CN115975083A - Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method - Google Patents
Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method Download PDFInfo
- Publication number
- CN115975083A CN115975083A CN202111201007.6A CN202111201007A CN115975083A CN 115975083 A CN115975083 A CN 115975083A CN 202111201007 A CN202111201007 A CN 202111201007A CN 115975083 A CN115975083 A CN 115975083A
- Authority
- CN
- China
- Prior art keywords
- compound
- catalyst component
- titanium
- ethylene
- reaction
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000005977 Ethylene Substances 0.000 title claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 30
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 23
- -1 alcohol compound Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 16
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000010438 heat treatment 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 17
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 229910052719 titanium Inorganic materials 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012456 homogeneous solution Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-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
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 claims description 3
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 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
- 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
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 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 26
- 230000000694 effects Effects 0.000 abstract description 9
- 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
- 239000000243 solution Substances 0.000 description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000012452 mother liquor Substances 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
- 150000003624 transition metals Chemical class 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 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
- 229910052799 carbon Inorganic materials 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
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 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
- 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
- 239000002002 slurry Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
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 catalyst component for ethylene polymerization, a catalyst and an ethylene polymerization reaction method, wherein the preparation method of the catalyst component comprises the following steps: 1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and a polar diluent, and stirring for reaction to obtain a uniform solution; 2) And (3) carrying out contact reaction on the uniform solution, a non-polar solvent and a titanium compound, heating to separate out solid particles, washing to obtain a catalyst component or preparing the catalyst component into a suspension, and preparing the suspension into the suspension. The catalyst component obtained by the method has the advantages of obviously higher activity, higher bulk density of the polymer, higher sphericity of the polymer, centralized particle size distribution of the polymer and better particle shape and particle size distribution of the polymer.
Description
Technical Field
The invention belongs to the technical field of ethylene polymerization, and particularly relates to a 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 electron donors 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 fixed form of porous spherical silica gel, as disclosed in patent document CN1158136, a main catalyst for producing ethylene high polymer, which comprises an inorganic carrier (preferably active silica carrier), a chlorine compound carried on the carrier, a magnesium compound carried on the carrier, a titanium compound carried 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 promoter and a halide of a transition metal titanium 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 better and is similar to a sphere, and the prepared polymer has better particle shape and higher bulk density.
Patent document CN1112373C is prepared by dissolving magnesium chloride in isooctyl alcohol 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, and the hydrogen regulation performance is better.
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 precipitation aid, and halides of transition metal titanium and derivatives thereof.
Patent document CN1958620 is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound and a lower alcohol to form a homogeneous solution, and reacting with at least one silane compound and a halide of transition metal titanium and its derivatives.
Disclosure of Invention
In view of the above situation, the present invention aims to provide a catalyst component for ethylene polymerization, a catalyst and an ethylene polymerization reaction method, wherein the catalyst of the present invention has the advantages of high bulk density of the polymer, high sphericity of the polymer, concentrated particle size distribution of the polymer, and good particle shape and particle size distribution of the polymer.
A first aspect of the present invention provides a catalyst component for ethylene polymerization, the catalyst component being prepared by a process comprising:
1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and a polar diluent, and stirring for reaction to obtain a uniform solution;
2) And (3) carrying out contact reaction on the uniform solution, a non-polar solvent and a titanium compound, heating to separate out solid particles, and washing to obtain a catalyst component or preparing the catalyst component into a suspension.
The second aspect of the present invention provides a catalyst for ethylene polymerization, which comprises the above-mentioned 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 catalyst component obtained by adding the nonpolar solvent in the preparation process has the advantages of obviously higher activity, higher bulk density of the polymer, higher sphericity of the polymer, concentrated particle size distribution of the polymer and better particle shape and particle size distribution of the polymer.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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 catalyst component for the polymerization of ethylene, the catalyst component being prepared by a process comprising:
1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and a polar diluent, and stirring for reaction to obtain a uniform solution;
2) And (3) carrying out contact reaction on the uniform solution, a non-polar solvent and a titanium compound, heating to separate out solid particles, and washing to obtain a catalyst component or preparing the catalyst component into a suspension.
According to the invention, the nonpolar solvent is added in the preparation process of the catalyst component, so that the catalyst activity can be improved, the bulk density and the sphericity of the polymer can be improved, the particle size distribution of the polymer is concentrated, and the nonpolar solvent and the titanium compound can be respectively or simultaneously in contact reaction with the uniform solution.
Preferably, the contact reaction of the homogeneous solution and the nonpolar solvent and the titanium compound is carried out according to any one of the following modes:
adding a nonpolar solvent into the uniform solution at 30-60 ℃, then cooling to-30 ℃ to 20 ℃, and adding a titanium compound for contact reaction;
secondly, cooling the uniform solution to-30 to 20 ℃, and then adding a non-polar solvent and a titanium compound into the uniform solution for contact reaction;
and thirdly, adding a nonpolar solvent into the uniform solution at the temperature of between 30 and 60 ℃, and then adding the obtained mixture into a titanium compound with the temperature of between-30 and 20 ℃ for contact reaction.
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 organic epoxy compound is selected from aliphatic olefins having 2 to 8 carbon atoms, dienes, halogenated aliphatic olefins, oxides of dienes, glycidyl ethers or internal ethers, etc. Preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.
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 polar diluent may be benzene, toluene, xylene, chlorobenzene, or derivatives thereof.
According to the invention, the non-polar diluent may be hexane, heptane, octane or decane.
According to the invention, the titanium compound has the general formula 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, 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 organic epoxy compound is used in an amount of 0.01 to 10 moles, preferably 0.02 to 4 moles, per mole of the magnesium compound; 0.01 to 10 moles, preferably 0.02 to 4 moles of the organophosphorus compound; the amount of the organic alcohol compound is 0.01 to 15 mol, preferably 0.05 to 10 mol; the dosage of the polar diluent is 0.2-5L; the dosage of the non-polar diluent is 0.2-5L; the amount of the titanium compound to be used is 0.2 to 30 mol, preferably 1 to 20 mol.
Preferably, in the step 1), the stirring speed is 350-500rpm, the reaction temperature is 50-100 ℃, and the reaction time is 0.5-1.5h.
Preferably, in step 2), the temperature for increasing the temperature is 60-110 ℃.
In the present invention, the solvent for preparing the suspension may be a straight or branched alkane such as hexane, heptane, octane, decane or derivatives thereof, etc.
According to a second aspect of the present invention, there is provided a catalyst for ethylene polymerization, which comprises the above-mentioned 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 of 0 < n < 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 aluminium in the organoaluminium compound to titanium in the catalyst component is in the range of from 5 to 5000: 1, preferably from 20 to 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 polymer and SPAN value: 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; the smaller the SPAN value, the more concentrated the particle size distribution.
Examples 1-6 are intended to illustrate the catalyst components and catalysts of the invention and the polymerization of ethylene.
Example 1
Adding 4.8 g of magnesium chloride, 40 ml of toluene, 3.0 ml of epichlorohydrin, 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 20 ml of hexane, cooling to-30 ℃, slowly dripping 40 ml of titanium tetrachloride within 4 hours, heating to 80 ℃ within 4 hours, keeping the temperature for 2.0 hours, filtering out mother liquor by using a filter, washing twice by using 120 ml of toluene and 60 ℃, washing by using an organic solvent hexane for 4 times, and finally adding 1000 ml of hexane to prepare a catalyst component suspension.
Ethylene polymerization: a2-liter polymerization kettle is alternately filled with nitrogen and vacuumized for three times, 1-liter normal hexane, 2mmol triethyl aluminum and 1 ml of catalyst component suspension are added, the temperature is raised to 60 ℃, ethylene is added to maintain the kettle pressure at 0.7MPa, and the reaction is carried out for 2 hours at 60 ℃. The catalyst activity was calculated and the polymer bulk density and particle size distribution were determined.
Example 2
Adding 4.8 g of magnesium chloride, 40 ml of toluene, 3.0 ml of epichlorohydrin, 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 ℃, cooling to-30 ℃, adding 80 ml of hexane and 40 ml of titanium tetrachloride within 4 hours, heating to 80 ℃ within 4 hours, keeping the temperature for 2.0 hours, filtering out a mother solution by using a filter, washing twice by using 120 ml of toluene at 60 ℃, washing by using an organic solvent hexane for 4 times, and finally adding 1000 ml of hexane to prepare a catalyst component suspension.
Ethylene polymerization: the same as in example 1.
Example 3
The preparation of the catalyst component differed from example 1 in that titanium tetrachloride was added dropwise by cooling to-10 ℃.
Ethylene polymerization: the same as in example 1.
Example 4
The catalyst component was prepared differently from example 1 in that titanium tetrachloride was added dropwise by cooling to 20 ℃.
Ethylene polymerization: the same as in example 1.
Example 5
The catalyst component was prepared in a manner different from that of example 1 in that 20 ml of hexane was added instead of 28 ml of decane.
Ethylene polymerization: the same as in example 1.
Example 6
The catalyst component was prepared as described in example 1, except that 20 ml of hexane was added instead of 55 ml of hexane.
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, filtering out mother liquor by using a filter, washing twice by using 120 ml of toluene at 60 ℃, washing by using an organic solvent hexane for 4 times, and drying to obtain the catalyst component.
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, 40 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 ℃, cooling to-30 ℃, slowly dripping 40 ml of titanium tetrachloride within 4 hours, heating to 80 ℃ within 4 hours, keeping the temperature for 2.0 hours, filtering out mother liquor by using a filter, washing twice by using 120 ml of toluene at 60 ℃, washing for 4 times by using an organic solvent hexane, and finally adding 1000 ml of hexane to prepare a catalyst component suspension.
Ethylene polymerization: the same as in example 1.
Comparative example 3
Adding 4.8 g of magnesium chloride, 40 ml of toluene, 3.0 ml of epichlorohydrin, 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 ℃, cooling to-30 ℃, adding 40 ml of titanium tetrachloride within 4 hours, heating to 80 ℃ within 4 hours, keeping the temperature for 2.0 hours, filtering out mother liquor by using a filter, washing twice by using 120 ml of toluene at 60 ℃, washing by using an organic solvent hexane for 4 times, and finally adding 1000 ml of hexane to prepare a catalyst component suspension.
Ethylene polymerization: the same as in example 1.
The catalyst activities and polymer properties of the examples and comparative examples are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst component of the present invention has significantly higher activity, higher bulk density of the polymer, higher sphericity of the polymer, concentrated particle size distribution of the polymer, and better particle shape and particle size distribution of the polymer.
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 catalyst component for the polymerization of ethylene, characterized in that it is prepared by a process comprising:
1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and a polar diluent, and stirring for reaction to obtain a uniform solution;
2) And (3) carrying out contact reaction on the uniform solution, a non-polar solvent and a titanium compound, heating to separate out solid particles, and washing to obtain a catalyst component or preparing the catalyst component into a suspension.
2. The catalyst component for ethylene polymerization according to claim 1, wherein a non-polar solvent, a titanium compound are separately or simultaneously contact-reacted with a homogeneous solution;
preferably, the contact reaction of the homogeneous solution and the nonpolar solvent and the titanium compound is carried out according to any one of the following modes:
adding a nonpolar solvent into the uniform solution at the temperature of 30-60 ℃, then cooling to-30 ℃ to 20 ℃, and adding a titanium compound for contact reaction;
secondly, cooling the uniform solution to-30 to 20 ℃, and then adding a non-polar solvent and a titanium compound into the uniform solution for contact reaction;
and thirdly, adding a nonpolar solvent into the uniform solution at the temperature of between 30 and 60 ℃, and then adding the obtained mixture into a titanium compound with the temperature of between-30 and 20 ℃ for contact reaction.
3. The catalyst component for ethylene polymerization according to claim 1, wherein the magnesium compound is a magnesium dihalide or a derivative of the formula of a magnesium dihalide in which one halogen atom is replaced by a hydrocarbon group or a haloalkyloxy group;
the organic epoxy compound is selected from aliphatic olefin with 2-8 carbon atoms, diene, halogenated aliphatic olefin, oxide of diene, glycidyl ether or internal ether; preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.
4. The catalyst component for the polymerization of ethylene according to 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; preferably trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite;
the organic alcohol compound is selected from straight-chain alcohol or isomeric alcohol with 1-8 carbon atoms; preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol and isooctanol.
5. The catalyst component for ethylene polymerization according to claim 1, wherein the polar diluent is benzene, toluene, xylene, chlorobenzene or derivatives thereof;
the non-polar diluent is hexane, heptane, octane or decane.
6. The catalyst component for the polymerization of ethylene according to claim 1, in which the titanium compound has the general formula 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 catalyst component for ethylene polymerization according to claim 1, wherein the organic epoxy compound is used in an amount of 0.01 to 10 moles, preferably 0.02 to 4 moles, per mole of magnesium compound; 0.01 to 10 moles, preferably 0.02 to 4 moles of the organophosphorus compound; the amount of the organic alcohol compound is 0.01 to 15 mol, preferably 0.05 to 10 mol; the dosage of the polar diluent is 0.2-5L; the dosage of the non-polar 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 catalyst component for ethylene polymerization according to claim 1, wherein in step 1), the stirring speed is 350 to 500rpm, the reaction temperature is 50 to 100 ℃, and the reaction time is 0.5 to 1.5 hours;
in the step 2), the temperature is increased to 60-110 ℃.
9. A catalyst for the polymerization of ethylene, characterized in that it comprises the 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 which is more than 0 and less than or equal to 3; the organic aluminum compound is preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, diethyl aluminum monohydrogen, diisobutyl aluminum monohydrogen, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, and more preferably triethyl aluminum and triisobutyl aluminum;
the molar ratio of aluminium in the organoaluminium compound to titanium in the catalyst component is in the range of from 5 to 5000: 1, preferably from 20 to 500: 1.
10. An ethylene polymerization process, characterized in that it comprises: reacting ethylene or ethylene with 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 |
|---|---|---|---|
| CN202111201007.6A CN115975083A (en) | 2021-10-14 | 2021-10-14 | Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111201007.6A CN115975083A (en) | 2021-10-14 | 2021-10-14 | Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115975083A true CN115975083A (en) | 2023-04-18 |
Family
ID=85962796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111201007.6A Pending CN115975083A (en) | 2021-10-14 | 2021-10-14 | Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975083A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353385A (en) * | 2008-09-27 | 2009-01-28 | 北京化工大学 | Catalyzer for ethylene polymerization and copolymerization and preparing method thereof |
| CN101407561A (en) * | 2008-11-28 | 2009-04-15 | 北京化工大学 | Olefin polymerizing catalyst |
| WO2019015638A1 (en) * | 2017-07-19 | 2019-01-24 | 中国石油化工股份有限公司 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
-
2021
- 2021-10-14 CN CN202111201007.6A patent/CN115975083A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353385A (en) * | 2008-09-27 | 2009-01-28 | 北京化工大学 | Catalyzer for ethylene polymerization and copolymerization and preparing method thereof |
| CN101407561A (en) * | 2008-11-28 | 2009-04-15 | 北京化工大学 | Olefin polymerizing catalyst |
| WO2019015638A1 (en) * | 2017-07-19 | 2019-01-24 | 中国石油化工股份有限公司 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20090318643A1 (en) | Catalyst Component for Ethylene Polymerization, Preparation Thereof and Catalyst Comprising the Same | |
| US7153804B2 (en) | Catalyst component for ethylene polymerization, the preparation thereof and catalyst comprising the same | |
| KR101571054B1 (en) | A Catalyst Component for Ethylene Polymerization, Preparation thereof and a Catalyst Comprising the Catalyst Component | |
| KR20050016498A (en) | A solid catalyst component for polymerization of ethylene, preparation thereof and a catalyst containing the same | |
| CN103772537B (en) | A kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE) | |
| US4258167A (en) | Process for producing powdery isotactic polyolefin | |
| CN106543316B (en) | Catalyst component for olefin polymerization, catalyst and preparation method thereof | |
| WO2017190543A1 (en) | Olefin coordination polymerization catalyst and preparation method and use thereof | |
| US4259461A (en) | Process for producing propylene-ethylene block copolymers | |
| CN110862472A (en) | Olefin polymerization reaction catalyst, preparation method and composite catalyst | |
| CN115975083A (en) | Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method | |
| CN114181334B (en) | Catalyst component and catalyst for olefin polymerization and preparation method thereof | |
| CN114426605B (en) | Catalyst component for olefin polymerization and preparation method and application thereof | |
| CN112661885B (en) | Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application | |
| CN112759678B (en) | Catalyst component for olefin polymerization and preparation method thereof, catalyst and olefin polymerization method | |
| CN101838352B (en) | Catalyst component for vinyl polymerization or copolymerization and catalyst thereof | |
| CN114181335A (en) | Catalyst component for olefin polymerization, catalyst and preparation method thereof | |
| CN112724284B (en) | Solid catalyst component, preparation method, olefin polymerization catalyst and application | |
| CN115975080A (en) | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method | |
| CN115490789B (en) | Micron-sized catalyst component for olefin polymerization, preparation method thereof and olefin polymerization method | |
| WO1996023006A1 (en) | Cyclopentadienyl group 6b metal-alkali metal alpha-olefin polymerization catalysts and their use in polymerization processes | |
| JP6282299B2 (en) | Catalysts for olefin polymerization and their polymerization | |
| CN117946299A (en) | Catalyst component for preparing polyethylene, and preparation method and application thereof | |
| CN117946298A (en) | Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof | |
| CN115975081A (en) | Solid catalyst component for ethylene polymerization and preparation method thereof |
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 |