CN116135892A - Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof - Google Patents
Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof Download PDFInfo
- Publication number
- CN116135892A CN116135892A CN202111352412.8A CN202111352412A CN116135892A CN 116135892 A CN116135892 A CN 116135892A CN 202111352412 A CN202111352412 A CN 202111352412A CN 116135892 A CN116135892 A CN 116135892A
- Authority
- CN
- China
- Prior art keywords
- compound
- ethylene
- groups
- polyethylene resin
- magnesium
- 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
- 230000002902 bimodal effect Effects 0.000 title claims abstract description 70
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 claims abstract description 107
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 103
- -1 aromatic ester compound Chemical class 0.000 claims abstract description 101
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 26
- 229920001519 homopolymer Polymers 0.000 claims abstract description 20
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 150000002681 magnesium compounds Chemical class 0.000 claims description 17
- 239000000155 melt Substances 0.000 claims description 16
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 11
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical class CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 150000003609 titanium compounds Chemical class 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 30
- 229920000573 polyethylene Polymers 0.000 abstract description 26
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003701 inert diluent Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 3
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006353 environmental stress Effects 0.000 description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- 235000011147 magnesium chloride Nutrition 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- GXXFZZLGPFNITM-UHFFFAOYSA-N Propyl phenylacetate Chemical compound CCCOC(=O)CC1=CC=CC=C1 GXXFZZLGPFNITM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- SNMLXTDVQDHSKS-UHFFFAOYSA-N ethyl 2,4,6-tri(propan-2-yl)benzoate Chemical compound CCOC(=O)C1=C(C(C)C)C=C(C(C)C)C=C1C(C)C SNMLXTDVQDHSKS-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RSDNCIKBJADZGY-UHFFFAOYSA-N (2-methylcyclohexyl) 2-phenylacetate Chemical compound C1(=CC=CC=C1)CC(=O)OC1C(CCCC1)C RSDNCIKBJADZGY-UHFFFAOYSA-N 0.000 description 1
- JYGXLMBDRQFQJN-UHFFFAOYSA-N (2-methylcyclohexyl) benzoate Chemical compound CC1CCCCC1OC(=O)C1=CC=CC=C1 JYGXLMBDRQFQJN-UHFFFAOYSA-N 0.000 description 1
- IENDTEDHWNXFQX-UHFFFAOYSA-N (4-butylphenyl) acetate Chemical compound CCCCC1=CC=C(OC(C)=O)C=C1 IENDTEDHWNXFQX-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- NMBQBIACXMPEQB-UHFFFAOYSA-N 2-butoxyethyl benzoate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1 NMBQBIACXMPEQB-UHFFFAOYSA-N 0.000 description 1
- KPHLTQOKDPSIGL-UHFFFAOYSA-N 2-ethoxyethyl benzoate Chemical compound CCOCCOC(=O)C1=CC=CC=C1 KPHLTQOKDPSIGL-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- SIOQSSIIVLKXCI-UHFFFAOYSA-N 2-methoxyethyl 2-phenylacetate Chemical compound COCCOC(=O)CC1=CC=CC=C1 SIOQSSIIVLKXCI-UHFFFAOYSA-N 0.000 description 1
- XRZZOPVYBXOXCN-UHFFFAOYSA-N 2-methoxyethyl benzoate Chemical compound COCCOC(=O)C1=CC=CC=C1 XRZZOPVYBXOXCN-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- SJSOFNCYXJUNBT-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1OC SJSOFNCYXJUNBT-UHFFFAOYSA-N 0.000 description 1
- UIXIPEPVSUVPQA-UHFFFAOYSA-N 3-methoxypropyl 2-phenylacetate Chemical compound COCCCOC(=O)CC1=CC=CC=C1 UIXIPEPVSUVPQA-UHFFFAOYSA-N 0.000 description 1
- APQLPNDPGHUOIS-UHFFFAOYSA-N 3-methoxypropyl benzoate Chemical compound COCCCOC(=O)C1=CC=CC=C1 APQLPNDPGHUOIS-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- WDNXINHBDNHNTI-UHFFFAOYSA-N 4-methoxybutyl 2-phenylacetate Chemical compound COCCCCOC(=O)CC1=CC=CC=C1 WDNXINHBDNHNTI-UHFFFAOYSA-N 0.000 description 1
- KTJBUAZPIUBTDM-UHFFFAOYSA-N 4-methoxybutyl benzoate Chemical compound COCCCCOC(=O)C1=CC=CC=C1 KTJBUAZPIUBTDM-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- RNHCXKFXAOBPDI-UHFFFAOYSA-N 5-acetyl-2-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(C)=O)C=C1C(O)=O RNHCXKFXAOBPDI-UHFFFAOYSA-N 0.000 description 1
- WAYPTMFXSWTBIY-UHFFFAOYSA-N 6-methoxyhexyl 2-phenylacetate Chemical compound C1(=CC=CC=C1)CC(=O)OCCCCCCOC WAYPTMFXSWTBIY-UHFFFAOYSA-N 0.000 description 1
- YIXIZHCBOHNDCD-UHFFFAOYSA-N 6-methoxyhexyl benzoate Chemical compound COCCCCCCOC(=O)C1=CC=CC=C1 YIXIZHCBOHNDCD-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- LDOXTQYWWYXYSQ-UHFFFAOYSA-N Butyl phenylacetate Chemical compound CCCCOC(=O)CC1=CC=CC=C1 LDOXTQYWWYXYSQ-UHFFFAOYSA-N 0.000 description 1
- MTAHGWGAEGVCLS-UHFFFAOYSA-N Hexyl phenylacetate Chemical compound CCCCCCOC(=O)CC1=CC=CC=C1 MTAHGWGAEGVCLS-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- FEXQDZTYJVXMOS-UHFFFAOYSA-N Isopropyl benzoate Chemical compound CC(C)OC(=O)C1=CC=CC=C1 FEXQDZTYJVXMOS-UHFFFAOYSA-N 0.000 description 1
- SSMBXPJYHMZLOJ-UHFFFAOYSA-N Isopropyl phenylacetate Chemical compound CC(C)OC(=O)CC1=CC=CC=C1 SSMBXPJYHMZLOJ-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QMJUEAKSVSCCQL-UHFFFAOYSA-N benzyl phosphite Chemical compound [O-]P([O-])OCC1=CC=CC=C1 QMJUEAKSVSCCQL-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- MNEAZOGMEQUJER-UHFFFAOYSA-N cyclohexyl 2-phenylacetate Chemical compound C1CCCCC1OC(=O)CC1=CC=CC=C1 MNEAZOGMEQUJER-UHFFFAOYSA-N 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RJYPOWRKMKNFHH-UHFFFAOYSA-N ethyl 2,4-dimethylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1C RJYPOWRKMKNFHH-UHFFFAOYSA-N 0.000 description 1
- NBBSIMLSNFENNF-UHFFFAOYSA-N ethyl 2,6-dimethylbenzoate Chemical compound CCOC(=O)C1=C(C)C=CC=C1C NBBSIMLSNFENNF-UHFFFAOYSA-N 0.000 description 1
- BTRGZBIXPLFVNK-UHFFFAOYSA-N ethyl 2-(4-methylphenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(C)C=C1 BTRGZBIXPLFVNK-UHFFFAOYSA-N 0.000 description 1
- SOUAXOGPALPTTC-UHFFFAOYSA-N ethyl 2-methylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C SOUAXOGPALPTTC-UHFFFAOYSA-N 0.000 description 1
- IHAAVLXHNOZMBC-UHFFFAOYSA-N ethyl 3,5-dimethylbenzoate Chemical compound CCOC(=O)C1=CC(C)=CC(C)=C1 IHAAVLXHNOZMBC-UHFFFAOYSA-N 0.000 description 1
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KOWXKIHEBFTVRU-UHFFFAOYSA-N nga2 glycan Chemical compound CC.CC KOWXKIHEBFTVRU-UHFFFAOYSA-N 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- AMZORBZSQRUXNC-UHFFFAOYSA-N o-Tolyl acetate Chemical compound CC(=O)OC1=CC=CC=C1C AMZORBZSQRUXNC-UHFFFAOYSA-N 0.000 description 1
- AVBRYQRTMPHARE-UHFFFAOYSA-N octyl formate Chemical compound CCCCCCCCOC=O AVBRYQRTMPHARE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QROFQHQXTMKORN-UHFFFAOYSA-N tert-butyl 2-phenylacetate Chemical compound CC(C)(C)OC(=O)CC1=CC=CC=C1 QROFQHQXTMKORN-UHFFFAOYSA-N 0.000 description 1
- LYDRKKWPKKEMNZ-UHFFFAOYSA-N tert-butyl benzoate Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1 LYDRKKWPKKEMNZ-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- 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 provides a method for preparing a bimodal polyethylene resin for a pipe material and the bimodal polyethylene resin thereof. The process comprises carrying out an ethylene homo-polymerization reaction in the presence of a Ziegler-Natta catalyst system comprising an aromatic ester compound, in the presence or absence of hydrogen, to obtain a stream comprising an ethylene homopolymer; ethylene monomer and the stream comprising ethylene homopolymer obtained in the previous stage are added to the comonomer for copolymerization in the presence or absence of hydrogen. The bimodal polyethylene resin has better tensile property, impact resistance and excellent thermal degradation resistance. The bimodal polyethylene resin is suitable for preparing high-performance and large-caliber bimodal polyethylene pipe material products.
Description
Technical Field
The invention relates to the field of polyethylene, in particular to a method for preparing bimodal polyethylene resin for pipe materials by using Ziegler Natta catalyst containing aromatic ester compounds and the bimodal polyethylene resin.
Background
Polyethylene plastic tubing is mainly divided into two main categories: high density polyethylene HDPE (low pressure polyethylene) and low density polyethylene LDPE (high pressure polyethylene). The application of polyethylene materials is very wide, and the field of pipes is only one important aspect in the field of polyethylene application. Because of the difference in physical properties of HDPE and LDPE, the two materials differ in the pipe application area: low Density Polyethylene (LDPE) has good flexibility. However, the compressive strength is low, so that the pipe can only be used for low-pressure small-diameter pipes, and the pipe is often manufactured into a coil pipe to be used for rural water change and some occasions which are not used for a long time. High Density Polyethylene (HDPE) materials are widely used in pressure pipe applications (e.g., PE80, PE 100) because of their relatively good compression resistance. The popular explanation for PE80 is: the material pipe is not damaged when continuously pressed for 50 years at 20 ℃, and the minimum required strength of the pipe wall is as follows: 80MPa, and so on. In the early stages of plastic pipe development, the use of polyethylene pressure tubing was much smaller than polyvinyl chloride tubing. With the appearance of new HDPE materials and new technology, the cost (weight) is greatly changed, and with the appearance of second-generation polyethylene pipe materials (equivalent to PE 80) and third-generation polyethylene pipe materials (equivalent to PE 100), the weight of polyethylene pipes with the same length is only 93% of the weight of UPVC pipes under the same pressure grade and condition at the same diameter of 200. Therefore, the polyethylene pipe materials of the second generation and the third generation not only obviously improve the minimum required strength of PE, but also improve the environmental stress cracking resistance of the material, have obvious crack resistance and rapid growth capacity, and more importantly, can reduce the wall thickness and increase the conveying section under the same using pressure. While increasing the pressure used at the same wall thickness increases the transport capacity (for example: natural gas transport at the same wall thickness, transport pressures of up to 10 bar with PE100 polyethylene pipe and up to 8 bar with PE80 polyethylene pipe). With the improvement of polyethylene technology, the economic benefit is remarkable. Recently, it has been reported that the fourth generation polyethylene pipe material PE125 has been developed successfully, so that it can be predicted that a larger diameter and more economical polyethylene pressure pipe has a wide application field.
The existing mature bimodal tube material products in the market adopt imported catalysts to produce PE100 tube materials, the catalysts improve the fine powder content of polymers and prolong the running period of devices, but the problems that the slurry process has more fine powder, more oligomers and short running period of the devices are not fundamentally solved. The imported catalyst has high price and has the problem of more oligomers, the running period of the device is about one month, and the device needs to be stopped for cooking after 5 months of running. Therefore, developing an excellent domestic slurry polyethylene catalyst with low fine powder content and low oligomer content will have great economic and social benefits, and will also make the technology in this field reach international level. Meanwhile, the research of China on the aspect of high-performance slurry catalyst is enhanced, the urgency and the necessity are provided, and the technical progress and the huge economic benefit of China in particular in the field are directly influenced.
Disclosure of Invention
Therefore, aiming at the problems in the prior art, the invention provides a Ziegler-Natta catalyst containing aromatic ester compounds, which is directly catalyzed and polymerized in a plurality of reactors connected in series, and further combines the different chain transfer agents, the hydrogen consumption and the comonomer consumption in the reaction to prepare the bimodal polyethylene resin with specific melt index, specific molecular weight and molecular weight distribution. The bimodal polyethylene resin disclosed by the invention has the advantages of no problem of precipitation of low molecular components, higher environmental stress cracking resistance, better tensile property and better thermal degradation resistance, and is very suitable for production of high-performance bimodal polyethylene pipe material resin.
It is an object of the present invention to provide a process for preparing a bimodal polyethylene resin for pipe material comprising the steps of:
first stage ethylene homopolymerization: comprising carrying out an ethylene homo-polymerization in the presence of a Ziegler-Natta catalyst system comprising an aromatic ester compound, in the presence or absence of hydrogen, to obtain a stream comprising an ethylene homopolymer;
second stage ethylene copolymerization: and adding ethylene monomer and the material flow containing ethylene homopolymer obtained in the previous stage into the comonomer to carry out copolymerization reaction in the presence or absence of hydrogen to obtain the bimodal polyethylene resin.
In the preparation method of the bimodal polyethylene resin, the ethylene homopolymerization reaction in the first stage and the ethylene copolymerization reaction in the second stage adopt the same catalyst system. Specifically, the reactor for the two-stage reaction only needs to inject the catalyst in the first-stage homopolymerization reaction, and the second-stage copolymerization reaction does not need to reinject the catalyst.
The Ziegler-Natta catalyst system containing the aromatic ester compound in the preparation method of the bimodal polyethylene resin can adopt the existing Ziegler-Natta catalyst system containing the aromatic ester compound in the prior art. Specific examples of Ziegler-Natta catalyst systems containing aromatic esters according to the present invention can be found in patent documents CN1958620A, CN1958622A, CN102344514A, CN102344515A, CN102875708A, CN103772536A, CN102875709A, CN102993344A, CN102875707A, etc. The entire contents of these patent documents are incorporated by reference into the present invention.
Preferably, in the preparation method of the bimodal polyethylene resin of the invention, the Ziegler-Natta catalyst system containing aromatic ester compound comprises the following components: (1) a magnesium-containing compound; (2) an organophosphorus compound; (3) an organic alcohol compound; (4) an organic epoxy compound; (5) aromatic ester compounds; (6) a titanium-containing compound; forming a magnesium complex by reacting a magnesium-containing compound in a solvent system comprising an organic phosphorus compound, an organic epoxy compound, and an organic alcohol compound; the magnesium compound and the aromatic ester compound and the titanium compound react to form the catalyst system.
The Ziegler-Natta catalyst system containing aromatic ester compound is prepared through forming magnesium compound with magnesium compound in solvent system containing organic phosphorus compound, organic epoxy compound and organic alcohol compound. Typically, such magnesium composites are homogeneous transparent solutions. Then the magnesium compound reacts with aromatic ester compound and titanium compound to form catalyst system.
The components of the Ziegler-Natta catalyst system containing the aromatic ester compound are as follows:
the magnesium-containing compound is selected from at least one of magnesium dihalide, water complex or alcohol complex of magnesium dihalide, and derivatives in which one halogen atom in the formula of magnesium dihalide is replaced by hydrocarbyloxy or halohydrocarbonyloxy. The magnesium dihalide is preferably magnesium dichloride, magnesium dibromide, magnesium diiodide. Among them, magnesium dichloride is preferable.
The organic phosphorus compound is at least one of hydrocarbyl ester of orthophosphoric acid, hydrocarbyl ester of phosphorous acid, halohydrocarbyl ester of orthophosphoric acid and halohydrocarbyl ester of phosphorous acid. The method specifically comprises the following steps: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, benzyl phosphite and the like. Of these, trimethyl orthophosphate, triethyl orthophosphate and tributyl orthophosphate are preferred, with tributyl orthophosphate being most preferred.
The organic epoxy compound is preferably selected from C 2 -C 8 Aliphatic olefins, C 2 -C 8 Aliphatic diolefins, C 2 -C 8 Or C 2 -C 8 At least one of an oxide, a glycidyl ether and a internal ether of a halogenated aliphatic diene; preferably at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, tetrahydrofuran, methyl glycidyl ether and diglycidyl ether; among them, ethylene oxide, propylene oxide, epichlorohydrin and tetrahydrofuran are preferable, and tetrahydrofuran and epichlorohydrin are most preferable.
The organic alcohol compound is C 1 -C 10 Straight-chain, branched or cyclic alkyl alcohols, or C 6 -C 20 At least one of the aryl group-containing alcohols. Examples of alcohols include fatty alcohols: methanolEthanol, propanol, isopropanol, butanol, isobutanol, glycerol, hexanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, decanol, and the like; cycloalkanols such as cyclohexanol, methylcyclohexanol, and the like; aromatic alcohol such as benzyl alcohol, methyl benzyl alcohol, alpha-methyl benzyl alcohol, alpha-dimethyl benzyl alcohol, etc. Ethanol, butanol, 2-ethylhexanol, glycerol are preferred. The proportion of each alcohol in the alcohol composition is not particularly limited.
The solvent system of the magnesium compound can be optionally added with inert diluents, and generally the inert diluents comprise aromatic hydrocarbon compounds or alkane compounds, and the aromatic hydrocarbon compounds comprise benzene, toluene, dimethylbenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, monochlorotoluene and derivatives thereof; the alkane includes one of straight-chain alkane of 3 to 20 carbons, branched alkane or cycloalkane, or a mixture thereof, such as butane, pentane, hexane, cyclohexane, heptane, etc., and may be used as long as it contributes to dissolution of magnesium halide. The above inert diluents may be used alone or in combination.
The general formula of the aromatic ester compound is R 1 n R 2 m C 6 H 5-n-m-x [(CH 2 ) y COOR 3 ] x Wherein R is 1 ，R 2 Each independently is C 1 -C 20 Alkyl, aryl, alicyclic, alkoxy, R 3 Is C 1 -C 20 Alkyl, aryl and alicyclic groups, n is more than or equal to 0 and less than or equal to 5, m is more than or equal to 0 and less than or equal to 5,0<x is less than 5, y is more than or equal to 0 and less than or equal to 9, n, m, x and y are integers, and n+m+x is less than 5. The aromatic ester compound of the invention comprises: methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate, tert-butyl benzoate, hexyl benzoate, octyl benzoate, cyclohexyl benzoate, 2-methylcyclohexyl benzoate, ethyl o-methylbenzoate, ethyl p-methylbenzoate, ethyl 2, 4-dimethylbenzoate, ethyl 2, 6-dimethylbenzoate, ethyl 3, 5-dimethylbenzoate, ethyl 2,4, 6-triisopropylbenzoate, methoxyethyl benzoate, methoxypropyl benzoate, methoxybutyl benzoate, methoxyhexyl benzoate, ethyl benzoateMethoxy octyl formate, ethoxy ethyl benzoate, ethoxy propyl benzoate, ethoxy butyl benzoate, ethoxy hexyl benzoate, ethoxy octyl benzoate, butoxy ethyl benzoate, butoxy butyl benzoate, butoxy hexyl benzoate, 5-acetyl-2-ethoxybenzoate, 3,4, 5-trimethoxybenzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, isopropyl phenylacetate, butyl phenylacetate, t-butyl phenylacetate, hexyl phenylacetate, octyl benzoate, cyclohexyl phenylacetate, 2-methylcyclohexyl phenylacetate, o-methylphenylacetate, ethyl p-methylphenylacetate, ethyl 2, 4-dimethylbenzylacetate, ethyl 2, 6-dimethylbenzylacetate, ethyl 3, 5-dimethylbenzylacetate, ethyl 2,4, 6-triisopropylbenzoate, methoxyethyl phenylacetate, methoxypropyl phenylacetate, methoxybutyl phenylacetate, methoxyhexyl phenylacetate, methoxy octyl phenylacetate, methoxy ethyl phenylacetate, ethoxy ethyl 2, 4-butylphenylacetate, methoxy ethyl 2-butylphenylacetate, ethoxy ethyl 2-2, 4-dimethylbenzylacetate. Ethyl benzoate, propyl benzoate, ethoxyethyl benzoate, ethyl phenylacetate, and propyl phenylacetate are preferred.
The general formula of the titanium-containing compound is Ti (OR 5 ) a X 2 b Wherein R is 5 Is C 1 -C 14 Aliphatic or aromatic hydrocarbon radicals, X 2 A is an integer of 1 to 4, b is an integer of 1 to 4, a+b=3 or 4.
The titanium-containing compound comprises: tiCl 4 、TiBr 4 、TiCl 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 2 H 5 )Br 3 、Ti(OC 2 H 5 ) 2 Cl 2 、Ti(OCH 3 ) 2 Cl 2 、Ti(OCH 3 ) 2 I 2 、Ti(OC 2 H 5 ) 3 Cl、Ti(OCH 3 ) 3 Cl、Ti(OC 2 H 5 ) 3 I、Ti(OC 2 H 5 ) 4 、Ti(OC 3 H 7 ) 4 、Ti(OC 4 H 9 ) 4 Etc. TiCl is preferred 4 、Ti(OC 2 H 5 )Cl 3 、Ti(OCH 3 )Cl 3 、Ti(OC 4 H 9 )Cl 3 、Ti(OC 4 H 9 ) 4 . By TiCl 4 Is most preferable.
The aromatic ester compound is 0.1 to 1 mole, preferably 0.1 to 0.5 mole, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 mole, per mole of the magnesium compound in the magnesium compound, among the components of the Ziegler-Natta catalyst system containing the aromatic ester compound according to the present invention; the titanium-containing compound is 1 to 20 moles, preferably 1 to 15 moles, and for example, 1, 2, 3,4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 moles can be specifically mentioned.
In the solvent system for forming the magnesium complex in the Ziegler-Natta catalyst system containing the aromatic ester compound, the organic epoxy compound is 0.2 to 10 mol, preferably 0.2 to 4 mol, for example, 0.2, 0.3, 0.5, 1, 2, 3,4,5, 6, 7, 8, 9 and 10 mol, based on each mol of the magnesium compound; the amount of the organic phosphorus compound is 0.1 to 10 moles, preferably 0.2 to 4 moles, and for example, 0.1, 0.2, 0.5, 1, 2, 3,4,5, 6, 7, 8, 9, 10 moles may be specifically mentioned; the organic alcohol compound is preferably 0 to 6 mol, more preferably 0 to 2 mol, and for example, 0, 1, 2, 3,4,5, and 6 mol may be used.
Preferably, the Ziegler-Natta catalyst system containing aromatic ester compound according to the present invention is prepared by a process comprising the steps of:
(1) Under the protection of inert gas, dissolving the magnesium-containing compound in a solvent system containing the organic epoxy compound and the organic phosphorus compound to form a uniform solution of a magnesium compound, wherein the dissolution temperature is 50-90 ℃; and adding the organic alcohol compound during or after the formation of the solution to obtain a magnesium compound reaction solution. The reaction is sufficient, and the reaction time is generally 0.5 to 6 hours, preferably 1 to 6 hours.
(2) The reaction solution is contacted and reacted with the titaniferous compound at the temperature of minus 30 ℃ to 0 ℃ and the aromatic ester compound is introduced before, after or during the reaction; and slowly heating the mixture to 50-120 ℃, and gradually precipitating solid matters and forming particles. The reaction is sufficient, and the reaction time is generally 0.5 to 10 hours, preferably 0.5 to 6 hours.
And then may further include: (3) Removing unreacted materials and solvent from the mixture (namely, the product after the reaction in the step (2)) to obtain the Ziegler-Natta catalyst system containing the aromatic ester compound.
Wherein the removal of unreacted materials and solvents can be carried out by methods generally known in the art, such as suction filtration. Furthermore, it is preferred to wash the reaction product with the inert diluent, such as hexane, to obtain the Ziegler-Natta catalyst system containing the ester compound.
The bimodal polyethylene resin of the invention uses Ziegler-Natta catalyst system containing aromatic ester compound, and can also add ethylene polymerization reaction common catalyst promoter, such as organic aluminum catalyst promoter, when in polymerization reaction, the dosage is common dosage.
The method comprises the steps of carrying out ethylene homopolymerization and ethylene copolymerization in series in the presence of a Ziegler-Natta catalyst system containing aromatic ester compounds. The process of the present invention is preferably carried out in two or more reactors operated in series.
The series of ethylene homo-and ethylene co-polymerization may comprise two or more reaction stages; wherein both ethylene homo-polymerization and ethylene co-polymerization may be carried out in one or more stages; preferably, the ethylene homopolymerization is carried out in one stage, and the ethylene copolymerization is carried out in one or two stages; more preferably, the series of ethylene homo-and ethylene co-polymerization comprises one ethylene homo-polymerization stage followed by one ethylene co-polymerization stage.
According to the process of the present invention, the first stage ethylene homo-polymerization comprises reacting a catalyst comprising an esterThe ethylene homo-polymerization reaction is carried out in the presence of a Ziegler-Natta catalyst system of the compound, in the presence or absence of hydrogen, to obtain a stream comprising ethylene homopolymers. The ethylene homopolymer melt index obtained in the first stage ethylene homo-polymerization is greater than or equal to 60g/10min, preferably greater than or equal to 65g/10min, under a load of 1.2 kg. The density range is more than or equal to 0.963g/cm 3 Preferably 0.963 to 0.980g/cm 3 More preferably 0.965 to 0.975g/cm 3 。
And a second stage of ethylene copolymerization reaction, wherein ethylene monomers and the material flow containing ethylene homopolymer obtained in the previous stage are added into the comonomer to carry out copolymerization reaction in the presence or absence of hydrogen, so that homo-and co-polymerized mixed bimodal polyethylene resin is produced.
The method comprises the steps of carrying out ethylene homopolymerization and ethylene copolymerization in series, and obtaining the bimodal polyethylene resin by controlling the hydrogen-ethylene ratio and the ethylene copolymerization condition to obtain two molecular weight distribution structures comprising a low molecular weight part (homo-polymerization part) and a high molecular weight part (copolymerization part).
More specifically, in the method of the invention:
wherein the reaction temperature of the ethylene homopolymerization reaction in the first stage is 60-100 ℃, and the preferable temperature is 70-90 ℃; the reaction pressure is 0.1-3.0 MPa, preferably 0.5-2 MPa.
Wherein the reaction temperature of the ethylene copolymerization reaction in the second stage is 60-100 ℃, and the preferable temperature is 70-90 ℃; the reaction pressure is 0.01 to 3.0MPa, preferably 0.05 to 2MPa.
Preferably, the first stage ethylene homo-polymerization is carried out in the presence of hydrogen, the hydrogen to ethylene molar ratio (%/%) of the ethylene homo-polymerization stage being in the range of 4.0 to 7.0, preferably 5.0 to 6.0, for example, it may be in particular 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0. The molar ratio (%/%) of hydrogen to ethylene is the ratio of the molar percentage concentration (mol%) of hydrogen to the molar percentage concentration (mol%) of ethylene in actual production.
Preferably, the second stage ethylene copolymerization is carried out in the presence of hydrogen, the hydrogen to ethylene ratio (%/%) of the ethylene copolymerization stage being in the range of from 0.01 to 0.2, preferably from 0.05 to 0.1, and may be, for example, specifically 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2. The molar ratio (%/%) of hydrogen to ethylene is the ratio of the molar percentage concentration (mol%) of hydrogen to the molar percentage concentration (mol%) of ethylene in actual production.
Preferably, the molar ratio (%/%) of the comonomer to ethylene of the second stage ethylene copolymerization is from 0.01 to 0.20, preferably from 0.03 to 0.08, for example, specifically 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2 may be mentioned. The molar ratio (%/%) of the comonomer to the ethylene is the ratio of the molar percentage concentration (mol%) of the comonomer to the molar percentage concentration (mol%) of the ethylene in actual production.
Preferably, the comonomer is of the formula: ch2=chr, wherein R is a linear or branched alkane having 1-10 carbon atoms; the comonomer is preferably at least one of propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1.
The above catalyst packing, the respective flow rates of each stage or the range of reaction times are routinely adjusted and selected according to the actual reactor load.
The bimodal polyethylene resin of the instant invention can be polymerized using slurry polymerization in at least two slurry reactors connected in series. The reactors in series give high molecular weight polyethylene (i.e. ethylene copolymerized fraction) and low molecular weight polyethylene (i.e. ethylene homo-polymerized fraction) with different molecular weights, which enable good reaction mixing in the reactors.
The slurry polymerization medium may be a conventional slurry polymerization medium including: at least one of inert solvents such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, e.g., isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.
In order to adjust the molecular weight of the final polymer, hydrogen is generally used as a molecular weight regulator.
It is a further object of the present invention to provide a bimodal polyethylene resin obtainable by said process.
The bimodal polyethylene resin for pipe materials according to the invention comprises a low molecular weight fraction (homo units), a high molecular weight fraction (co-units), i.e. has a bimodal molecular weight distribution.
Further, the method comprises the steps of,
the melt index of the bimodal polyethylene resin according to the invention is 0.10 to 0.40g/10min, preferably 0.15 to 0.35g/10min, under a load of 5 kg.
The density range of the bimodal polyethylene resin is 0.943-0.963 g/cm 3 Preferably 0.945 to 0.955g/cm 3 。
According to one aspect of the present invention, the homo unit fraction of the bimodal polyethylene resin; the density range is more than or equal to 0.963g/cm 3 Preferably 0.963 to 0.980g/cm 3 More preferably in the range of 0.965 to 0.975g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index is greater than or equal to 60g/min, preferably greater than or equal to 65g/10min, under a load of 1.2 kg.
According to one aspect of the present invention, the bimodal polyethylene resin contains copolymerized units derived from a comonomer copolymerized with ethylene. The comonomer of the copolymerized unit includes an alpha-olefin monomer.
Further, the comonomer is preferably of the formula CH 2 =chr; wherein R is preferably a linear or branched alkane having from 1 to 10 carbon atoms; the comonomer is more preferably at least one of propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1, most preferably at least one of hexene-1, butene-1, octene-1.
The comonomer content of the copolymerized units in the bimodal polyethylene resin is greater than 0 and equal to or less than 1.0wt%, preferably 0.001 to 0.8wt%, specifically, for example, 0.001, 0.005, 0.01, 0.05, 0.1, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.5, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.0wt%.
According to one aspect of the technical scheme of the invention, the bimodal polyethylene resin has better tensile property, less low-molecular wax precipitation and good processability.
The bimodal polyethylene resin of the invention has a nominal strain at tensile break of greater than or equal to 500%.
The tensile yield stress of the bimodal polyethylene resin is greater than or equal to 20MPa.
The notch impact strength of the bimodal polyethylene resin of the invention at 23 ℃ is more than or equal to 20kJ/m 2 。
It is a further object of the present invention to provide a tubular article made from the bimodal polyethylene resin. When the method is specifically applied, various extrusion processes and molding methods existing in the field can be adopted to obtain bimodal pipe material polyethylene products, such as cable materials, natural gas pipelines and the like.
The invention relates to a bimodal polyethylene resin for pipe materials, which is prepared by adopting a Ziegler Natta catalyst system containing aromatic ester compounds in a plurality of reactors connected in series. The catalyst system has the advantages of controllable particles, narrow particle size distribution, higher catalytic activity, better hydrogen regulation sensitivity, high comonomer content and the like. The bimodal polyethylene resin prepared by the catalyst containing the aromatic ester compound has the characteristics of small content of large particles and fine powder, small amount of oligomer generation, outstanding mechanical property and excellent thermal degradation resistance. The Ziegler Natta catalyst system containing aromatic ester compounds is used in a plurality of reactor processes connected in series, solves the problems of more fine powder, more oligomers and short device operation period which have long plagued the slurry process, obviously improves the mechanical properties of the resin, and has considerable economic benefit.
The invention relates to a bimodal polymer prepared by using the aromatic ester compound-containing Ziegler Natta catalyst systemThe vinyl resin has good particle morphology, concentrated particle size distribution, and less large particles and fine powder content, so that the vinyl resin has good fluidity and is beneficial to processing; meanwhile, the bimodal polyethylene resin has the characteristics of few oligomers, adjustable molecular weight and molecular weight distribution and good processability. Furthermore, the bimodal polyethylene resin of the invention does not have the problem of containing low molecular precipitations. The unique resin structure of the bimodal polyethylene resin ensures that the prepared polyethylene pipe material product has excellent environmental stress cracking resistance and mechanical property. The bimodal polyethylene resins of the invention have a melt index of 0.10 to 0.40g/10min (5 kg), preferably 0.15 to 0.35g/10min, and a density of 0.943 to 0.963g/cm 3 Preferably 0.945 to 0.955g/cm 3 When in use, the material is very suitable for pipe material products.
Detailed Description
The invention will be further described by means of specific examples, which do not constitute any limitation of the invention.
The polymer-related data in the examples were obtained as follows:
(1) Resin tensile properties: the test speed was 50mm/min, measured according to the method described in GB/T1040.2-2006.
(2) Melt mass flow rate (also known as melt index, MI): the melt index of the resin after the ethylene homopolymerization was measured under a load of 1.2kg at 190℃using a CEAST model 7026 melt index apparatus according to the method described in ASTM D1238-2038, and the melt index of the resin after the ethylene copolymerization was measured under a load of 5 kg. The measurement was performed using a 1.00mm die.
(3) Notched impact strength of simply supported beams: measured according to the method described in GB/T1043.1.
(4) Resin density: measured according to the method described in GB/T1033.2-2010. The extruded bars were used as the test pieces for measuring density when testing melt flow rate, and the test pieces were smooth, void-free, burr-free. The sample strips were cut out and placed on a cold metal plate, then the sample strips were immersed in a beaker containing distilled water, covered with a lid, boiled in 200ml of boiling distilled water for 30min for annealing, and then the beaker was cooled to room temperature in a laboratory environment for testing within 24 hours.
(5) Comonomer content in bimodal polyethylene resin: and (5) measuring by adopting a nuclear magnetic resonance method. A 10 mm probe specific was used with an Avance iii 400MHz nuclear magnetic resonance spectrometer (NMR) from Bruker, switzerland. The solvent was deuterated o-dichlorobenzene and about 250mg of the sample was placed in 2.5ml deuterated solvent and heated in an oil bath at 140 ℃ to dissolve the sample and form a homogeneous solution. 13C-NMR is acquired, the probe temperature is 125 ℃, 90-degree pulse is adopted, the sampling time AQ is 5 seconds, the delay time D1 is 10 seconds, and the scanning times are more than 5000 times.
(6) Particle size distribution of resin powder: screening is carried out by using a German Retsch screening instrument, and the particle size distribution of the resin powder is examined.
(7) Oxidation induction time: measured according to the method described in GB/T19466.6-2009. The plastic sample and an inert reference (e.g., alumina) are placed in a differential thermal analyzer to rapidly displace inert gas (e.g., nitrogen) within the sample chamber with oxygen at a temperature. The change in DTA profile (differential spectrum) due to sample oxidation was tested and the oxidation induction period (time) OIT (min) was obtained to assess the heat aging resistance of the plastic.
(8) Flexural modulus: measured according to the method described in GB/T9341-2008.
The raw materials used in the examples and comparative examples of the present invention are all commercially available.
Example 1
(1) Preparation of the Ziegler-Natta catalyst system containing the ester compound:
the preparation method of the solid catalyst is the same as that of patent CN201210397456.7 (CN 103772536A). 4.0g of magnesium dichloride, 50ml of toluene, 3.0ml of epichlorohydrin, 9.0ml of tributyl phosphate and 4.4ml of ethanol are sequentially added into a reactor fully replaced by high-purity nitrogen, and the temperature is raised to 70 ℃ under stirring, and after the solid is completely dissolved to form a uniform solution, the reaction is carried out for 2 hours. The system was cooled to-10℃and 4.0ml of ethyl benzoate was slowly added dropwise, followed by dropwise addition of 60ml of titanium tetrachloride after 10 minutes of constant temperature. Slowly heating to 85 ℃, and reacting for 2 hours. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing with hexane for four times, and drying with high-purity nitrogen to obtain the solid Ziegler-Natta catalyst system containing the ester compound, which has good popularity and narrow particle size distribution.
(2) Polymerization reaction:
the polymerization is carried out in two slurry reactors connected in series.
Continuously feeding the Ziegler-Natta catalyst system containing the ester compound and a cocatalyst (triethylaluminum) into a first reactor through a catalyst storage tank to complete the ethylene homopolymerization reaction of the first stage; the polymerization temperature of the first reactor was 84℃and the reaction pressure was 0.78MPa. Hydrogen is added to the feed to the first reactor, hydrogen as a molecular weight regulator, and hexane as a diluent. The hydrogen addition was 21kg/h, with a hydrogen/ethylene molar ratio (%/%) of 5.6, yielding an ethylene homopolymer. The ethylene homopolymer produced in the first reactor had a melt index of 90g/10min and a density of 0.9688g/cm 3 。
The stream containing ethylene homopolymer obtained from the first reactor enters the second reactor; the polymerization temperature of the second reactor was 78℃and the reaction pressure was 0.24MPa. In the feeding of the second reactor, the hydrogen adding amount is 1.25kg/h, and the comonomer butene adding amount is 514kg/h; hydrogen/ethylene molar ratio (%/%) was 0.105; the butene/ethylene molar ratio (%/%) was 0.041. The melt index of the bimodal polyethylene resin obtained by the reaction in the second reactor is 0.24g/10min; density of 0.950g/cm 3 . The melt index of the bimodal polyethylene resin pellets obtained after the end of the reaction in the second reactor was 0.22g/10min; density of 0.950g/cm 3 The bimodal polyethylene resin had a comonomer content of 0.069% wt. The test data of the basic performance, the mechanical performance and the like of the specific resin are shown in tables 1-6.
The obtained bimodal polyethylene resin adopts the existing technology to prepare the pipe material, and the resin has good processability and no problem of low molecular precipitate. The unique resin structure of the bimodal polyethylene resin of the invention improves the tensile strength and the rapid crack growth resistance of the prepared polyethylene pipe material.
Comparative example 1
The bimodal polyethylene tubing resin was prepared using a TH series catalyst assigned by Lyondellbasell corporation.
After the solid catalyst component is activated, continuously entering a first reactor through a catalyst storage tank to complete the ethylene polymerization reaction of the first stage, wherein the polymerization reaction temperature of the first reactor is 85 ℃ and the reaction pressure is 0.78MPa; the hydrogen addition was 25kg/h, with a hydrogen/ethylene molar ratio (%/%) of 6.5, yielding an ethylene homopolymer. The ethylene homopolymer produced in the first reactor had a melt index of 102g/10min and a density of 0.9694g/cm 3 。
The stream containing ethylene homopolymer obtained from the first reactor enters the second reactor; the polymerization temperature of the second reactor was 82℃and the reaction pressure was 0.24MPa. The butene charge in the second reactor was 639kg/h, butene/ethylene molar ratio (%/%) 0.051; the hydrogen/ethylene molar ratio (%/%) was 0.290; the melt index of the bimodal polyethylene resin obtained by the reaction in the second reactor is 0.23g/10min; density of 0.949g/cm 3 . The melt index of the granular bimodal polyethylene resin obtained after the reaction of the second reactor is finished is 0.22g/10min; density of 0.949g/cm 3 . The bimodal polyethylene resin had a comonomer content of 0.061% wt. The test data of the basic performance, the mechanical performance and the like of the specific resin are shown in tables 1-6.
Comparative example 2
The imported Z501 series catalyst is adopted to prepare the bimodal polyethylene pipe material resin.
After the solid catalyst component is activated, continuously entering a first reactor through a catalyst storage tank to complete the ethylene polymerization reaction of the first stage, wherein the polymerization reaction temperature of the first reactor is 84 ℃ and the reaction pressure is 0.78MPa; the hydrogen addition was 12.5kg/h, with a hydrogen/ethylene molar ratio (%/%) of 3.23, yielding an ethylene homopolymer. The ethylene homopolymer produced in the first reactor had a melt index of 103g/10min and a density of 0.9697g/cm 3 。
The stream containing ethylene homopolymer obtained from the first reactor enters the second reactor; the polymerization temperature of the second reactor was 78℃and the reaction pressure was 0.24MPa. The butene charge to the second reactor was 645kg/h with a butene/ethylene molar ratio (%/%) of 0.052; hydrogen/ethylene molar ratio (%/%) is 0.006; the melt index of the bimodal polyethylene resin obtained by the reaction in the second reactor is 0.28g/10min; secret keyThe degree of the reaction is 0.949g/cm 3 . The melt index of the granular bimodal polyethylene resin obtained after the reaction of the second reactor is finished is 0.25g/10min; density of 0.949g/cm 3 . The bimodal polyethylene resin had a comonomer content of 0.060% wt. The test data of the basic performance, the mechanical performance and the like of the specific resin are shown in tables 1-6.
TABLE 1 particle size distribution of resin powders and catalyst Activity
As can be seen from the data in Table 1, the aromatic ester compound-containing Ziegler Natta catalyst prepared by the method provided by the invention is used for carrying out ethylene polymerization in more than two reactions connected in series, so that the bimodal polyethylene resin with good particle morphology, less large particles and small particles and concentrated particle size distribution can be prepared, wherein the 75-150 μm area accounts for about 95%, and the flowability is good. Is beneficial to the stable operation of a feeding system of the device and improves the production load of the device.
TABLE 2 Hydrogen-ethylene ratio and Polymer powder Density in polymerizer
TABLE 3 melt index of polymer powders in polymerizers
As can be seen from tables 2 and 3, when the bimodal polyethylene resin with specific density and specific melt index is produced, the Ziegler Natta catalyst containing the ester compound prepared by the method provided by the invention is subjected to ethylene polymerization in more than two reactions connected in series, and the hydrogen-ethylene ratio of the first reaction kettle can meet the production requirement under the lower condition; the hydrogen adding amount of the second reaction kettle is easy to control, the production is stable, and the produced resin product index is qualified.
TABLE 4 butene-ethylene ratio and comonomer content in Polymer powder in polymerizer
As can be seen from Table 4, the Ziegler Natta catalyst containing the ester compound prepared by the method provided by the invention is used for carrying out ethylene polymerization in more than two reactions connected in series, and the content of the comonomer of the polymer is obviously improved under the condition of small addition of the comonomer butene, thereby being beneficial to improving the mechanical properties of the resin.
TABLE 5 content of ethane in gas phase Components of polymerizers
| Polymeric unit | 1PE | 2PE |
| Ethane (ethane) | ％(V) | ％(V) |
| Example 1 | 4.1 | 0.79 |
| Comparative example 1 | 13.24 | 2.17 |
| Comparative example 2 | 10.98 | 1.85 |
As can be seen from the data in Table 5, the aromatic ester compound-containing Ziegler Natta catalyst prepared by the method provided by the invention is used for carrying out ethylene polymerization in more than two reactions connected in series, and the ethane conversion of ethylene in two polymerization reaction kettles is obviously reduced, so that the conversion rate of ethylene is improved, and the pressure of a post-treatment unit is reduced.
TABLE 6 mechanical Properties of the resin
As can be seen from the data in Table 6, the aromatic ester compound-containing Ziegler Natta catalyst prepared by the method provided by the invention is subjected to ethylene polymerization in more than two reactions connected in series, and the bimodal polyethylene resin prepared by the method provided by the invention has higher tensile strength, higher impact strength and better thermal degradation resistance than the polyethylene resin of the comparative example, and is suitable for preparing large-caliber bimodal polyethylene pipe material products.
Claims (11)
1. A method of preparing a bimodal polyethylene resin for pipe material comprising the steps of:
first stage ethylene homopolymerization: comprising carrying out an ethylene homo-polymerization in the presence of a Ziegler-Natta catalyst system comprising an aromatic ester compound, in the presence or absence of hydrogen, to obtain a stream comprising an ethylene homopolymer;
second stage ethylene copolymerization: and adding ethylene monomer and the material flow containing ethylene homopolymer obtained in the previous stage into the comonomer to carry out copolymerization reaction in the presence or absence of hydrogen to obtain the bimodal polyethylene resin.
2. The method according to claim 1, wherein:
the Ziegler-Natta catalyst system containing the aromatic ester compound comprises the following components: (1) a magnesium-containing compound; (2) an organophosphorus compound; (3) an organic alcohol compound; (4) an organic epoxy compound; (5) aromatic ester compounds; (6) a titanium-containing compound; forming a magnesium complex by reacting a magnesium-containing compound in a solvent system comprising an organic phosphorus compound, an organic epoxy compound, and an organic alcohol compound; the magnesium compound and the aromatic ester compound and the titanium compound react to form the catalyst system.
3. The method according to claim 2, characterized in that:
the magnesium-containing compound is selected from at least one of magnesium dihalide, water complex or alcohol complex of magnesium dihalide, and derivatives in which one halogen atom in the formula of magnesium dihalide is replaced by hydrocarbyloxy or halohydrocarbonyloxy; and/or the number of the groups of groups,
the organic phosphorus compound is at least one of hydrocarbyl ester of orthophosphoric acid, hydrocarbyl ester of phosphorous acid, halohydrocarbyl ester of orthophosphoric acid and halohydrocarbyl ester of phosphorous acid; and/or the number of the groups of groups,
the organic epoxy compound is C 2 -C 8 Aliphatic olefins, C 2 -C 8 Aliphatic diolefins, C 2 -C 8 Halogenated aliphatic olefins, C 2 -C 8 At least one of an oxide, a glycidyl ether, and a internal ether of a halogenated aliphatic diene; and/or the number of the groups of groups,
the organic alcohol compound is C 1 -C 10 Straight-chain, branched or cyclic alkyl alcohols, or C 6 -C 20 At least one of aryl-containing alcohols; and/or the number of the groups of groups,
the general formula of the aromatic ester compound is R 1 n R 2 m C 6 H 5-n-m-x [(CH 2 ) y COOR 3 ] x Wherein R is 1 ，R 2 Each independently is C 1 -C 20 Alkyl, aryl, alicyclic, alkoxy, R 3 Is C 1 -C 20 Alkyl, aryl and alicyclic groups, n is more than or equal to 0 and less than or equal to 5, m is more than or equal to 0 and less than or equal to 5,0<x＜5，0≤y≤9，n、m, x and y are integers, and n+m+x is less than 5; and/or the number of the groups of groups,
the general formula of the titanium-containing compound is Ti (OR 5 ) a X 2 b Wherein R is 5 Is C 1 -C 14 Aliphatic or aromatic hydrocarbon radicals, X 2 A is an integer of 1 to 4, b is an integer of 1 to 4, a+b=3 or 4.
4. The method according to claim 2, characterized in that:
in the solvent system for forming the magnesium compound in the Ziegler-Natta catalyst system containing the aromatic ester compound, the organic alcohol compound is 0 to 6 moles, preferably 0 to 2 moles, of the organic alcohol compound per mole of the magnesium compound; the organic epoxy compound is 0.2 to 10 moles, preferably 0.2 to 4 moles; the amount of the organic phosphorus compound is 0.1 to 10 moles, preferably 0.2 to 4 moles; and/or the number of the groups of groups,
the components of the Ziegler-Natta catalyst system containing the aromatic ester compound are 0.1 to 1 mole, preferably 0.1 to 0.5 mole, of the aromatic ester compound per mole of the magnesium compound in the magnesium compound; the titanium-containing compound is 1 to 20 moles, preferably 1 to 15 moles.
5. The method according to claim 2, characterized in that:
the Ziegler-Natta catalyst system containing the aromatic ester compound is prepared by a method comprising the following steps:
(1) Under the protection of inert gas, dissolving the magnesium-containing compound in a solvent system containing an organic epoxy compound and an organic phosphorus compound to form a uniform solution of a magnesium compound, wherein the dissolution temperature is 50-90 ℃; adding an organic alcohol compound during or after the formation of the solution to obtain a magnesium compound reaction solution;
(2) The reaction solution is contacted and reacted with the titaniferous compound at the temperature of minus 30 ℃ to 0 ℃ and the aromatic ester compound is introduced before, after or during the reaction; and slowly heating the mixture to 50-120 ℃ to obtain the Ziegler-Natta catalyst system.
6. The method according to claim 1, characterized in that:
the reaction temperature of the ethylene homopolymerization reaction in the first stage is 60-100 ℃, preferably 70-90 ℃; the reaction pressure is 0.1-3.0 MPa, preferably 0.5-2.0 MPa; and/or the number of the groups of groups,
the first stage ethylene homo-polymerization is carried out in the presence of hydrogen, wherein the molar ratio of hydrogen to ethylene is from 4.0 to 7.0, preferably from 5.0 to 6.0.
7. The method according to claim 1, characterized in that:
the melt index of the ethylene homopolymer obtained by the ethylene homo-polymerization reaction in the first stage is greater than or equal to 60g/10min, preferably greater than or equal to 65g/10min, under a load of 1.2 kg; and/or the number of the groups of groups,
the density of the ethylene homopolymer obtained by the ethylene homopolymerization in the first stage is greater than or equal to 0.963g/cm 3 Preferably 0.963 to 0.980g/cm 3 More preferably 0.965 to 0.975g/cm 3 。
8. The method according to claim 1, characterized in that:
the reaction temperature of the ethylene copolymerization reaction in the second stage is 60-100 ℃, preferably 70-90 ℃; the reaction pressure is 0.01-3.0 MPa, preferably 0.05-2.0 MPa; and/or the number of the groups of groups,
the second stage ethylene copolymerization is carried out in the presence of hydrogen, wherein the molar ratio of hydrogen to ethylene is 0.01 to 0.2, preferably 0.05 to 0.1; and/or the number of the groups of groups,
the molar ratio of the comonomer to ethylene of the second stage ethylene copolymerization is 0.01 to 0.2, preferably 0.03 to 0.08.
9. The method according to claim 1, wherein:
the comonomer has the structural formula: CH (CH) 2 =chr, wherein R is a linear or branched alkane having 1-10 carbon atoms; the comonomer is preferably propylene, butene-1,At least one of pentene-1, hexene-1, octene-1 and decene-1.
10. Bimodal polyethylene resin obtainable by the process according to any one of claims 1 to 9.
The melt index of the bimodal polyethylene resin is 0.10-0.40 g/10min, preferably 0.15-0.35 g/10min under a 5kg load; the density of the bimodal polyethylene resin is 0.943-0.963 g/cm 3 Preferably 0.945 to 0.955g/cm 3 。
The comonomer content in the bimodal polyethylene resin is greater than 0 and less than or equal to 1.0wt%, preferably 0.001 to 0.8wt%.
11. A tubular article made from the bimodal polyethylene resin according to claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111352412.8A CN116135892B (en) | 2021-11-16 | 2021-11-16 | Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111352412.8A CN116135892B (en) | 2021-11-16 | 2021-11-16 | Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116135892A true CN116135892A (en) | 2023-05-19 |
| CN116135892B CN116135892B (en) | 2024-10-15 |
Family
ID=86334056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111352412.8A Active CN116135892B (en) | 2021-11-16 | 2021-11-16 | Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116135892B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616963A (en) * | 2007-05-04 | 2009-12-30 | 弗纳技术股份有限公司 | Bimodal polyethylene resins with high stiffness and high ESCR |
| CN103772536A (en) * | 2012-10-18 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst component for polymerization or copolymerization of ethylene and catalyst thereof |
| CN103998471A (en) * | 2011-12-12 | 2014-08-20 | 沙特基础工业公司 | A process for the production of bimodal polyethylene in the presence of this catalyst system |
| CN112724301A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Polyethylene resin, preparation method thereof and injection blow molding hollow product thereof |
| CN112745408A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Bimodal polyethylene resin for extrusion blow molding of small hollow articles, preparation method and application thereof |
-
2021
- 2021-11-16 CN CN202111352412.8A patent/CN116135892B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616963A (en) * | 2007-05-04 | 2009-12-30 | 弗纳技术股份有限公司 | Bimodal polyethylene resins with high stiffness and high ESCR |
| CN103998471A (en) * | 2011-12-12 | 2014-08-20 | 沙特基础工业公司 | A process for the production of bimodal polyethylene in the presence of this catalyst system |
| CN103772536A (en) * | 2012-10-18 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst component for polymerization or copolymerization of ethylene and catalyst thereof |
| CN112724301A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Polyethylene resin, preparation method thereof and injection blow molding hollow product thereof |
| CN112745408A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Bimodal polyethylene resin for extrusion blow molding of small hollow articles, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116135892B (en) | 2024-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8138264B2 (en) | Bimodal polyethylene resins that have high stiffness and high ESCR | |
| US9249286B2 (en) | Multimodal polyethylene pipe resins and process | |
| CN112745408B (en) | Bimodal polyethylene resin for extrusion blow molding of small hollow articles, preparation method and application thereof | |
| CN112724301B (en) | Polyethylene resin, preparation method thereof and injection blow molding hollow product thereof | |
| US10584196B2 (en) | Process for producing LLDPE resins | |
| AU2014256451C1 (en) | Two-stage process for producing polypropylene compositions | |
| CN108368203B (en) | Catalyst composition and process for preparing ultra high molecular weight poly (alpha-olefin) drag reducing agents | |
| CN116135892B (en) | Method for preparing bimodal polyethylene resin for pipe material and bimodal polyethylene resin thereof | |
| CN106220768B (en) | A kind of high impact polyvinyl resin with super-high molecular weight and preparation method thereof | |
| CN116063604B (en) | Bimodal polyethylene resin for pipe material product, preparation method thereof and pipe material product | |
| CN110016096B (en) | Catalyst carrier for olefin polymerization and preparation method thereof, solid catalyst component, catalyst system and olefin polymerization method | |
| JP5501384B2 (en) | Enlarging the molecular weight distribution of polyolefin materials produced in a horizontal stirred gas phase reactor | |
| CN111057168B (en) | Catalyst for olefin polymerization and preparation method and application thereof | |
| CN108203481A (en) | Method for producing ultra-high molecular weight polyethylene | |
| CN116082566A (en) | Preparation method of bimodal polyethylene resin and obtained bimodal polyethylene resin and tubular product | |
| CN115232235A (en) | Method for producing olefin polymer and olefin polymer | |
| CN108602916B (en) | Procatalyst for olefin polymerization | |
| CN117924571A (en) | Process for preparing heterophasic propylene copolymers | |
| CN114181349B (en) | Polyethylene pipe material and preparation method and application thereof | |
| CN118791658A (en) | Bimodal polyethylene resin for pipes and its preparation method and application | |
| JPS617306A (en) | Preparation of polyolefin | |
| CN111057169B (en) | Catalyst for olefin polymerization and preparation method and application thereof | |
| CN107880163B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880169B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| US20240018171A1 (en) | Novel titanium complexes as catalysts for alpha 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 |