CN115073628A - Metallocene catalyst system loaded by porous organic polymer carrier and preparation method and application thereof - Google Patents
Metallocene catalyst system loaded by porous organic polymer carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN115073628A CN115073628A CN202110276240.4A CN202110276240A CN115073628A CN 115073628 A CN115073628 A CN 115073628A CN 202110276240 A CN202110276240 A CN 202110276240A CN 115073628 A CN115073628 A CN 115073628A
- Authority
- CN
- China
- Prior art keywords
- organic polymer
- porous organic
- carrier
- monomer
- styrene
- 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
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 84
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 88
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 66
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 34
- -1 polypropylene Polymers 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- 239000003381 stabilizer Substances 0.000 claims description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical group [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 6
- 150000003440 styrenes Chemical group 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000003254 radicals Chemical class 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- SQAKQVFOMMLRPR-UHFFFAOYSA-N 2-[2-[4-[4-[2-(2-sulfophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=C(C=2C=CC(C=CC=3C(=CC=CC=3)S(O)(=O)=O)=CC=2)C=C1 SQAKQVFOMMLRPR-UHFFFAOYSA-N 0.000 claims description 3
- UBUANBABJDKKFE-UHFFFAOYSA-N 2-ethenyl-4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C=C)=C1 UBUANBABJDKKFE-UHFFFAOYSA-N 0.000 claims description 3
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 claims description 3
- ATBDZSAENDYQDW-UHFFFAOYSA-N 3-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=C)=C1 ATBDZSAENDYQDW-UHFFFAOYSA-N 0.000 claims description 3
- HIMSZPVHDPPXHO-UHFFFAOYSA-N ethenyl 4-methylbenzenesulfonate;sodium Chemical compound [Na].CC1=CC=C(S(=O)(=O)OC=C)C=C1 HIMSZPVHDPPXHO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 claims description 3
- PQVFIKHKSFZHLT-UHFFFAOYSA-M sodium;3-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(C=C)=C1 PQVFIKHKSFZHLT-UHFFFAOYSA-M 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 150000003624 transition metals Chemical group 0.000 claims description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 102
- 238000003756 stirring Methods 0.000 description 54
- 238000001914 filtration Methods 0.000 description 35
- 239000012046 mixed solvent Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 26
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 25
- 239000003153 chemical reaction reagent Substances 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 229910007926 ZrCl Inorganic materials 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 229940120638 avastin Drugs 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- JMYQTVXVDLDIFI-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)[Zr+2](C1C=CC=C1)CCCC Chemical compound [Cl-].[Cl-].C(CCC)[Zr+2](C1C=CC=C1)CCCC JMYQTVXVDLDIFI-UHFFFAOYSA-L 0.000 description 11
- AATHLPHPRXGBAI-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate;hydrate Chemical compound O.[Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 AATHLPHPRXGBAI-UHFFFAOYSA-M 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000037048 polymerization activity Effects 0.000 description 9
- 239000000969 carrier Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 238000012674 dispersion polymerization Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 101100043261 Caenorhabditis elegans spop-1 gene Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- IZYHZMFAUFITLK-UHFFFAOYSA-N 1-ethenyl-2,4-difluorobenzene Chemical compound FC1=CC=C(C=C)C(F)=C1 IZYHZMFAUFITLK-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- BGGKSZPSSRGVTP-UHFFFAOYSA-L 2-methyl-1h-inden-1-ide;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C1=CC=C2[CH-]C(C)=CC2=C1.C1=CC=C2[CH-]C(C)=CC2=C1 BGGKSZPSSRGVTP-UHFFFAOYSA-L 0.000 description 1
- MUTWDAVIXJBTAC-UHFFFAOYSA-N 3-ethenyl-2-methylbenzenesulfonic acid Chemical compound CC1=C(C=C)C=CC=C1S(O)(=O)=O MUTWDAVIXJBTAC-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LWDDCULLELBRKM-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)[Hf+2](C1C=CC=C1)CCCC Chemical compound [Cl-].[Cl-].C(CCC)[Hf+2](C1C=CC=C1)CCCC LWDDCULLELBRKM-UHFFFAOYSA-L 0.000 description 1
- VSXSFAWMVZKEAW-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC(CCCC2)=C2C1[Hf+2]C1C=CC2=C1CCCC2 Chemical compound [Cl-].[Cl-].C1=CC(CCCC2)=C2C1[Hf+2]C1C=CC2=C1CCCC2 VSXSFAWMVZKEAW-UHFFFAOYSA-L 0.000 description 1
- IMGRVQQBDRHUIF-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC(CCCC2)=C2C1[Ti+2]C1C=CC2=C1CCCC2 Chemical compound [Cl-].[Cl-].C1=CC(CCCC2)=C2C1[Ti+2]C1C=CC2=C1CCCC2 IMGRVQQBDRHUIF-UHFFFAOYSA-L 0.000 description 1
- ZKDLNIKECQAYSC-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC(CCCC2)=C2C1[Zr+2]C1C=CC2=C1CCCC2 Chemical compound [Cl-].[Cl-].C1=CC(CCCC2)=C2C1[Zr+2]C1C=CC2=C1CCCC2 ZKDLNIKECQAYSC-UHFFFAOYSA-L 0.000 description 1
- YVAJTQPCQNUSIG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Hf+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Hf+2]C1C2=CC=CC=C2C=C1 YVAJTQPCQNUSIG-UHFFFAOYSA-L 0.000 description 1
- JXBKMHHGNJJERO-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Ti+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Ti+2]C1C2=CC=CC=C2C=C1 JXBKMHHGNJJERO-UHFFFAOYSA-L 0.000 description 1
- GVILDFZVSFXAIF-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 GVILDFZVSFXAIF-UHFFFAOYSA-L 0.000 description 1
- FCRHLOATKYIXLU-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC2=CC=CC=C2C1[Hf+2]C1C2=CC=CC=C2C=C1C Chemical compound [Cl-].[Cl-].CC1=CC2=CC=CC=C2C1[Hf+2]C1C2=CC=CC=C2C=C1C FCRHLOATKYIXLU-UHFFFAOYSA-L 0.000 description 1
- NTIDFCAIBVLTMI-UHFFFAOYSA-L [Cl-].[Cl-].CC1=Cc2c(ccc3ccccc23)C1[Hf++]C1C(C)=Cc2c1ccc1ccccc21 Chemical compound [Cl-].[Cl-].CC1=Cc2c(ccc3ccccc23)C1[Hf++]C1C(C)=Cc2c1ccc1ccccc21 NTIDFCAIBVLTMI-UHFFFAOYSA-L 0.000 description 1
- VDKBHMAQJKZUSE-UHFFFAOYSA-L [Cl-].[Cl-].CC1=Cc2c(ccc3ccccc23)[C@H]1[Zr++][C@@H]1C(C)=Cc2c1ccc1ccccc21 Chemical compound [Cl-].[Cl-].CC1=Cc2c(ccc3ccccc23)[C@H]1[Zr++][C@@H]1C(C)=Cc2c1ccc1ccccc21 VDKBHMAQJKZUSE-UHFFFAOYSA-L 0.000 description 1
- UAWXAANPZSEZHY-UHFFFAOYSA-L [Cl-].[Cl-].CC=1C(C2=CC=CC(=C2C1)C1=CC=CC=C1)[Hf+2]C1C(=CC2=C(C=CC=C12)C1=CC=CC=C1)C Chemical compound [Cl-].[Cl-].CC=1C(C2=CC=CC(=C2C1)C1=CC=CC=C1)[Hf+2]C1C(=CC2=C(C=CC=C12)C1=CC=CC=C1)C UAWXAANPZSEZHY-UHFFFAOYSA-L 0.000 description 1
- IQTGDGZBSKVCKJ-UHFFFAOYSA-L [Cl-].[Cl-].CCCCC1([Hf++]C2(CCCC)C=CC=C2)C=CC=C1 Chemical compound [Cl-].[Cl-].CCCCC1([Hf++]C2(CCCC)C=CC=C2)C=CC=C1 IQTGDGZBSKVCKJ-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CZQIDPLTQBOKMO-UHFFFAOYSA-L butylcyclopentane;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCC[C]1[CH][CH][CH][CH]1.CCCC[C]1[CH][CH][CH][CH]1 CZQIDPLTQBOKMO-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 description 1
- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 150000001354 dialkyl silanes Chemical class 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- PUSCJUIYJNKDRK-UHFFFAOYSA-N dimethylalumanylium;2-methylpropan-2-olate Chemical compound C[Al](C)OC(C)(C)C PUSCJUIYJNKDRK-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LVKUAMRYYGCOLC-UHFFFAOYSA-N n-methylmethanamine;hydrofluoride Chemical compound [F-].C[NH2+]C LVKUAMRYYGCOLC-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 101150036301 spop gene Proteins 0.000 description 1
- ZCCKUOITFYNSQG-UHFFFAOYSA-N styrene;hydrate Chemical compound O.C=CC1=CC=CC=C1 ZCCKUOITFYNSQG-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a metallocene catalyst system loaded by a porous organic polymer carrier, and a preparation method and application thereof. The porous organic polymer carrier is composed of basic monomer divinyl benzene and functional monomer containing benzene sulfonic acidThe copolymer is obtained by dispersing and polymerizing acid functional groups or styrene containing sulfonic acid groups, wherein the mass percentage of the functional monomers accounts for 5-60% of the porous organic polymer carrier. The invention forms stable ion pair species [ POP-C ] by designing and regulating the chemical environment of the organic polymeric pore structure and the metal active center through the functional monomer 6 H 4 ‑SO 3 ...Al‑MAO‑Cl] ‑ [Cp 2 MMe] + Thereby improving the effective metallocene active center and obtaining higher catalytic activity. In addition, the preparation route of the porous organic polymer carrier is simple, the obtained particles have good surface appearance and narrow particle size distribution, and the porous organic polymer carrier has good industrial prospect.
Description
Technical Field
The invention relates to a metallocene catalyst system and a preparation method and application thereof, in particular to a metallocene catalyst system loaded by a porous organic polymer carrier and a preparation method and application thereof.
Background
In order to make metallocene catalysts suitable for commercial slurry or gas phase polymerization, it is important to support metallocenes to prepare supported metallocene catalysts. The supports currently used for supporting metallocene catalysts are generally inorganic supports and polymeric supports.
Inorganic supports have been reported very extensively as metallocene catalyst supports. U.S. Pat. No. 4,808,561, U.S. Pat. No. 5,026,797, U.S. Pat. No. 5,763,543, U.S. Pat. No. 5,661,098, U.S. Pat. No. 6,455,647, Chinese patent CN1174549, CN1356343 report the preparation of supported metallocene catalysts on supports of inorganic substances such as silica, magnesium chloride, alumina, etc. The inorganic carrier can affect the performance of the polyolefin after being introduced into the polymer, such as leading to high polymer ash content and causing fish eyes of the film. Furthermore, the presence of "acidic" groups on the surface of the inorganic support used in metallocene catalysts can lead to catalyst deactivation, requiring complex surface treatments of the inorganic support prior to loading the metallocene catalyst.
In recent ten years, the reason is thatOrganic polymer carriers containing porous structures have unique properties, such as high activity and good copolymerization performance, the molecular weight of polymers can be regulated and controlled through the polymer pore structures through a nanometer confinement effect during olefin polymerization, and prepared polymer products have low inorganic ash content and the like, and are increasingly concerned by the industrial and academic fields. U.S. Pat. No. 4,5,587,439 discloses an ethylene/methacrylate copolymer supported metallocene, which can be used for supporting CpZrCl after reaction of a carrier and sodium cyclopentadienyl 3 Or ZrCl 4 (THF) 2 Ethylene was catalytically polymerized in toluene solution using MAO as cocatalyst. Chinese patent CN1624005 performs chloromethyl functionalization on linear polystyrene, and performs crosslinking through D-a reaction. The main disadvantage of this method is the undefined structure of the functional groups of the support and the inhomogeneous distribution of the functional groups in the support. Chinese patent CN1396186 adopts cross-linked polystyrene copolymerization allyl alcohol as a high molecular carrier. The solid carrier is not beneficial to the loading of the catalyst, and on the other hand, the solid carrier is not easy to be broken in the process of catalyzing the polymerization of ethylene and is not beneficial to the release of the active center. European patent EP528092 discloses the loading of Me with polypropylene particles 2 Si(Ind) 2 ZrCl 2 The polymer supported metallocene catalyst prepared by the method has better stability, and the corresponding polyolefin product has better appearance. Chinese patent CN101440137A discloses a copolymer carrier prepared by loading metallocene with polystyrene, divinylbenzene and acrylonitrile copolymer, wherein the copolymer carrier is a monodisperse porous polymer. However, the copolymer carrier prepared by the two methods has smaller pore volume and average pore diameter, which are not beneficial to the loading of the metallocene catalyst, and the activity of the catalyst is lower.
Organic polymer carriers can be classified into natural macromolecules and artificially synthesized polymers according to their sources. (1) Natural polymers, especially natural polymers having certain specific functional groups on the surface, such as cyclodextrin; (2) synthetic polymers, mainly Polyethylene (PE) such as WO 2001036096 and WO 2004092230, polypropylene (PP) such as WO 6,152,543 and WO 6,403,519, poly-1, 2-polybutadiene WO 4,161,462, polysiloxanes and styrene, divinylCopolymer carriers of benzene crosslinking monomer (optional) and another functional monomer such as vinyl nitrile, methyl methacrylate, etc., such as U.S. Pat. Nos. 4,623,707, 4,623,912, 5,139,985, 5,463,000, 5,498,582, EP344,755 and CN101440137A, and copolymer carriers of divinylbenzene and a functional monomer, such as U.S. Pat. No. 5,168,104, using gas phase silica gel as a porogen, carrying out a copolymer of divinylbenzene and hydroxyethyl methacrylate by suspension polymerization, and then etching the silica gel with a strong base to obtain porous polymer particles having a particle size of greater than 0.1 μm; US6,583,082 and US6,750,303 disclose a suspension polymerization method, which is adopted to copolymerize hydroxyethyl methacrylate functional monomer and divinylbenzene monomer to obtain a polymer carrier, and the specific surface area is more than 10m 2 A polymer carrier with a particle diameter of 0.1-1000 μm and a pore volume of more than 0.2 mL/g. However, the particle size and distribution of the particles prepared by the suspension polymerization method are large, the particle size can reach more than 200 μm, and the prepared carrier needs to be carried with the olefin polymerization catalyst after the particles with the particle size of 20-100 μm are screened out.
In addition, Chinese patents CN104558262B, CN104558261B and CN104558260B adopt a dispersion polymerization method to prepare a porous organic polymer carrier by using divinylbenzene, styrene and hydroxyethyl methacrylate, and the specific surface area of the carrier is 300g/m 2 The bulk density of the polymer is more than 0.25g/cm 3 And then the prepared carrier is used for loading a metallocene catalyst, and the catalyst has good ethylene polymerization activity. New Journal of Chemistry, volume 40 of "Synthesis and catalysis of Organic Polymers as effective Metal Catalyst Support" and Polymer volume 2018 of volume 10 of "Feasibility study on the design and Synthesis of Functional Porous Polymers with Porous structure metals catalysts", the design and Synthesis of Porous Organic Support (POP) were carried out using methyldiethylene and styrene as basic monomers and hydroxymethyl methacrylate (HEMA), hydroxypropyl methacrylate (HEPA), glycidyl methacrylate and p-chloromethylstyrene as Functional monomersThe agent has good ethylene polymerization activity. However, the solubility parameters of the monomer, the solvent system and the prepared polymer in the system may be greatly different, so that thermodynamic compatibility between the monomer, the solvent system and the polymer is poor, and the parameters such as pore structure parameters and morphology of the prepared carrier, polymerization activity of the catalyst and the like are difficult to have good results at the same time.
US20100036072a1 and US20090062492a1 adopt a method of activating an assistant, and increase the activity of a supported catalyst by increasing the concentration of Zr + ions in a metallocene active center by adding the activating assistant during the process of supporting the metallocene catalyst. Such a co-activator is generally composed of a carrier such as silica or the like, an organoaluminum oxy-compound such as Methylaluminoxane (MAO), and an ionic compound containing N, N-dimethylamine and perfluorophenol; can also be prepared from a carrier such as silica, an organoaluminum compound such as dimethylaluminum monochloride Al (Me) 2 Cl, Dimethylammonium fluoride Al (Me) 2 F or tert-butoxydimethylaluminum Al (Me) 2 (O t Bu), an oxygen-containing source compound such as perfluorophenol dimethylaluminum Al (Me) 2 (OC 6 F 5 ) Or (2, 6-tert-butyl-4-methyl) phenol dimethylaluminum Al (Me) 2 (BHT) optionally with the addition of a Lewis base. The assistant system can improve the concentration of Zr + ion active center by forming stable anions, thereby effectively improving the activity of the metallocene catalyst.
Different from the method disclosed above, the invention regulates and controls the prepared carrier pore structure through the design and optimization of the functional monomer, and simultaneously effectively regulates and controls the metallocene active center active environment through the designed functional monomer to promote the concentration of effective active center ions, thereby preparing the high-efficiency metallocene catalyst. The invention adopts a dispersion polymerization method and adopts a monomer containing benzenesulfonic acid functional groups or styrene containing sulfonic acid groups to prepare the porous organic polymer carrier with high specific surface area, the prepared carrier is suitable for a metallocene catalyst, and the prepared metallocene catalyst has ultrahigh olefin polymerization activity. Meanwhile, stable anions are formed by the benzenesulfonic acid functional group and the cocatalyst, and the effective Zr + active center concentration is improved by the influence of the ion pair effect on the metallocene active center chemistry, so that the prepared metallocene catalyst can obtain higher olefin polymerization activity compared with other organic polymer carriers and inorganic carriers.
Disclosure of Invention
The invention aims to provide a metallocene catalyst system loaded by a porous organic polymer carrier, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a metallocene catalyst system supported by a porous organic polymer carrier, which mainly comprises a porous organic polymer carrier, a cocatalyst and a metallocene compound.
The porous organic polymer carrier is a copolymer of a basic monomer and a functional monomer, wherein the basic monomer is divinylbenzene, and the functional monomer is styrene containing a benzenesulfonic acid functional group or a sulfonic acid group; wherein the mass percentage of the functional monomer accounts for 5-60% of the porous organic polymer carrier.
When the basic monomer and the functional monomer are copolymerized, a third comonomer can be added, wherein the third comonomer is at least one selected from styrene, alkyl substituted styrene and chloromethyl substituted styrene.
The porous organic polymer carrier of the present invention is prepared by a radical polymerization method, for example, a dispersion polymerization method, a suspension polymerization method, an emulsion polymerization method, etc., wherein the content of the functional monomer in the porous organic polymer carrier is determined by the addition of divinylbenzene and styrene containing benzenesulfonic acid functional groups or styrene containing sulfonic acid groups, so as to prepare the benzenesulfonic acid functionalized or sulfonic acid functionalized porous organic polymer carrier.
The benzene sulfonic acid functionalized or sulfonic acid functionalized porous organic polymer carrier with narrow dispersion and good fluidity can be prepared by adopting a dispersion polymerization process method, and the porous organic polymer carrier is marked as sPoP.
The styrene functional monomer containing a benzenesulfonic acid functional group or a sulfonic acid group of the present invention includes, but is not limited to, sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, sodium 2-methyl-4-sulfonate-based styrene, 2-methyl-3-sulfonate-based styrene, vinyl-4-methylbenzenesulfonic acid, sodium vinyl-4-methylbenzenesulfonate, sodium 2-ethyl-3-sulfonate-based styrene, 4' -bis (2-sulfonate-styryl) -1,1' -biphenyl, 2- (2-styryl) benzenesulfonic acid, and hydrates thereof.
The preparation of the metallocene catalyst system of the present invention requires the activation of the porous organic polymer support with a cocatalyst, which is alkylaluminoxane, including but not limited to Methylaluminoxane (MAO) or alkyl Modified Methylaluminoxane (MMAO), or a mixture of both. Wherein the alkyl modified MMAO may be, but not limited to, butyl modified alkylaluminoxane or isobutyl modified alkylaluminoxane, etc.
The metallocene compounds of the invention are of the general formula Cp x MA y B z Where Cp is unsubstituted or substituted cyclopentadienyl, indenyl, fluorenyl, the indenyl or fluorenyl ligands may also be present in hydrogenated form; m is a transition metal atom, A, B is a halogen atom, a hydrogen atom or an alkyl group, and x, y and z are integers of 0 to 3. Preferably, in the above metallocene compound formula, the transition metal atom M is zirconium or hafnium, the Cp group is an unsubstituted or substituted cyclopentadienyl group, indenyl group or fluorenyl group, x is at least 1, and the substituent on the cyclopentadienyl group is preferably a straight-chain alkyl group having 1 to 6 carbon atoms.
In the porous organic polymer carrier supported metallocene catalyst system of the present invention, the molar ratio of the cocatalyst (in moles of aluminum Al) to the metallocene compound (in moles of metal atom M in the metal compound) Al: m is 75 to 500, preferably 100 to 300. The amount ratio of cocatalyst (in moles of aluminium Al) to porous organic polymer support is from 1 to 12 mmol/g support, preferably from 3 to 8 mmol/g support. The metal active center metal atom content of the procatalyst metallocene compound is from 5 micromoles per gram of support to 100 micromoles per gram of support, preferably from 10 micromoles per gram of support to 50 micromoles per gram of support.
The invention also provides a preparation method of the metallocene catalyst system loaded on the porous organic polymer carrier, and the metallocene catalyst system is prepared by the following method (mass ratio is not specified below):
first step, preparation of porous organic Polymer support
Step (1): preparation of dispersion: the dispersion is composed of C 1 -C 4 Lower alcohol or C 1 -C 4 A mixed solvent system of alcohol and water; c in the dispersion 1 -C 4 The mass ratio of the alcohol to the water is 5-15: 1, C 1 -C 4 The alcohol is methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, etc.
Adding a reaction monomer: at room temperature, sequentially adding a comonomer divinyl benzene and a functional monomer containing a benzene sulfonic acid functional group or styrene containing a sulfonic acid group into the dispersion liquid, wherein the polymerization inhibitor is removed, and the mass ratio of the total addition amount of the basic monomer and the functional monomer to the dispersion liquid is 1: 5-20, so that the system is uniformly dispersed. The mass ratio of the functional monomer containing benzene sulfonic acid functional groups or styrene containing sulfonic acid groups to the basic monomer divinylbenzene is 0.2-2: 1.
step (2): preparation of porous organic polymer support: adding stabilizer and initiator, and dissolving the stabilizer in the system at 20-50 deg.C, wherein the stabilizer is polyvinyl alcohol or polypropylene oxide-polyethylene oxide copolymer. The weight average molecular weight of the stabilizer is controlled to be between 6,000 and 100,000, and the mass ratio of the addition amount of the stabilizer to the total addition amount of the basic monomer and the functional monomer is 0.5-3: 100. adding free radical initiator including Azobisisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO), heating to 60-80 deg.c, stirring and reacting for 3-12 hr. The mass ratio of the addition amount of the free radical initiator to the total addition amount of the basic monomer and the functional monomer is 0.5-3: 100. the polymer obtained by the reaction is washed to remove impurities.
And (3): acidifying: the functional monomer is styrene containing benzenesulfonic acid functional group or sulfonate group, and it needs to add dilute acid, such as dilute hydrochloric acid or dilute sulfuric acid, to make acidification at the end of reaction, after making acidification reaction at 20-70 deg.C, adopting solvent to wash and dry so as to obtain the free-flowing benzenesulfonic or sulfonated porous organic polymer carrier sPP.
Second, preparation of metallocene catalyst loaded with porous organic polymer carrier containing benzenesulfonic acid function or sulfonic acid function
And (4): removing impurities such as unreacted comonomers and stabilizers from the porous organic polymer carrier obtained in the step (3), drying, adding the dried porous organic polymer carrier into an inert solvent under the anhydrous and anaerobic operating condition, adding a cocatalyst, reacting for 15-120 minutes, adding a metallocene compound, adjusting the temperature to-40-80 ℃, reacting for 15-180 minutes, and washing the product by using the inert solvent to obtain the metallocene catalyst loaded on the porous organic polymer carrier.
In the present invention, the cocatalyst is MAO or MMAO, and the ratio of the amount of the cocatalyst (based on the moles of aluminum Al) to the porous organic polymer support is 1 mmol/g support to 12 mmol/g support, preferably 5 mmol/g support to 8 mmol/g support. The metallocene procatalyst has Cp x MA y B z The compound of the general formula, the addition amount of the metallocene main catalyst compound is as follows: molar ratio of cocatalyst (in moles of aluminium Al) to metallocene compound (in moles of metal atom M in the compound) Al: m is 75 to 300.
The monomer used in the preparation process of the metallocene catalyst system of the invention is divinylbenzene (abbreviated as DVB in English), sodium p-styrene sulfonate and p-styrene sulfonic acid, and can be a commercially available monomer, for example, 55% or 80% of DVB content can be used for divinylbenzene, and a commercially available reagent containing crystal water with concentration of more than 90% can be used for the sodium p-styrene sulfonate monomer, and can be directly used. The divinylbenzene is pretreated before use, and the polymerization inhibitor is removed before use, and the methods for removing the polymerization inhibitor in the prior art are many, such as sodium hydroxide solution and distilled water washing.
The porous organic polymer carrier used in the present invention is washed with a solvent to remove impurities such as unreacted comonomers, stabilizers, etc., and the solvent may be a lower alcohol having 1 to 4 carbon atoms (e.g., ethanol, propanol, etc.), an ester such as ethyl acetate, methyl acetate, ethyl formate, methyl formate, etc., water, and an alkane having 1 to 6 carbon atoms (e.g., isopentane, hexane, etc.).
In the invention, the particle size of the prepared free-flowing benzene sulfonated or sulfonated porous organic polymer carrier is tested by a Markov laser particle sizer Mastersizer 2000, the porous organic polymer carrier can be directly tested without ultrasonic dispersion after being dried, and a monodisperse particle size distribution curve can be obtained after the porous organic polymer carrier is stabilized, wherein the average particle size is 20-60 mu m; the specific surface area of the carrier is tested by using a BET nitrogen adsorption method by using Nova 2000e, and the specific surface area of the porous organic polymer carrier prepared by the invention is controlled to be more than 200m 2 At 200-600m 2 Between/g. The surface appearance of the porous organic polymer carrier is characterized by adopting a scanning electron microscope, and the surface appearance is good.
The benzene sulfonated or sulfonated porous organic polymer carrier prepared by the invention has good fluidity and the specific surface area can be controlled to be 200-600m 2 The pore volume is more than 0.2mL/g, the average particle diameter of D (50) is between 20 and 60 mu m, the particle diameter is unimodal, the distribution is narrow, and the distribution Span is [ D (90) -D (10)]the/D (50) is less than 2. The metallocene catalyst loaded on the porous organic polymer carrier is suitable for slurry, gas phase and other processes.
The metallocene compounds of the invention have the general formula Cp x MA y B z When x in the formula is equal to 2, the Cp ligands may also be bridged by polymethylene or dialkylsilane, for example by-Si (CH) 3 ) 2 -、-C(CH 3 ) 2 -、-CH 2 -、-CH 2 -CH 2 Similar bridging. The substituents A and B in the above metallocene compounds of the general formula may be halogen atoms, preferably y + z is equal to or less than 3, provided that x + y + z is equal to 4. When the substituents A and B in the general formula of the metallocene compound are alkyl, the substituents A and B are preferably straight-chain or branched alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propylAlkyl, n-butyl, isobutyl or n-pentyl. Suitable metallocene compounds include bis (cyclopentadienyl) metal dihalides, bis (cyclopentadienyl) metal monoalkyl monohalides, bis (cyclopentadienyl) metal dialkyl compounds and bis (indenyl) metal dihalides, the metal atom group IVB atoms including titanium, zirconium, hafnium metal atoms, typically the metal atom is zirconium or hafnium, the halide group is preferably chlorine and the alkyl group is an alkyl group having from 1 to 6 carbon atoms.
The following metallocene compounds, which include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) hafnium dimethyl, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) hafnium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) hafnium dimethyl, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (tetramethylcyclopentadienyl) hafnium dimethyl, bisindenyl zirconium dichloride, methylene-bridged bisindenyl zirconium dichloride and bis (4,5,6, 7-tetrahydro-1-indenyl) zirconium dichloride, ethylene-bridged-bis (indenyl) zirconium dichloride, bisindenyl hafnium dichloride, hafnium dichloride, Methylene bridged bis-indenyl hafnium dichloride and bis (4,5,6, 7-tetrahydro-1-indenyl) hafnium dichloride, ethylene bridged bis (indenyl) titanium dichloride, bis (4,5,6, 7-tetrahydro-1-indenyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dichloride, dimethylsilyl bridged bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilyl bridged bis (2-methyl-4-phenylindenyl) hafnium dichloride, dimethylsilyl bridged bis (2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilyl bridged bis (2-methylindenyl) zirconium dichloride, dimethylsilyl bridged bis (2-methylindenyl) hafnium dichloride, Dimethylsilyl-bridged bis (2-methyl-benzoindenyl) zirconium dichloride, dimethylsilyl-bridged bis (2-methyl-benzoindenyl) hafnium dichloride, dimethylsilyl-bridged bis (2-methyl-benzoindenyl) zirconium dimethyl, dimethylsilyl-bridged bis (2-methylindenyl) zirconium dimethyl, methylsilyl-bridged bis (2-methyl-4-phenylindenyl) zirconium dimethyl, and the like.
In the present invention, when preparing the metallocene compound and the cocatalyst solution thereof, a suitable solvent is required to be selected, and the suitable solvent includes aromatic hydrocarbon, halogenated aromatic hydrocarbon, ether, cyclic ether or ester, wherein toluene is preferably used as the solvent.
In the invention, Al and metal active center atoms such as Zr and Hf in the metallocene catalyst loaded by the porous organic polymer carrier are analyzed and tested by using VISTA-MPX inductively coupled plasma emission spectrum of Warian corporation in America. A sample is firstly burnt into ash in a muffle furnace, then perchloric acid and aqua regia are added, heating and digestion are carried out, 2% HCL solution is used for dissolving, and the volume is 100 mL. Then measuring the characteristic intensity peaks of Al and metal active center atoms, and calculating the content according to a standard curve.
The invention further provides an application of the porous organic polymer carrier-loaded metallocene catalyst system, the loaded metallocene catalyst system is suitable for gas phase, bulk or slurry polymerization, and the suitable reaction conditions are that the temperature is 30-120 ℃, and the pressure is 0.5-1.5 MPa. Suitable solvents for slurry polymerization are alkanes having 5 to 10 carbon atoms, and the preferred solvent is hexane.
The supported metallocene catalyst system can be used for the polymerization reaction or copolymerization reaction of olefin, and is particularly suitable for the homopolymerization reaction of ethylene, the homopolymerization reaction of propylene, the copolymerization reaction of ethylene and other alpha-olefin or the copolymerization reaction of propylene and other alpha-olefin; wherein the alpha-olefin is butene, pentene, hexene, octene, 4-methyl-1-pentene, etc. A small amount of alkyl aluminum compounds, such as triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-hexyl aluminum and the like, can also be added in the polymerization reaction to be used as an impurity removing agent of the polymerization reaction system.
The cocatalyst alkyl aluminoxane of the invention reacts with a porous organic polymer carrier functionalized by benzenesulfonic acid groups and is loaded on the porous organic polymer carrier, such as Al-CH in Methyl Aluminoxane (MAO) 3 With C on the benzenesulfonic acid group 6 H 4 -SO 3 By reaction of the hydroxyl group of H, by removal of CH 4 Form POP-C 6 H 4 -SO 3 - -Al- -MAO activating the support. When metallocene compound is added, MAO on the carrier is activatedMethylation of metallocene compounds to form [ Cp 2 MMe] + [POP-C 6 H 4 -SO 3 ...Al-MAO-Cl] - The ion pair is considered to be an effective active center (M ═ Zr, Ti, Hf, Cp is cyclopentadienyl, POP is a porous organic polymer carrier prepared, and the molecular structure is a brief molecular structure and is only illustrative).
The benzene sulfonated and sulfonated porous organic polymer carrier and the loaded metallocene catalyst prepared by the invention have high specific surface area, and form stable ion pair species [ POP-C ] by designing and regulating the organic polymerization pore structure and the chemical environment of the metal active center through the functional monomer 6 H 4 -SO 3 ...Al-MAO-Cl] - [Cp 2 MMe] + Thereby improving the effective metallocene active center and obtaining higher catalytic activity. Compared with the metallocene catalyst loaded by a porous organic carrier prepared by an inorganic silica gel carrier and other functional monomers, the metallocene catalyst has higher olefin polymerization activity. In addition, the preparation route of the porous organic polymer carrier is simple, and the prepared porous organic polymer carrier has the characteristics of good particle surface appearance, narrow particle size distribution and the like, so that the porous organic polymer carrier has a good industrial prospect.
Drawings
FIG. 1 is a scanning electron microscope SEM image of a sulfonated porous organic polymer carrier, sPOP-5, prepared in example 5.
FIG. 2 is a plot of the particle size distribution of the sulfonated porous organic polymer carrier, sPop-5, prepared in example 5.
Detailed Description
The following provides a detailed description of embodiments of the invention. The present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
Treatment of the comonomer: before the divinyl benzene is used, firstly, a 10% NaOH solution is used for removing a polymerization inhibitor, and then, deionized water is used for washing for 3 times; the monomers such as sodium p-styrene sulfonate or sodium p-styrene sulfonate hydrate are solid particles at normal temperature, and are directly used without post-treatment.
Preparation of sulfonated porous organic polymer support: in a 250mL glass reactor, 130mL of ethanol and 15mL of deionized water were added followed by 5mL (Aladdin reagent, 55%) (about 4.8g) of divinylbenzene and 1.8g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%). Stirring for 5min at normal temperature, then adding 2% of monomer mass of polyvinyl alcohol PVA (PVA, polymerization degree 1750), stirring for 1h at 45 ℃, completely dissolving the stabilizer, adding 2.0% (0.132g) of AIBN (AIBN) of monomer mass, heating to 70 ℃, reacting for 2h, then heating to 80 ℃, reacting for 5 h, stirring at 350 r/min, filtering, adding 100mL of the ethanol and water mixed solvent, adding 10mL of HCl solution with mass ratio of 36.5%, reacting for 2h at 50 ℃, filtering, washing for 3 times by using the ethanol and water mixed solvent, filtering, and drying to obtain free flow 3.8g of porous sPOP-1.
Example 2
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were added, then 4.8g (about 5.0mL) of 55% divinylbenzene (avastin reagent, 55%) and 3.2g of sodium p-styrenesulfonate hydrate (avastin reagent, 90%), stirring at room temperature for 5min, adding 2% monomer mass of polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000), stirring for 1h at 45 ℃, completely dissolving the stabilizer, adding AIBN with the mass of 2.0 percent of the monomer, heating to 70 ℃, reacting for 2 hours, then the temperature is raised to 80 ℃, after 5 hours of reaction, the stirring speed is 350 r/min, after filtration, 100mL of the mixed solvent of ethanol and water is added, 10mL of HCl solution with the mass ratio of 36.5 percent is added, reacting for 2h at 50 ℃, filtering, washing for 3 times by using an alcohol-water mixed solvent, filtering and drying to obtain the porous sPOP-2 with free flow of 3.7 g.
Example 3
In a 250mL glass reactor, 130mL of isobutanol and 14mL of deionized water were added, 4.8g (about 5.0mL) of 55% divinylbenzene (avastin reagent, 55%) and 3.2g of 2-methyl-3-sulfostyrene (95%) were stirred at room temperature for 5min, then 2% by mass of a monomer of polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000) was added, stirred at 45 ℃ for 1h to completely dissolve the stabilizer, AIBN (2.0% by mass of the monomer) was added, heated to 70 ℃ for reaction for 2 hours, then the temperature was raised to 80 ℃ and after 5 hours, the stirring speed was 350 rpm, after filtration, the above alcohol-water mixed solvent 100mL was added, 10mL of an HCl solution (36.5% by mass) was added, reacted at 50 ℃ for 2h, filtered, washed 3 times with an alcohol-water mixed solvent, and washed 3 times with an alcohol-water mixed solvent, after filtration and drying, free-flowing 4.1g of porous sPOP-3 was obtained.
Example 4
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were added, then 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 55%) and 1.9g of sodium p-styrenesulfonate hydrate (avastin reagent, 90%), stirring at normal temperature for 5min, adding polyvinyl alcohol PVA (PVA, polymerization degree 1750) with 2% of monomer mass, stirring for 1h at 45 ℃, completely dissolving the stabilizer, adding AIBN with the mass of 2.0 percent of the monomer, heating to 70 ℃, reacting for 3 hours, then the temperature is raised to 80 ℃, the stirring speed is 350 r/min after 5 hours of reaction, 100mL of the mixed solvent of ethanol and water is added after filtration, 10mL of HCl solution with the mass ratio of 36.5 percent is added, reacting for 2h at 50 ℃, filtering, washing for 3 times by using an alcohol-water mixed solvent, filtering and drying to obtain the porous sPOP-4 with free flow of 4.1 g.
Example 5
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were added, then 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 80%) and 2.4g of sodium p-styrenesulfonate hydrate (avastin reagent, 90%), stirring at normal temperature for 5min, adding polyvinyl alcohol PVA (PVA, polymerization degree 1750) with 2% of monomer mass, stirring for 1h at 45 ℃, completely dissolving the stabilizer, adding AIBN with the mass of 2.0 percent of the monomer, heating to 70 ℃, reacting for 3 hours, then the temperature is raised to 80 ℃, after 5 hours of reaction, the stirring speed is 350 r/min, after filtration, 100mL of the mixed solvent of ethanol and water is added, 10mL of HCl solution with the mass ratio of 36.5 percent is added, reacting for 2h at 50 ℃, filtering, washing for 3 times by using an alcohol-water mixed solvent, filtering and drying to obtain the porous sPOP-5 with free flow of 4.2 g.
Example 6
In a 250mL glass reactor, 126mL ethanol and 14mL deionized water were added, followed by 4.8g (about 5.0mL) divinylbenzene (avastin reagent, 80%) and 3.8g sodium p-styrenesulfonate hydrate (90%), stirring at room temperature for 5min, then polyvinyl alcohol PVA (PVA, polymerization degree 1750) of 2% monomer mass was added, stirring at 45 ℃ for 1h, completely dissolving the stabilizer, adding AIBN of 2.0% monomer mass, heating to 70 ℃, reacting for 3 hours, then raising the temperature to 80 ℃, after reacting for 5 hours, the stirring speed was 350 rpm, after filtering, adding 100mL of the above ethanol and water mixed solvent, adding 10mL HCl solution of 36.5% mass ratio, reacting at 50 ℃ for 2 hours, filtering, washing 3 times with an alcohol and water mixed solvent, filtering, and drying to obtain free-flowing 5.2g porous sPOP-6.
Example 7
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were charged, followed by 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 55%) and 1.6g of 4,4 '-bis (2-sulfostyryl) -1,1' -biphenyl (wuhan jinnuo chemical co., ltd,>95%) at room temperature for 5min, adding 2% by mass of a polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000), stirring at 45 deg.C for 1H to completely dissolve the stabilizer, adding 2.0% by mass of AIBN, heating to 70 deg.C, reacting for 3H, heating to 80 deg.C, reacting for 5H, stirring at 600 rpm, filtering, adding 100mL of the above mixed solvent of ethanol and water, adding 15mL of H10% by mass 2 SO 4 The solution was reacted at 50 ℃ for 2 hours, washed with ethanol 3 times, filtered, washed with an alcohol-water mixed solvent 3 times, filtered, and dried to obtain free-flowing porous sPO-7 of 4.0 g.
Example 8
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were added, followed by 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 80%) and 2.4g of 4,4' -bis (2-sulfolane)Acyloxystyrene) -1,1' -biphenyl (wuhanjinuo chemical ltd,>95%) at normal temperature for 5min, adding 2% monomer mass of polyvinyl alcohol PVA (PVA, polymerization degree 1750), stirring at 45 deg.C for 1H, dissolving stabilizer completely, adding 2.0% monomer mass of AIBN, heating to 70 deg.C, reacting for 3H, heating to 80 deg.C, reacting for 5H, stirring at 350 r/min, filtering, adding 100mL of the above mixed solvent of ethanol and water, adding 15mL of H10% by mass 2 SO 4 The solution was reacted at 50 ℃ for 2 hours, washed 3 times with an alcohol-water mixed solvent, filtered and dried to obtain 4.3g of porous sPO-8 as a free-flowing substance.
Example 9
Adding 126mL of ethanol and 14mL of deionized water into a 250mL glass reactor, adding 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 80%) and 2.4g of sodium p-styrenesulfonate hydrate (avastin reagent, 90%), stirring at room temperature for 5min, adding 2% of polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000), stirring at room temperature for 1H, completely dissolving the stabilizer, adding 2.0% of BPO (monomer mass), heating to 70 ℃, reacting for 3H, heating to 80 ℃, reacting for 5H, stirring at 600 r/min, filtering, adding 100mL of the above ethanol-water mixed solvent, adding 15mL of H (10% by mass) of H 2 SO 4 The solution is reacted for 2h at 50 ℃, filtered, washed for 3 times by using an alcohol-water mixed solvent, filtered and dried to obtain the porous sPOP-9 with free flow of 4.5 g.
Example 10
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were added, followed by addition of 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 80%) and 2.4g of sodium p-2-ethyl-3-sulfonate-based styrene hydrate (90%), stirring at room temperature for 5min, then addition of polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000) of 2% monomer mass, stirring at room temperature for 1h, complete dissolution of the stabilizer, addition of BPO of 2.0% monomer mass, heating to 70 deg.C, reaction for 3 h, then heating to 80 deg.C, reaction for 5 h, stirring at 600 rpmAfter filtration, 100mL of the above mixed solvent of ethanol and water was added, and 15mL of 10% by mass H was added 2 SO 4 The solution is reacted for 2 hours at 50 ℃, filtered, washed for 3 times by using an alcohol-water mixed solvent, filtered and dried to obtain the porous sPOP-10 with free flow of 4.3 g.
Example 11
In a 250mL glass reactor, 126mL of ethanol and 14mL of deionized water were added, then 4.8g (about 5.0mL) of divinylbenzene (avastin reagent, 80%) and 1.2g of sodium p-styrenesulfonate hydrate (avastin reagent, 90%), stirring at normal temperature for 5min, adding polyvinyl alcohol PVA (PVA, polymerization degree 1750) with 2% of monomer mass, stirring for 1h at 45 ℃, completely dissolving the stabilizer, adding AIBN with the mass of 2.0 percent of the monomer, heating to 70 ℃, reacting for 3 hours, then the temperature is increased to 80 ℃, after 5 hours of reaction, the stirring speed is 600 r/min, after filtration, 100mL of the mixed solvent of ethanol and water is added, 10mL of HCl solution with the mass ratio of 36.5 percent is added, reacting for 2h at 50 ℃, filtering, washing for 3 times by using an alcohol-water mixed solvent, filtering and drying to obtain the porous sPOP-11 with free flow of 4.2 g.
Example 12
In a 250mL glass reactor, 130mL of ethanol and 20mL of deionized water were added, 4.8g (about 5.0mL) of divinylbenzene (Aladdin reagent, 55%) and 3.2g of 4,4 '-bis (2-sulfostyryl) -1,1' -biphenyl (Wuhan jin chemical Co., Ltd. > 95%) were added, and stirred at room temperature for 5min, then 2% by mass of monomer of polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000) was added, and stirred at 45 ℃ for 1h to completely dissolve the stabilizer, 2.0% by mass of monomer of AIBN, and heated to 70 ℃ for 3 hours, and then the temperature was raised to 80 ℃ for 5 hours, and after the stirring rotation speed was 600 rpm, washing was performed 3 times with ethanol, filtering, washing was performed 3 times with an alcohol-water mixed solvent, and 100mL of the above-mentioned alcohol-water mixed solvent was added, 10mL of 36.5% HCl solution by mass is added, reaction is carried out for 2h at 50 ℃, and after filtration, filtration and drying, free flow 4.0g of porous sPOP-12 is obtained.
Example 13
In a 250mL glass reactor, 135mL of methanol and 15mL of deionized water were added, followed by 4.8g (about 5.0mL) of divinylbenzene (Aladdin reagent, 55%) and 2.4g of sodium p-styrenesulfonate hydrate (Aladdin reagent, 90%), stirring at room temperature for 5min, then adding 2% by mass of monomer of polypropylene oxide-polyethylene oxide copolymer F127(BASF, MW 12000), stirring at 45 ℃ for 1h to completely dissolve the stabilizer, 2.0% by mass of AIBN, heating to 65 ℃ for reaction for 3 hours, then heating to 75 ℃, after 5 hours reaction, stirring at 600 rpm, washing 3 times with ethanol, adding 100mL of the above alcohol-water mixed solvent, adding 10mL of 36.5% by mass of HCl solution, reacting at 50 ℃ for 2h, filtering, after filtration, washing 3 times with the alcohol-water mixed solvent, filtering, After drying, a free-flowing, 4.3g, porous sPO-13 was obtained.
Comparative examples 14 to 16
Comparative example 14
POP carrier prepared by using HEMA functional monomer: in a 250mL glass reactor, 130mL of ethanol and 15mL of deionized water were added followed by 4.8g of 80% divinylbenzene and 2.4g of hydroxyethyl methacrylate. Stirring at normal temperature for 5min, adding 2% monomer mass of polypropylene oxide-polyethylene oxide copolymer F127(BASF, molecular weight 12000), stirring at 45 deg.C for 1h, dissolving the stabilizer completely, heating to 70 deg.C, reacting for 3 h, heating to 80 deg.C, reacting for 5 h, stirring at 350 r/min, washing with ethanol for 3 times, filtering, and drying to obtain 4.3g (DVB-co-HEMA) carrier POP 14.
Comparative example 15
Non-acidified sPP support: in a 250mL glass reactor, 126mL ethanol and 14mL deionized water were added, then 4.8g (about 5.0mL) divinylbenzene (avadin reagent, 80%) and 1.9g sodium p-styrenesulfonate hydrate (avadin reagent, 90%) were added, stirred at room temperature for 5min, then polyvinyl alcohol PVA (PVA, degree of polymerization 1750) of 2% monomer mass was added, stirred at 45 ℃ for 1h, stabilizer was completely dissolved, AIBN of 2.0% monomer mass was added, heated to 70 ℃, reacted for 3 h, then the temperature was raised to 80 ℃, reacted for 5 h, the stirring speed was 350 rpm, after filtration, washing 3 times with alcohol-water mixed solvent, filtration, drying, and free-flowing porous sPOP-15 of 4.1g was obtained.
Comparative example 16
Non-acidified sPP support: in a 250mL glass reactor, 126mL ethanol and 14mL deionized water were added, then 4.8g (about 5.0mL) divinylbenzene (avastin reagent, 80%) and 4.2g sodium p-styrenesulfonate hydrate (90%) were added, stirred at room temperature for 5min, then polyvinyl alcohol PVA (PVA, degree of polymerization 1750) of 2% monomer mass was added, stirred at 45 ℃ for 1h to completely dissolve the stabilizer, AIBN of 2.0% monomer mass was added, heated to 70 ℃ to react for 3 hours, then the temperature was raised to 80 ℃ to react for 5 hours, after which the stirring speed was 350 rpm, after filtration, washing 3 times with an alcohol-water mixed solvent, filtration, and drying, a free-flowing 5.2g porous sPOP-16 was obtained.
The specific surface area, pore volume, average particle diameter and particle size distribution results of the porous organic polymer supports prepared in examples 1 to 13 and comparative examples 14 to 16 are shown in the following table 1:
TABLE 1 results of specific surface area, pore volume, average particle diameter and particle diameter distribution of organic vehicle
As can be seen from the test results, the sulfonated porous organic polymer carrier prepared by the invention has good fluidity and surface morphology (as shown in FIG. 1), and the porous organic polymer carrier has high specific surface area which can be controlled at 200-600m 2 Between/g, the porous organic polymer carrier has a pore volume of more than 0.2mL/g, higher than other organic polymer carriers. The fluidity of the porous organic polymer carrier is superior to that of other porous organic carriers prepared by adopting a dispersion polymerization strategy, the porous organic polymer carrier prepared by the invention has no obvious agglomeration, and the particle size of the particles is singleThe peak distribution (as shown in FIG. 2) is narrow, generally less than 2.
Examples 17-32 metallocene catalyst preparation
Example 17
3.2g of the organic porous support sPop-1 prepared by the process according to the invention were suction filtered in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, and 18mL of 10% (mass percent) toluene solution of MAO (produced by the chemical research center of Petroleum Lanzhou, and having a TMA content of less than 0.2%, see below) was added and stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at 0 ℃ for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and is marked as Cat-1, wherein the Al content in the catalyst is 5.0 mmol/g, and the Zr content is 41.3 micromole/g.
Example 18
3.2g of the organic porous support sPop-2 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and recorded as Cat-2, wherein the Al content in the catalyst is 4.9 mmol/g, and the Zr content is 42.6 micromole/g.
Example 19
3.0 g of the organic porous support sPop-4 prepared by the process according to the invention were suction filtered in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.15 g (n-BuCp) is added 2 ZrCl 2 (bis-n-butyl)Cyclopentadienyl zirconium dichloride) metallocene compound, 10mL of toluene, stirring for 0.5 hour, then reacting for 3 hours at room temperature, removing the solvent after the reaction, and drying to obtain the catalyst which is recorded as Cat-3, wherein the content of Al in the catalyst is 5.2 mmol/g, and the content of Zr is 44.5 micromol/g.
Example 20
3.2g of the organic porous support sPop-5 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and is marked as Cat-4, wherein the Al content in the catalyst is 5.6 mmol/g, and the Zr content is 44.3 micromole/g.
Example 21
3.2g of the organic porous support sPop-6 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, and 20mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added and stirred at 20 ℃ for 1 hour. Then 0.10 g (1-Me-3-n-BuCp) was added 2 ZrCl 2 Stirring 10mL of toluene for 0.5 hour, then reacting at 0 ℃ for 3 hours, removing the solvent after the reaction, and drying to obtain a catalyst named Cat-5, wherein the Al content in the catalyst is 6.1 mmol/g, and the Zr content is 32.3 micromol/g.
Example 22
3.2g of the organic porous support sPop-7 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) toluene solution was added,stirring was carried out at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and is marked as Cat-6, wherein the Al content in the catalyst is 4.9 mmol/g, and the Zr content is 40.3 micromole/g.
Example 23
3.2g of the organic porous support sPop-8 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.12 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at-20 ℃ for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and is marked as Cat-7, wherein the Al content in the catalyst is 4.8 mmol/g, and the Zr content is 38.9 micromol/g.
Example 24
3.2g of the organic porous support sPop-12 prepared by the process according to the invention were suction filtered in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and recorded as Cat-8, wherein the Al content in the catalyst is 4.8 mmol/g, and the Zr content is 27.6 micromole/g.
Example 25
3.2g of the organic porous support sPop-5 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen purged reactor, and 18mL 10% (by mass) was addedAmount percent) of MAO (produced by central chemical research, central petroleum, lan) in toluene was stirred at 20 ℃ for 1 hour. Then 0.13 g of En (Ind) was added 2 ZrCl 2 (ethylene bridge bisindenyl zirconium dichloride) metallocene compound was stirred in 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, after the reaction the solvent was removed and dried to give the catalyst Cat-9, the Al content of the catalyst was 4.9 mmol/g and the Zr content was 39.8. mu. mol/g.
Example 26
4.2g of the organic porous support sPop-13 prepared by the process according to the invention were suction-filtered in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was charged into a 250mL nitrogen-purged reactor, and 20mL of 10 mass% MAO (produced by Central chemical research, Petroleum Lanzhou) in toluene was added thereto, followed by stirring at 20 ℃ for 1 hour. Then 0.13 g (1-Me-3-n-BuCp) was added 2 ZrCl 2 [ bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride]After stirring the metallocene compound and 10mL of toluene for 0.5 hour, reacting at-20 ℃ for 3 hours, removing the solvent after the reaction, and drying, the catalyst was recorded as Cat-10, and the Al content in the catalyst was 5.7 mmol/g, and the Zr content was 42.7. mu. mol/g.
Example 27
3.2g of the organic porous support sPop-13 prepared by the process according to the invention were suction filtered in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 HfCl 2 (di-n-butyl cyclopentadienyl hafnium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at-20 ℃ for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and is marked as Cat-11, wherein the Al content in the catalyst is 5.4 mmol/g, and the Zr content is 40.7 micromole/g.
Example 28
3.2g of the organic porous support sPOP-5 prepared by the method of the invention are filtered in a vacuum drier under vacuum at 120 DEG CFor 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, and 22mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added and stirred at 20 ℃ for 1 hour. Then 0.10 g (n-BuCp) was added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and recorded as Cat-12, wherein the Al content in the catalyst is 6.5 mmol/g, and the Zr content is 32.3 micromole/g.
Example 29
3.2g of the organic porous support sPop-5 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was charged into a 250mL nitrogen-purged reactor, and 20mL of 10 mass% MAO (produced by Central chemical research, Petroleum Lanzhou) in toluene was added thereto, followed by stirring at 20 ℃ for 1 hour. Then 0.13 g rac-Me2Si- (2-Me-benz [ e ] was added]Ind) 2 ZrCl 2 [ dimethylsilyl-bridged bis (2-methyl-benzoindenyl) zirconium dichloride]After stirring the metallocene compound and 10mL of toluene for 0.5 hour, reacting at room temperature for 3 hours, removing the solvent after the reaction, and drying, the catalyst was recorded as Cat-13, and the catalyst had an Al content of 6.1 mmol/g and a Zr content of 36.3. mu. mol/g.
Comparative example 30
3.2g of the organic porous carrier POP-14 prepared by the method of the invention are filtered in a vacuum drier for 12 hours in vacuum at 120 ℃. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) was added 2 ZrCl 2 (bis-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and is marked as Cat-14, wherein the Al content in the catalyst is 5.2 mmol/g, and the Zr content is 38.7 micromole/g.
Comparative example 31
3.2g of the organic porous support sPop-15 prepared by the process according to the invention were filtered with suction in a vacuum desiccator at 120 ℃ for 12 hours. The treated carrier was placed in a 250mL nitrogen-purged reactor, 18mL of 10% (mass percent) MAO (produced by Mitsubishi chemical research center) in toluene was added, and the mixture was stirred at 20 ℃ for 1 hour. Then 0.13 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is dried and recorded as Cat-15, wherein the Al content in the catalyst is 4.8 mmol/g, the Zr content is 24.1 mmol/g, the Al content in the catalyst is 5.4 mmol/g, and the Zr content is 42.8 mmol/g.
Comparative example 32
5.0 g of Grace 955 silica gel is dried at 600 ℃ for 8 hours to remove surface water and a large amount of hydroxyl groups, cooled to room temperature under nitrogen, and then the treated silica gel carrier is introduced into 250mL of a reactor substituted with nitrogen, 28mL of 10 mass% MAO (produced by the central chemical research center of Petroleum Lanzhou) in toluene is added, and stirred at 20 ℃ for 1 hour. Then 0.20 g (n-BuCp) is added 2 ZrCl 2 (di-n-butylcyclopentadienyl zirconium dichloride) metallocene compound is stirred with 10mL of toluene for 0.5 hour, then reacted at room temperature for 3 hours, the solvent is removed after the reaction, and the catalyst is obtained after drying and recorded as Cat-16, wherein the Al content in the catalyst is 5.1 mmol/g, and the Zr content is 43.6 micromole/g.
Examples 33-48 catalysts for ethylene polymerization
In one polymerization reactor, ethylene slurry polymerization and copolymerization of ethylene with alpha-olefins were carried out using the metallocene catalysts cat 1-16 prepared in examples 17-29 and comparative examples 30-32.
Ethylene homopolymerization: 2.0L of dry hexane was charged into a 5L stainless autoclave purged with nitrogen and dried, and then 5mL of triethylaluminum TEA (1.0 mol/L) was charged with stirring at 450 rpm, and then 0.2 g of the above catalyst was added, and polymerization was carried out with ethylene being introduced to maintain the internal pressure of the autoclave at 1.0MPa under a condition of stirring at 80 ℃ for 1 hour at 450 rpm, and the reaction was terminated, cooled to room temperature, and dried to obtain a polyethylene product.
Copolymerization of ethylene with α -olefins:
2.0L of dry hexane was charged into a 5L stainless autoclave purged with nitrogen and dried, then 5mL of triethylaluminum TEA (1.0 mol/L) was added, 30mL of hexene-1 was added, the stirring speed was 450 rpm, then 0.2 g of the above catalyst was added, ethylene was introduced to maintain the internal pressure of the autoclave at 1.0MPa, polymerization was carried out at 80 ℃ under stirring at 450 rpm for 1 hour, the reaction was terminated, cooling was carried out to room temperature, and drying was carried out to obtain a polyethylene product.
Examples 33-48 catalysts the olefin polymerization results are shown in table 2 below:
TABLE 2 results of olefin polymerization with catalysts from examples 33-48
From the ethylene homopolymerization and the copolymerization result of ethylene and hexene-1, it is known that the metallocene catalyst loaded by the benzene sulfonic acid functionalized or sulfonic acid functionalized porous organic polymer carrier has higher catalytic activity than the inorganic carrier and the porous organic polymer carrier functionalized by hydroxyethyl methacrylate, in addition, the prepared sulfonate porous organic polymer carrier is not acidified, the activity of the loaded catalyst is lower and is similar to that of the common inorganic carrier loaded metallocene catalyst, and the sulfonic acid functionalized carrier obtained by acidifying the sulfonate group has ultrahigh polymerization activity and can reach 3-4 times of that of a silica gel carrier.
Polymerization of propylene
Example 49
Propylene homopolymerization: 1.0kg of dry propylene was charged into a 5 liter stainless steel autoclave purged with nitrogen and dried, and the autoclave pressure was 3.4MPa, then 20ml of triisobutylaluminum (5 wt% hexane solution) was added with a stirring speed of 450 rpm, then 0.1 g of cat-13 catalyst was added, and polymerization was carried out at 70 ℃ under stirring at 450 rpm for 1 hour, the reaction was terminated, cooled to room temperature, and dried to obtain 805 g of polypropylene with a polymerization activity of 8050gpp/gcat.
Copolymerization of ethylene and octene
Example 50
2.0 liters of dry hexane was charged into a 5 liter stainless steel autoclave purged with nitrogen and dried, then 5mL of triethylaluminum TEA (1.0 mol/liter) was added, 30mL of octene-1 was added, the stirring speed was 450 rpm, then the catalyst cat-50.2 g was added, the internal pressure of the autoclave was maintained at 1.0MPa by feeding ethylene, polymerization was carried out at 80 ℃ under stirring at 450 rpm for 1 hour, the reaction was terminated, cooled to room temperature, and after drying, 912 g of polymer was obtained, the polymerization activity was 4560 g/gcat.h.
Claims (19)
1. A metallocene catalyst system loaded on a porous organic polymer carrier mainly comprises the porous organic polymer carrier, a metallocene compound and a cocatalyst, and is characterized in that the porous organic polymer carrier is a copolymer of a basic monomer and a functional monomer, the basic monomer is divinylbenzene, the functional monomer is styrene containing benzenesulfonic acid functional groups or sulfonic acid groups, and the mass percentage of the functional monomer accounts for 5% -60% of the porous organic polymer carrier.
2. The porous organic polymer support-supported metallocene catalyst system of claim 1, wherein a third comonomer is added when the base monomer is copolymerized with the functional monomer.
3. The porous organic polymer supported metallocene catalyst system of claim 2, wherein the third comonomer is at least one selected from the group consisting of styrene, alkyl substituted styrene, and chloromethyl substituted styrene.
4. The porous organic polymer supported metallocene catalyst system of claim 1, wherein the functional monomer is selected from sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, sodium 2-methyl-4-sulfonate-based styrene, 2-methyl-3-sulfonate-sodium-based styrene, 2-methyl-3-sulfonate-based styrene, vinyl-4-methylbenzenesulfonic acid, sodium vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sulfonate-sodium-based styrene, 2-ethyl-3-sulfonate-sulfonic-styrene, 4' -bis (2-sulfonate-styryl) -1,1' -biphenyl, 2- (2-styryl) benzenesulfonic acid, and hydrates thereof.
5. The porous organic polymer support-supported metallocene catalyst system of claim 1, wherein the cocatalyst is an alkylaluminoxane.
6. The porous organic polymer supported metallocene catalyst system of claim 1, wherein the metallocene compound has the general formula Cp x MA y B z (ii) a Wherein Cp is unsubstituted cyclopentadienyl, substituted cyclopentadienyl, indenyl, fluorenyl, indenyl ligand in a hydrogenated form or fluorenyl ligand in a hydrogenated form, M is transition metal zirconium or hafnium, A, B is respectively a halogen atom, a hydrogen atom or an alkyl group, x is an integer of 1 to 3, and y and z are integers of 0 to 3.
7. The porous organic polymer support-supported metallocene catalyst system of claim 1, wherein the cocatalyst is calculated as aluminum Al, the metallocene compound is calculated as metal atom M, and the molar ratio of cocatalyst to metallocene compound is Al: m is 75-500; the amount ratio of the cocatalyst to the porous organic polymer carrier is 1 mmol/g carrier to 12 mmol/g carrier, calculated by aluminum Al; the metallocene compound has a metal active center metal atom content of 5 to 100. mu. mol/g of support.
8. The porous organic polymer supported metallocene catalyst system according to claim 7, wherein the cocatalyst is calculated as aluminum Al, the metallocene compound is calculated as metal atom M, and the molar ratio of cocatalyst to metallocene compound is Al: m is 100-300; the amount ratio of the cocatalyst to the porous organic polymer carrier is 3 mmol/g carrier to 8 mmol/g carrier, calculated by aluminum Al; the metallocene compound has a metal active center metal atom content of 10 to 50. mu. mol/g of carrier.
9. A process for the preparation of a porous organic polymer support supported metallocene catalyst system according to any of claims 1 to 8, characterized in that it comprises the following steps:
step (1): at room temperature, adding a basic monomer of divinylbenzene, a functional monomer of styrene containing benzenesulfonic acid functional groups or sulfonic acid group and removing the polymerization inhibitor to the mixture C 1 -C 4 Alcohol or C 1 -C 4 In the dispersion liquid composed of alcohol and water, the mass ratio of the total amount of the added basic monomer and the added functional monomer to the dispersion liquid is 1: 5-20, so that the system is uniformly dispersed, and the mass ratio of the functional monomer to the basic monomer is 0.2-2: 1;
step (2): dissolving a stabilizer in a system at 20-50 ℃, wherein the mass ratio of the addition amount of the stabilizer to the total addition amount of the basic monomer and the functional monomer is 0.5-3: 100, adding a free radical initiator, then heating to 60-80 ℃, and reacting for 3-12 hours, wherein the mass ratio of the addition amount of the free radical initiator to the total addition amount of the basic monomer and the functional monomer is 0.5-3: 100, after the reaction is finished, washing to remove impurities;
and (3): adding dilute acid, carrying out acidification reaction at 20-70 ℃, washing and drying to obtain a porous organic polymer carrier;
and (4): and (3) adding the porous organic polymer carrier obtained in the step (3) into an inert solvent under the anhydrous and anaerobic operation condition, then adding a cocatalyst, reacting for 15-120 minutes, adding a metallocene compound, adjusting the temperature to-40-80 ℃, reacting for 15-180 minutes, and washing the product by using the inert solvent to obtain the metallocene catalyst loaded by the porous organic polymer carrier.
10. The method of claim 9, wherein C is the dispersion of step (1) 1 -C 4 The alcohol is at least one of methanol, ethanol, propanol, isopropanol, 1-butanol and isobutanol, and the dispersion liquid C 1 -C 4 The mass ratio of the alcohol to the water is 5-15: 1.
11. the method for preparing a porous organic polymer supported metallocene catalyst system according to claim 9, wherein the stabilizer in step (2) is polyvinyl alcohol or polypropylene oxide-polyethylene oxide copolymer.
12. The method of claim 11 wherein the weight average molecular weight of the stabilizer is 6,000-100,000.
13. The method of claim 9, wherein the free radical initiator in step (2) is azobisisobutyronitrile or dibenzoyl peroxide.
14. The method of claim 9, wherein the dilute acid in step (3) is dilute hydrochloric acid or dilute sulfuric acid.
15. The method of claim 9, wherein a third comonomer is added in step (1).
16. The method of claim 15, wherein the third comonomer is at least one of styrene, alkyl substituted styrene, and chloromethyl substituted styrene.
17. The method of claim 9, wherein the functional monomer of step (1) is selected from the group consisting of sodium p-styrenesulfonate, p-styrenesulfonic acid, sodium m-styrenesulfonate, m-styrenesulfonic acid, o-styrenesulfonic acid, sodium o-styrenesulfonate, sodium 2-methyl-4-sulfonate-based styrene, 2-methyl-3-sulfonate-based styrene, vinyl-4-methylbenzenesulfonic acid, sodium vinyl-4-methylbenzenesulfonate, 2-ethyl-3-sulfonate-based styrene, 2-ethyl-3-sulfonate-styrene, sodium, 4,4 '-bis (2-sulfostyryl) -1,1' -biphenyl, 2- (2-styryl) benzenesulfonic acid, and hydrates thereof.
18. Use of a porous organic polymer support supported metallocene catalyst system according to any of claims 1 to 8, wherein the catalyst system is used in the polymerisation or copolymerisation of olefins.
19. Use according to claim 18, wherein the polymerization or copolymerization of olefins is an ethylene homopolymerization, a propylene homopolymerization, a copolymerization of ethylene and propylene, a copolymerization of ethylene and α -olefins, or a copolymerization of propylene and α -olefins; the alpha-olefin is butene, pentene, hexene, octene or 4-methyl 1-pentene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276240.4A CN115073628B (en) | 2021-03-15 | 2021-03-15 | Metallocene catalyst system loaded by porous organic polymer carrier and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276240.4A CN115073628B (en) | 2021-03-15 | 2021-03-15 | Metallocene catalyst system loaded by porous organic polymer carrier and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115073628A true CN115073628A (en) | 2022-09-20 |
| CN115073628B CN115073628B (en) | 2023-09-26 |
Family
ID=83241813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110276240.4A Active CN115073628B (en) | 2021-03-15 | 2021-03-15 | Metallocene catalyst system loaded by porous organic polymer carrier and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115073628B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5168104A (en) * | 1991-09-13 | 1992-12-01 | Chembiomed, Ltd. | Macroporous particles as biocompatible chromatographic supports |
| US5587439A (en) * | 1995-05-12 | 1996-12-24 | Quantum Chemical Corporation | Polymer supported catalyst for olefin polymerization |
| US5599889A (en) * | 1994-08-16 | 1997-02-04 | Stoever; Harald D. H. | Method of forming polymer microspheres |
| JP2009280544A (en) * | 2008-05-26 | 2009-12-03 | Nitto Denko Corp | Carrier for solid phase synthesis of nucleic acid |
| CN104530267A (en) * | 2014-12-19 | 2015-04-22 | 中国石油天然气股份有限公司 | Preparation method of organic carrier of olefin polymerization catalyst |
| CN104558260A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of terpolymer for olefin polymerization catalyst carrier |
| CN104558262A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of terpolymer for olefin polymerization catalyst carrier |
| CN109453814A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | Containing sulfonic group and the polymer supported rhodium catalyst of Phosphine ligands multi-stage porous and preparation and application |
-
2021
- 2021-03-15 CN CN202110276240.4A patent/CN115073628B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5168104A (en) * | 1991-09-13 | 1992-12-01 | Chembiomed, Ltd. | Macroporous particles as biocompatible chromatographic supports |
| US5599889A (en) * | 1994-08-16 | 1997-02-04 | Stoever; Harald D. H. | Method of forming polymer microspheres |
| US5587439A (en) * | 1995-05-12 | 1996-12-24 | Quantum Chemical Corporation | Polymer supported catalyst for olefin polymerization |
| JP2009280544A (en) * | 2008-05-26 | 2009-12-03 | Nitto Denko Corp | Carrier for solid phase synthesis of nucleic acid |
| CN104558260A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of terpolymer for olefin polymerization catalyst carrier |
| CN104558262A (en) * | 2013-10-29 | 2015-04-29 | 中国石油天然气股份有限公司 | Preparation method of terpolymer for olefin polymerization catalyst carrier |
| CN104530267A (en) * | 2014-12-19 | 2015-04-22 | 中国石油天然气股份有限公司 | Preparation method of organic carrier of olefin polymerization catalyst |
| CN109453814A (en) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | Containing sulfonic group and the polymer supported rhodium catalyst of Phosphine ligands multi-stage porous and preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| 朱博超、王雄、胡杰、徐人威、韩晓昱、李彦锋: "负载型茂金属烯烃聚合催化剂有机载体研究进展", 高分子通报 * |
| 肖娴、傅智盛、范志强: "烯烃聚合用茂金属催化剂负载化机理的研究进展", 合成树脂及塑料 * |
| 葛腾杰、王世华、李瑞: "茂金属催化剂负载化的研究进展", 合成树脂及塑料 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115073628B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101981064A (en) | Metallocene supported catalyst composition and a process for the preparation of polyolefin using the same | |
| KR20010042207A (en) | Polymeric supported catalysts for olefin polymerization | |
| EP2646480A1 (en) | Processes for the polymerization of olefins with extracted metal carboxylate salts | |
| EP1064092A1 (en) | Bimetallic catalysts for ethylene polymerization reactions activated with paraffin-soluble alkylalumoxanes | |
| CN104558261B (en) | Supported metallocene catalyst system and preparation method thereof | |
| EP2041189A2 (en) | Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins | |
| US20030050413A1 (en) | Supported olefin polymerization catalysts | |
| WO2003047752A1 (en) | Method of making mixed ziegler-natta/metallocene catalysts | |
| US6583082B2 (en) | Functional organic particles for catalyst supports | |
| KR20110045077A (en) | Perfluorinated Boronic Acid Based Activation Support | |
| KR101421309B1 (en) | Catalyst activators, processes for making same, and use thereof in catalysts and polymerization of olefins | |
| JP2003342316A (en) | Composition for olefin polymerization catalyst and its production | |
| CN104558265B (en) | Metallocene catalyst system and preparation method thereof | |
| US8524627B2 (en) | Activating supports with controlled distribution of OH groups | |
| CN115073628B (en) | Metallocene catalyst system loaded by porous organic polymer carrier and preparation method and application thereof | |
| US6765074B2 (en) | Olefin polymerization process | |
| CN115073627B (en) | Porous organic polymer carrier metallocene catalyst system and preparation method and application thereof | |
| CN115073629B (en) | Supported metallocene catalyst system and preparation method and application thereof | |
| JP7222094B2 (en) | Method for preparing catalyst for olefin polymerization | |
| KR101498814B1 (en) | The preparation of supported Metallocene catalyst | |
| US20020107344A1 (en) | Supprt materials for use with polymerization catalysts | |
| JP3496955B2 (en) | Method for producing solid catalyst component for olefin polymerization | |
| KR101396318B1 (en) | Preparation method for supported metallocene catalyst and polyolefin using the same | |
| KR100466511B1 (en) | High activity olefin polymerization silica supported catalyst | |
| CA2499414A1 (en) | Supported catalysts for gas phase olefin polymerization |
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 |