-09 | 2021-04-09 | 中国石油化工股份有限公司 | Titanium catalyst component for olefin polymerization, preparation method thereof, catalyst containing titanium catalyst component and application of catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115975080B (en) | 2024-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2749731B2 (en) | Method for producing catalyst for olefin polymerization | |
| KR101571054B1 (en) | A Catalyst Component for Ethylene Polymerization, Preparation thereof and a Catalyst Comprising the Catalyst Component | |
| US4258167A (en) | Process for producing powdery isotactic polyolefin | |
| US4259461A (en) | Process for producing propylene-ethylene block copolymers | |
| JP4917533B2 (en) | Catalyst component for ethylene polymerization, preparation method thereof, catalyst and polymerization method | |
| CN115975083B (en) | Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method | |
| CN115975080B (en) | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method | |
| CN114181335B (en) | Catalyst component and catalyst for olefin polymerization and preparation method thereof | |
| CN114181334B (en) | Catalyst component and catalyst for olefin polymerization and preparation method thereof | |
| US20150376303A1 (en) | Process for the preparation of ethylene polymers | |
| CN115975081B (en) | Solid catalyst component for ethylene polymerization and preparation method thereof | |
| JP6282299B2 (en) | Catalysts for olefin polymerization and their polymerization | |
| KR101885812B1 (en) | Process of preparation of drag reducing polymers and usage thereof | |
| CN114478861B (en) | Catalyst component for olefin polymerization, preparation method thereof, catalyst, method for preparing ultrahigh molecular weight polyolefin and application of catalyst component | |
| CN115490789B (en) | Micron-sized catalyst component for olefin polymerization, preparation method thereof and olefin polymerization method | |
| JP7445722B2 (en) | Method for preparing catalyst for olefin polymerization | |
| CN117946299A (en) | Catalyst component for preparing polyethylene, and preparation method and application thereof | |
| JPH07678B2 (en) | Method for producing ethylene copolymer | |
| JPS5919567B2 (en) | Improved method for producing ethylene polymers | |
| CN109153743B (en) | Solid PMAO composition and method for producing same | |
| KR800000343B1 (en) | Manufacturing method of ethylene | |
| EP0493637A1 (en) | Process for (co-)polymerizing ethylene | |
| CN112724284A (en) | Solid catalyst component, preparation method thereof, olefin polymerization catalyst and application | |
| KR800001659B1 (en) | Method of Making Polyethylene | |
| CN114478854A (en) | Catalyst component for olefin polymerization, preparation method thereof, catalyst, method for preparing ultrahigh molecular weight polyolefin and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |