CN114316110B - Propylene-butene random copolymer production system and preparation method - Google Patents
Propylene-butene random copolymer production system and preparation method Download PDFInfo
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- CN114316110B CN114316110B CN202210002111.0A CN202210002111A CN114316110B CN 114316110 B CN114316110 B CN 114316110B CN 202210002111 A CN202210002111 A CN 202210002111A CN 114316110 B CN114316110 B CN 114316110B
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- butene
- propylene
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- 229920005675 propylene-butene random copolymer Polymers 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 30
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 127
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 125
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 103
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 103
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 79
- 239000007789 gas Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000002216 antistatic agent Substances 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 38
- 238000007670 refining Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 3
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 claims description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 2
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- PUWYGFIZYVEULY-UHFFFAOYSA-N CO[SiH](C)OC(C1CCCC1)C2CCCC2 Chemical compound CO[SiH](C)OC(C1CCCC1)C2CCCC2 PUWYGFIZYVEULY-UHFFFAOYSA-N 0.000 claims 2
- 229920005604 random copolymer Polymers 0.000 abstract description 18
- 238000002844 melting Methods 0.000 abstract description 11
- 230000008018 melting Effects 0.000 abstract description 11
- 239000002035 hexane extract Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 67
- -1 polypropylene Polymers 0.000 description 37
- 239000000047 product Substances 0.000 description 33
- 239000004743 Polypropylene Substances 0.000 description 26
- 229920001155 polypropylene Polymers 0.000 description 26
- 239000012159 carrier gas Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 21
- 150000002978 peroxides Chemical class 0.000 description 19
- 239000003963 antioxidant agent Substances 0.000 description 18
- 230000003078 antioxidant effect Effects 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000012535 impurity Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- QTLWINPABCWCSU-UHFFFAOYSA-N dicyclopentylmethyl(dimethoxy)silane Chemical compound C1(CCCC1)C(C1CCCC1)[SiH](OC)OC QTLWINPABCWCSU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical group CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- UDBVWWVWSXSLAX-UHFFFAOYSA-N 4-[2,3-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)C(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)CC1=CC(C(C)(C)C)=C(O)C=C1C UDBVWWVWSXSLAX-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- FDTGUDJKAXJXLL-UHFFFAOYSA-N acetylene Chemical compound C#C.C#C FDTGUDJKAXJXLL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 1
- KOWXKIHEBFTVRU-UHFFFAOYSA-N nga2 glycan Chemical compound CC.CC KOWXKIHEBFTVRU-UHFFFAOYSA-N 0.000 description 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of olefin copolymerization, and discloses a production system and a preparation method of a propylene-butene random copolymer. The preparation method comprises the steps of carrying out first gas phase random copolymerization on refined propylene and A-strand butene in the presence of a main catalyst, a cocatalyst, hydrogen, an external electron donor and an optional antistatic agent to obtain a first random copolymerization product; then, the first random copolymerization product is contacted with B strands of butene and optional hydrogen to carry out a second gas phase random copolymerization reaction, so as to obtain a product containing propylene-butene random copolymer; wherein the mass ratio of the A-strand butene to the B-strand butene is 1:0.1-0.6. The method can effectively reduce the melting temperature of the polymer and obtain the propylene-butene binary random copolymer with low n-hexane extract content.
Description
Technical Field
The invention relates to the technical field of olefin copolymerization, in particular to a production system and a preparation method of a propylene-butene random copolymer.
Background
In recent years, propylene-butene binary random copolymers are increasingly receiving attention, and many reports of research on propylene-butene binary random copolymers have been made. The butene can achieve the effect of copolymerization modification of long-chain alpha-olefin on polypropylene, namely, the crystallization of polypropylene can be destroyed, the glass transition temperature of the polypropylene can be reduced, the low-temperature toughness, printing performance, transparency and processing performance of the polypropylene material are greatly improved, and the melting point and initial heat sealing temperature of the polymer film material are reduced, so that the propylene-butene binary random copolymer is widely used as a special sealing layer of a coextrusion film structure.
In the prior art, the propylene-butene binary random copolymer has a wider production process selection range, and mainly comprises a gas phase method, a solution method, a solvent method, a liquid phase method and the like. The solution method and the solvent method are to dissolve propylene and comonomer butene in a solvent, polymerize the propylene and the comonomer butene in the solvent, and the subsequent solvent recovery process is complex, long in flow and high in energy consumption. And the liquid phase method generally adopts a loop reaction kettle, and a propylene-butene binary random copolymer produced by polymerization is very easy to block a pipeline, so that production stopping is caused, and the production efficiency of enterprises is influenced. The propylene-butene binary random copolymer prepared by adopting a gas phase method has no problems of pipeline blockage and solvent recovery, but the butene content in the propylene-butene binary random copolymer is not easy to control, and partial hot spots are easy to form by gas phase reaction to cause the agglomeration of the propylene-butene binary random copolymer, so that the product performance is uneven, and continuous and stable production cannot be realized.
Disclosure of Invention
The invention aims to solve the problems of propylene-butene binary random copolymer agglomeration and low butene content in the propylene-butene binary random copolymer in a gas phase reaction of propylene-butene copolymerization, and provides a production system and a preparation method of the propylene-butene random copolymer.
In order to achieve the above object, the first aspect of the present invention provides a process for preparing a propylene-butene random copolymer, comprising the steps of:
a. refining raw material propylene and raw material butene to obtain refined propylene and refined butene respectively, and dividing the refined butene into A-strand butene and B-strand butene;
b. in the presence of a main catalyst, a cocatalyst, hydrogen, an external electron donor and an optional antistatic agent, carrying out first gas phase random copolymerization on refined propylene and A-strand butene to obtain a first random copolymerization product;
c. contacting the first random copolymerization product with B-strand butene and optional hydrogen to carry out a second gas-phase random copolymerization reaction to obtain a product containing propylene-butene random copolymer;
d. compressing and separating gas in a product containing the propylene-butene random copolymer to obtain liquid propylene and liquid butene, and returning the liquid propylene and the liquid butene to the step a for refining respectively;
wherein the mass ratio of the A-strand butene to the B-strand butene is 1:0.1-0.6.
In a second aspect, the present invention provides a system for producing a propylene-butene random copolymer, the system comprising: a raw material refining unit, a copolymerization unit and a separation recovery unit, wherein,
the raw material refining unit comprises a propylene refining unit and a butene refining unit which are respectively used for refining raw material propylene and raw material butene to obtain refined propylene and refined butene;
the copolymerization unit comprises a first vertical gas-phase stirring kettle and a second vertical gas-phase stirring kettle which are connected in series, wherein the first vertical gas-phase stirring kettle is used for carrying out first gas-phase random copolymerization on refined propylene and refined butene, and the second vertical gas-phase stirring kettle is used for carrying out second gas-phase random copolymerization on a product of the first gas-phase random copolymerization and the refined butene to obtain a product containing propylene-butene random copolymer;
the separation and recovery unit is used for separating unreacted propylene and butene in the product from the copolymerization unit, returning the separated propylene to the propylene refining unit, and returning the separated butene to the butene refining unit.
Through the technical scheme, the invention has the following beneficial effects:
(1) The invention takes propylene and butylene cracked by coal-based naphtha as raw materials, and carries out polymerization reaction after refining by a polypropylene device and a polyethylene device. Based on the original polypropylene production device, the propylene-butene binary random copolymer is carried out by adopting a double vertical gas-phase stirring reaction kettle which is independently designed and developed, and the limitation of the original process package is broken through by combining a polyethylene production device and a cracking device, so that the continuous production of the propylene-butene binary random copolymer is realized.
(2) The propylene-butene binary random copolymer production device does not need to additionally increase a recovery system and a raw material refining unit, and has the advantages of less equipment investment and lower running cost.
(3) The method can lead the butene to be effectively introduced into the propylene-butene random copolymer at a very high polymerization rate, improves the butene content in the copolymer, and can effectively reduce the melting temperature of the polymer to obtain the propylene-butene binary random copolymer with low n-hexane extract content.
(4) According to the invention, the propylene-butene binary random copolymer is carried out by adopting the double vertical gas-phase stirring reaction kettles, and butene is respectively added into the two vertical gas-phase stirring reaction kettles according to a certain mass ratio, so that a massive polymer is effectively prevented from being generated in the polymerization process, and the device can stably run for a long time.
Drawings
FIG. 1 is a schematic illustration of a system for producing propylene-butene random copolymers provided by the present invention.
Description of the reference numerals
11. Propylene stripping tower 12, propylene desulfurizing tower 13 and propylene drying tower
14. Butene stripper 15, butene dryer 31, first vertical gas phase stirred tank
32. Second vertical gas-phase stirring kettle 33, discharge bin 41 and carrier gas compression device
42. Carrier gas separation column 43, low pressure depropanizer
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for preparing a propylene-butene random copolymer comprising the steps of:
a. refining raw material propylene and raw material butene to obtain refined propylene and refined butene respectively, and dividing the refined butene into A-strand butene and B-strand butene;
b. in the presence of a main catalyst, a cocatalyst, hydrogen, an external electron donor and an optional antistatic agent, carrying out first gas phase random copolymerization on refined propylene and A-strand butene to obtain a first random copolymerization product;
c. contacting the first random copolymerization product with B-strand butene and optional hydrogen to carry out a second gas-phase random copolymerization reaction to obtain a product containing propylene-butene random copolymer;
d. compressing and separating gas in a product containing the propylene-butene random copolymer to obtain liquid propylene and liquid butene, and returning the liquid propylene and the liquid butene to the step a for refining respectively;
wherein the mass ratio of the A-strand butene to the B-strand butene is 1:0.1-0.6.
In the present invention, preferably, the mass ratio of the a-butene to the B-butene is 1:0.1-0.3.
In the present invention, preferably, in the step b, the amount of the a-butene is 8 to 10 parts by weight, the amount of the main catalyst is 0.004 to 0.01 part by weight, the amount of the cocatalyst is 0.02 to 0.03 part by weight, the amount of the hydrogen is 0.001 to 0.004 part by weight, and the amount of the external electron donor is 0.005 to 0.01 part by weight, based on 100 parts by weight of the purified propylene.
In the present invention, preferably, in the step b, the antistatic agent is added after being mixed with the external electron donor, and more preferably, the weight ratio of the antistatic agent to the external electron donor is 1:1-2.
In the present invention, preferably, the antistatic agent is glycerol monostearate and/or ethoxylated alkylamine; more preferably, the antistatic agent is an ethoxylated alkylamine; further preferably, the ethoxylated alkylamine is an ethoxylated-C12-18-alkylamine (CAS: 72968-37-7).
In the present invention, preferably, in the step b, the conditions of the first gas-phase random copolymerization reaction include: the temperature is 70-76 ℃, preferably 73-75 ℃, the pressure is 2-3MPa, preferably 2.5-2.8MPa, and the residence time is 1-2h, preferably 1-1.5h.
In the present invention, preferably, in the step c, the conditions of the second gas phase random copolymerization reaction include: the temperature is 65-75deg.C, preferably 70-75deg.C, the pressure is 1.3-2MPa, preferably 1.5-1.8MPa, and the residence time is 0.5-1.5 hr, preferably 0.5-1 hr.
In the present invention, preferably, in the step c, the hydrogen gas is used in an amount of 0.001 to 0.004 parts by weight with respect to 100 parts by weight of the purified propylene.
In the present invention, preferably, the first gas-phase random copolymerization reaction and the second gas-phase random copolymerization reaction are each independently carried out under stirring, and more preferably, the stirring speed is 20 to 30rmp.
In the present invention, the pressure of the first gas phase copolymerization is preferably 0.5 to 1MPa, more preferably 0.5 to 0.8MPa, higher than the pressure of the second gas phase copolymerization.
In the present invention, preferably, the temperature of the first gas-phase random copolymerization reaction is 1 to 5 ℃ higher than the temperature of the second gas-phase random copolymerization reaction.
In the present invention, it is preferable that the time of the first gas-phase random copolymerization is 0.5 to 1 hour longer than the temperature time of the second gas-phase random copolymerization.
In the present invention, preferably, after the first gas phase random copolymerization reaction and the second gas phase random copolymerization reaction, the conversion rate of the refined propylene can reach 80-90%, and the conversion rate of the refined butene can reach 80-90%.
In the present invention, the main catalyst is a commercial Ziegler/Natta catalyst, preferably, the effective components in the main catalyst include Ti, mg, cl and an internal electron donor, wherein the internal electron donor is phthalate, preferably phthalate. For example, the main catalyst is CS-1 type catalyst produced by Yingkou-to-yang chemical plant.
In the invention, preferably, the main catalyst contains 1.5 to 3 weight percent of titanium, 15 to 25 weight percent of magnesium, 50 to 64 weight percent of chlorine and 6 to 11 weight percent of internal electron donor; more preferably, the main catalyst contains 2 to 3 weight percent of titanium, 16 to 23 weight percent of magnesium, 55 to 64 weight percent of chlorine and 6 to 10 weight percent of internal electron donor.
In the present invention, the cocatalyst is preferably an alkylaluminum, preferably at least one of triethylaluminum, diethylaluminum chloride and triisobutylaluminum, more preferably triethylaluminum.
In the present invention, the external electron Donor is preferably a non-phenyl siloxane, preferably cyclohexylmethyldimethoxysilane (CHMMS, donor C), dicyclopentylmethyldimethoxysilane (DCPDMS, donor D), diisopropyldimethoxysilane (DIPMS, donor P) and diisobutyldimethoxysilane (dimbs, donor B), more preferably dicyclopentylmethyldimethoxysilane (Donor D).
In the present invention, preferably, the method further includes step e: granulating propylene-butene random copolymer powder in a product containing the propylene-butene random copolymer, wherein the granulating process comprises the steps of mixing the propylene-butene random copolymer powder with a composite auxiliary agent and granulating; more preferably, the granulation is carried out by extrusion granulation, wherein the extrusion granulation comprises extruding a mixture of propylene-butene random copolymer powder and a compounding auxiliary agent through an extruder at a melting temperature of 200-240 ℃ and granulating, and then cooling and granulating in a water bath of 50-70 ℃ to obtain polymer granules.
In the present invention, preferably, the compounding ingredients include a primary antioxidant, a secondary antioxidant, an acid absorber, and optionally a polypropylene-based peroxide.
In the present invention, it is preferable that the primary antioxidant is used in an amount of 400 to 450mg, the secondary antioxidant is used in an amount of 850 to 950mg, and the acid absorber is used in an amount of 290 to 350mg per kg of the propylene-butene random copolymer powder.
In the present invention, preferably, the peroxide is used in an amount of 100 to 200mg per kg of the propylene-butene random copolymer powder.
In the present invention, preferably, the primary antioxidant comprises a hindered phenol antioxidant, wherein the hindered phenol antioxidant comprises at least one of 2, 6-di-tert-butyl-4-methylphenol, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecyl ester of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (i.e., antioxidant 1010), thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and 2, 2-methylenebis (4-methyl-6-tert-butylphenol); more preferred is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
In the present invention, preferably, the auxiliary antioxidant is a phosphite antioxidant comprising tris (2, 4-di-t-butylphenyl) phosphite and/or p- (2, 4-di-t-butylphenyl) pentaerythritol diphosphite. It is further preferred that tris (2, 4-di-tert-butylphenyl) phosphite be the secondary antioxidant.
In the present invention, preferably, the acid acceptor is hydrotalcite or calcium stearate ((C) 17 H 35 COO) 2 Ca). Further preferably, the hydrotalcite adsorbs and fixes Cl-in the stable crystal by anion exchange, and the extrusion granulation process after propylene polymerization absorbs halogen ions remained in the polymerization stage of polypropylene, thereby improving the stability of polypropylene.
In the present invention, preferably, the peroxide in the polypropylene-based peroxide is 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and more preferably, the peroxide content in the polypropylene-based peroxide is 10 to 20wt%. The peroxide is prepared into polypropylene-based peroxide because the peroxide is added in a small amount, so as to improve the dispersion uniformity of the peroxide in the mixing process of the propylene-butene random copolymer and the composite auxiliary agent, and polypropylene in the polypropylene-based peroxide is not particularly limited, and can be commercially available polypropylene or polypropylene prepared according to the prior literature.
In a second aspect, the present invention provides a system for producing a propylene-butene random copolymer, the system comprising: a raw material refining unit, a copolymerization unit and a separation recovery unit, wherein,
the raw material refining unit comprises a propylene refining unit and a butene refining unit which are respectively used for refining raw material propylene and raw material butene to obtain refined propylene and refined butene;
the copolymerization unit comprises a first vertical gas-phase stirring kettle 31 and a second vertical gas-phase stirring kettle 32 which are connected in series, wherein the first vertical gas-phase stirring kettle 31 is used for carrying out first gas-phase random copolymerization on refined propylene and refined butene, and the second vertical gas-phase stirring kettle 32 is used for carrying out second gas-phase random copolymerization on a product of the first gas-phase random copolymerization and the refined butene to obtain a product containing propylene-butene random copolymer;
the separation and recovery unit is used for separating unreacted propylene and butene in the product from the copolymerization unit, returning the separated propylene to the propylene refining unit, and returning the separated butene to the butene refining unit.
In the present invention, the first gas-phase random copolymerization reaction product is obtained from the first vertical gas-phase stirred tank 31. The product from the copolymerized unit is the product of the propylene-butene containing random copolymer.
In the specific embodiment provided by the invention, the propylene refining unit may comprise a propylene stripping tower 11, a propylene desulfurizing tower 12 and a propylene drying tower 13, preferably, the propylene stripping tower 11 is used for removing at least one of carbon monoxide, carbon dioxide and oxygen in raw propylene, the propylene desulfurizing tower 12 is used for removing sulfur-containing compounds in the raw propylene, and the propylene drying tower 13 is used for removing water and/or alcohol in the raw propylene.
In the embodiments provided herein, the butene refining unit may include a butene stripper 14 and a butene dryer 15. Preferably, the butene stripper 14 is used to remove at least one of carbon monoxide, carbon dioxide and oxygen from the feed butene and the butene dryer 15 is used to remove water from the butene feed.
In the specific embodiment provided by the invention, the first vertical gas-phase stirring kettle 31 and the second vertical gas-phase stirring kettle 32 are respectively and independently provided with a stirrer.
In the embodiment provided by the invention, the copolymerization unit can further comprise a discharge bin 33 for separating the propylene-butene random copolymer in the product from the copolymerization unit from a carrier gas comprising hydrogen, nitrogen and unreacted propylene and butene.
In the embodiments provided herein, the separation recovery unit may include a carrier gas compression device 41, a carrier gas separation column 42, and a low pressure depropanizer column 43, wherein,
the carrier gas compressing device 41 is used for compressing the carrier gas and sending the carrier gas into the carrier gas separating tower 42;
the carrier gas separation tower 42 is used for separating the mixed liquid of propylene and butene in the compressed carrier gas;
the low pressure depropanizer 43 is used for separating the mixture of propylene and butene to obtain propylene and butene.
In the specific embodiment of the present invention, the carrier gas compressing device 41 compresses and boosts the carrier gas with the pressure of 0.1-0.2MPa to 3-4MPa, and then sends the compressed carrier gas into the carrier gas separating tower 42 for separation.
In the specific embodiment provided by the invention, in the carrier gas separation tower 42, hydrogen and nitrogen in the carrier gas are discharged as light components from the top of the carrier gas separation tower, and a mixed solution of propylene and butene is discharged as heavy components from the bottom of the carrier gas separation tower.
In the specific embodiment provided by the present invention, the operating conditions of the low pressure depropanizer 43 may be those commonly used in the art, preferably, the temperature of the top of the low pressure depropanizer is 5-20 ℃, the temperature of the bottom of the low pressure depropanizer is 70-80 ℃ and the pressure is 0.6-0.9MPa.
In a specific embodiment provided by the invention, the propylene refining unit can be a propylene refining unit in a polypropylene production system; the butene refining unit may be a butene refining unit in a polyethylene production system; the low pressure depropanizer can be a low pressure depropanizer in a petroleum cracker. Thus, the increase of equipment and the increase of the input cost of production can be avoided.
The following describes a process flow diagram of the production system of the propylene-butene random copolymer of the present invention with reference to FIG. 1.
The method comprises the steps of feeding raw material propylene into a propylene stripping tower 11 to remove impurities such as carbon monoxide, carbon dioxide and oxygen in the raw material propylene, feeding the raw material propylene into a propylene desulfurization tower 12 to remove impurities such as sulfur-containing compounds in the raw material propylene, and feeding the raw material propylene into a propylene drying tower 13 to remove impurities such as water and/or alcohol in the raw material propylene to obtain refined propylene; simultaneously, the raw material butene is sent to a butene stripping tower 14 to remove impurities such as carbon monoxide, carbon dioxide, oxygen and the like in the raw material butene, then sent to a butene drying tower 15 to remove impurities such as water and the like in the butene raw material to obtain refined butene, and the refined butene is divided into two parts. Feeding a main catalyst, a cocatalyst, hydrogen, an external electron donor, refined propylene and A-strand butene into a first vertical gas-phase stirring kettle 31 according to mass ratio for a first gas-phase random copolymerization reaction to obtain a first random copolymerization product; the first random copolymerization product and the B-butene are then fed into a second vertical gas-phase stirred tank 32, and a certain amount of hydrogen is added, and then a second gas-phase random copolymerization reaction is performed to obtain a product containing a propylene-butene random copolymer. The propylene-butene random copolymer powder and gas in the propylene-butene random copolymer-containing product are separated by sending the propylene-butene random copolymer-containing product into a discharge bin 33, the separated propylene-butene random copolymer powder enters an extrusion unit for granulation to obtain propylene-butene random copolymer particles, the gas is separated by a carrier gas compression device 41, a carrier gas separation tower 42 and a low pressure depropanizer 43 to obtain liquid propylene and liquid butene, the liquid propylene is returned to the propylene stripping tower 11, and the liquid butene is returned to the butene stripping tower 14.
The present invention will be described in detail by examples. In the following examples of the present invention,
the main catalyst is a Ziegler/Natta catalyst, the model is CS-I, the manufacturer is a Yingkou open-to-the-sun chemical plant, and the main catalyst comprises the effective components: titanium content 2.1wt%, magnesium content 18.9wt%, chlorine content 59.1wt%, and internal electron donor (phthalate) content 6wt%.
The manufacturer of polypropylene based peroxide was Manntek, and the content of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane in the polypropylene based peroxide was 20wt%.
The cocatalyst is triethylaluminum.
The external electron donor is dicyclopentylmethyl dimethoxy silane.
The feed propylene and feed butenes are derived from coal-based naphtha cracking products.
Example 1
This example is for explaining the preparation method of propylene-butene random copolymer
a. Feeding raw material propylene into a propylene stripping tower to remove impurities such as carbon monoxide, carbon dioxide and oxygen in the raw material propylene, feeding the raw material propylene into a propylene desulfurizing tower to remove impurities such as sulfur-containing compounds in the raw material propylene, feeding the raw material propylene into a propylene drying tower to remove impurities such as water and/or alcohol in the raw material propylene to obtain refined propylene, wherein the composition of the refined propylene is shown in a table 1; and simultaneously, feeding the butene into a butene stripping tower to remove impurities such as carbon monoxide, carbon dioxide and oxygen in raw material butene, and feeding the butene into a butene drying tower to remove impurities such as water in the butene raw material to obtain refined butene, wherein the composition of the refined butene is shown in table 2. Dividing the refined butene into two strands, wherein the mass ratio of the A-strand butene to the B-strand butene is 1:0.1.
b. feeding refined propylene and the A-strand butene into a first vertical gas-phase stirring kettle for first gas-phase random copolymerization reaction in the presence of a main catalyst, a cocatalyst, hydrogen and an external electron donor to obtain a first random copolymerization product powder, wherein the amount of the refined propylene is 100 parts by weight, the amount of the A-strand butene is 10 parts by weight, the amount of the main catalyst is 0.007 parts by weight, the amount of the cocatalyst is 0.025 parts by weight, the amount of the hydrogen is 0.003 parts by weight, and the amount of the external electron donor is 0.008 parts by weight; wherein the external electron donor and the antistatic agent (ethoxylated-C12-18-alkylamine) are mixed according to a ratio of 1:1, and adding the mixture after mixing. The conditions for the first gas phase random copolymerization reaction include: the temperature was 75℃and the pressure was 2.8MPa, the residence time was 1.5h and the stirring rate was 29rpm.
c. After the first gas phase random copolymerization reaction is finished, intermittently pressing and conveying the first random copolymerization product powder to a second reactor, conveying the B-strand butene and hydrogen to a second vertical gas phase stirring kettle, and carrying out the second gas phase random copolymerization reaction by utilizing the residual activity of the first gas phase stirring kettle to obtain a product containing the propylene-butene random copolymer. Wherein the hydrogen gas is used in an amount of 0.001 parts by weight based on 100 parts by weight of the purified propylene. The conditions for the second gas phase copolymerization reaction include: the temperature was 70 ℃, the pressure was 1.8MPa, the residence time was 0.5h, and the stirrer speed was 29rpm; and separating the product containing the propylene-butene random copolymer by a discharge bin to obtain propylene-butene random copolymer powder and gas.
d. And c, compressing and separating the gas obtained by separating the discharge bin to obtain liquid propylene and liquid butene, and returning the liquid propylene and the liquid butene to the step a for refining respectively.
e. Uniformly mixing propylene-butene random copolymer powder with a main antioxidant (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), an auxiliary antioxidant (tri (2, 4-di-tert-butylphenyl) phosphite) and an acid absorber (calcium stearate) through a spiral mixing device, feeding the mixture into an extrusion unit, extruding the mixture through an extruder at the melting temperature of 230 ℃, granulating the mixture, and cooling and granulating the mixture in a water bath at the temperature of 60 ℃ to obtain propylene-butene random copolymer particles. Wherein, relative to each kilogram of propylene-butene random copolymer powder, the weight dosage of the main antioxidant is 440mg, the weight dosage of the auxiliary antioxidant is 890mg, and the weight dosage of the acid absorber is 290mg.
TABLE 1
| Component (A) | Unit (B) | Specification of raw material components |
| Propylene | mol％ | >99.6 |
| Methane | ppm(mol) | <100 |
| Propane | ppm(mol) | <0.4 |
| Ethane (ethane) | ppm(mol) | <200 |
| Ethylene | ppm(mol) | <10 |
| Acetylene (acetylene) | ppm(mol) | <0.5 |
| MAPD | ppm(mol) | <5 |
| Butadiene | ppm(mol) | <1 |
| Butene (B) | ppm(mol) | <10 |
| More than four carbon atoms | ppm(mol) | <10 |
| Hydrogen gas | ppm(mol) | <5 |
| Carbon monoxide | ppm(mol) | <0.05 |
| Carbon dioxide | ppm(mol) | <5 |
| Oxygen gas | ppm(mol) | 1.3 |
| Water and its preparation method | ppm(mol) | 25 |
| Methanol | ppm(mol) | 4 |
| Chlorides (CPS) | ppm(mol) | 1 |
| Total sulfur (S) | ppm(mol) | <2 |
| Total carbonyl group | ppm(mol) | <1 |
| Oxide compound | ppm(mol) | <1 |
TABLE 2
Example 2
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer preparation was carried out as in example 1, except that the mass ratio of the a-butene to the B-butene was 1:0.2.
example 3
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer preparation was carried out as in example 1, except that the mass ratio of the a-butene to the B-butene was 1:0.3.
example 4
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer preparation was carried out as in example 1, except that the mass ratio of the a-butene to the B-butene was 1:0.4.
example 5
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer preparation was carried out as in example 1, except that the mass ratio of the a-butene to the B-butene was 1:0.5.
example 6
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer preparation was carried out as in example 1, except that the mass ratio of the a-butene to the B-butene was 1:0.6.
example 7
This example is for explaining the preparation method of propylene-butene random copolymer
Preparation of propylene-butene random copolymer was carried out in the same manner as in example 2 except that in step b, hydrogen was used in an amount of 0.002 parts by weight; hydrogen is not added in the step c; in step e, a polypropylene-based peroxide is also added, the amount of peroxide in the polypropylene-based peroxide being 100mg per kg of propylene-butene random copolymer powder.
Example 8
This example is for explaining the preparation method of propylene-butene random copolymer
Preparation of propylene-butene random copolymer was carried out in the same manner as in example 2 except that in step b, hydrogen was used in an amount of 0.002 parts by weight; hydrogen is not added in the step c; in step e, a polypropylene-based peroxide is also added, the amount of peroxide in the polypropylene-based peroxide being 150mg per kg of propylene-butene random copolymer powder.
Example 9
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer was produced in the same manner as in example 2 except that 100 parts by weight of purified propylene was used and 15 parts by weight of A-butene was used.
Example 10
This example is for explaining the preparation method of propylene-butene random copolymer
a. The same as in example 1.
b. Feeding refined propylene and the A-strand butene into a first vertical gas-phase stirring kettle for first gas-phase random copolymerization reaction in the presence of a main catalyst, a cocatalyst, hydrogen and an external electron donor to obtain a first random copolymerization product powder, wherein the amount of the A-strand butene is 8 parts by weight, the amount of the main catalyst is 0.005 part by weight, the amount of the cocatalyst is 0.03 part by weight, the amount of the hydrogen is 0.002 part by weight and the amount of the external electron donor is 0.01 part by weight relative to 100 parts by weight of the refined propylene; wherein the external electron donor and the antistatic agent (ethoxylated-C12-18-alkylamine) are mixed according to a ratio of 2:1, and adding the mixture after mixing. The conditions for the first gas phase random copolymerization reaction include: the temperature was 73℃and the pressure was 2.5MPa, the residence time was 1h and the stirring rate was 20rpm.
c. After the first gas phase random copolymerization reaction is finished, intermittently pressing and conveying the first random copolymerization product powder to a second reactor, conveying the B-strand butene and hydrogen to a second vertical gas phase stirring kettle, and carrying out the second gas phase random copolymerization reaction by utilizing the residual activity of the first gas phase stirring kettle to obtain a product containing the propylene-butene random copolymer. Wherein the hydrogen gas is used in an amount of 0.001 parts by weight based on 100 parts by weight of the purified propylene. The conditions for the second gas phase copolymerization reaction include: the temperature was 70 ℃, the pressure was 1.5MPa, the residence time was 0.5h, and the stirrer speed was 20rpm; and separating the product containing the propylene-butene random copolymer by a discharge bin to obtain propylene-butene random copolymer powder and gas.
d. And c, compressing and separating the gas obtained by separating the discharge bin to obtain liquid propylene and liquid butene, and returning the liquid propylene and the liquid butene to the step a for refining respectively.
e. Uniformly mixing propylene-butene random copolymer powder with a main antioxidant (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), an auxiliary antioxidant (tri (2, 4-di-tert-butylphenyl) phosphite) and an acid absorber (calcium stearate) through a spiral mixing device, feeding the mixture into an extrusion unit, extruding the mixture through an extruder at the melting temperature of 230 ℃, granulating the mixture, and cooling and granulating the mixture in a water bath at the temperature of 60 ℃ to obtain propylene-butene random copolymer particles. Wherein, relative to each kilogram of propylene-butene random copolymer powder, the weight dosage of the main antioxidant is 400mg, the weight dosage of the auxiliary antioxidant is 850mg, and the weight dosage of the acid absorber is 320mg.
Example 11
Propylene-butene random copolymer preparation was carried out as in example 2 except that no antistatic agent (ethoxylated-C12-18-alkylamine) was added in step b.
Example 12
Propylene-butene random copolymer preparation was carried out as in example 2, except that the conditions for the first gas phase random copolymerization reaction included: the temperature was 80 ℃, the pressure was 3.1MPa, the residence time was 1.5h, and the stirring rate was 29rpm; the second gas phase random copolymerization reaction was carried out at 78℃and a pressure of 2.5MPa.
Example 13
Propylene-butene random copolymer preparation was carried out as in example 2, except that ethoxylated-C12-18-alkylamine was replaced with equal mass of glycerol monostearate.
Comparative example 1
This example is for explaining the preparation method of propylene-butene random copolymer
The propylene-butene random copolymer preparation was carried out as in example 1, except that the mass ratio of the a-butene to the B-butene was 1:1.
comparative example 2
The propylene-butene random copolymer was prepared in the same manner as in example 2, but only the first vertical gas-phase stirred tank was charged with butene and hydrogen, and the second vertical gas-phase stirred tank was not charged with butene and hydrogen, and the amount of butene charged in the first vertical gas-phase stirred tank was the sum of the amounts of butene charged in the two reaction tanks in example 2, and the amount of hydrogen charged was the sum of the amounts of hydrogen charged in the two reaction tanks in example 2.
Comparative example 3
Propylene-butene random copolymer preparation was carried out as in example 2, except that both the a-butene and the B-butene were replaced with ethylene of equal mass.
Test example 1
The propylene-butene random copolymer powders obtained in the step c of the above examples and comparative examples were tested for melting point, molecular weight distribution and olefin content, and the results are shown in Table 3.
The melting point is obtained by a differential scanning method.
The melt flow rate test method is the first part of GB/T3682.1-2018 thermoplastic melt Mass Flow Rate (MFR) determination; the test conditions included: the test temperature was 230℃and the nominal load was 2.16kg.
The molecular weight and molecular weight distribution test method is high temperature gel permeation chromatography, the mobile phase solvent is 1,2, 4-trichlorobenzene, the concentration is controlled at 1mg/mL, the temperature is heated to 150 ℃, the solution is dissolved for 3 hours, and the standard sample is monodisperse polystyrene.
The method for testing the content of the olefin is a high-temperature 13CNMR test, the solvent is dichloro deuterated benzene, the temperature is 120 ℃, and the magnetic field frequency is 400MHz.
TABLE 3 Table 3
As can be seen from Table 3, the propylene-butene random copolymer having a higher butene content and a lower melting point can be produced by the method of the present invention, and thus the propylene-butene random copolymer prepared by the present invention has better processability. Meanwhile, the method of the invention does not produce bulk polymer in the polymerization process, so the method of the invention is more suitable for industrial production. Particularly preferably, with the process of the present invention according to examples 1 to 3 and 10, it is possible to obtain a propylene-butene random copolymer having a butene content of 8 to 9% by weight and a melting point in the range of 146 to 148℃while ensuring that a bulk polymer is not produced.
Test example 2
The propylene-butene random copolymer particles obtained in step e of the above examples and comparative examples were subjected to performance test, and the results are shown in Table 4.
The test method of the impact strength of the cantilever beam is the measurement of the impact strength of GBT 1843-2008 plastic cantilever beam.
The tensile yield strength test method is GB/T1040.3-2006 test conditions for determining the tensile properties of plastics in part 3, films and sheets.
The flexural modulus test method is the measurement of the flexural performance of GB/T9341-2008 plastics.
The haze test method is GB/T2410-2008.
The heat distortion temperature was measured in accordance with GB/T1634.1-2004.
The test method of the n-hexane extract is GB/T5009.71-2003 analytical method of Polypropylene resin sanitation Standard for food packaging.
TABLE 4 Table 4
As can be seen from the results of Table 4, the content of n-hexane extract in the propylene-butene random copolymer particles prepared by the method of the present invention is significantly lower than the upper limit of 2% of n-hexane extract defined in the national Standard for Polypropylene resin for food packaging, sanitary Standard, so that the propylene-butene random copolymer particles prepared by the present invention can be used as transparent random copolymer Polypropylene injection-molded resins. In addition, the invention also ensures better comprehensive mechanical property and processing property of the propylene-butene random copolymer particles under the condition of ensuring that the content of the n-hexane extract reaches the national standard.
As is clear from tables 3 and 4, propylene-butene random copolymers having a high butene content and a low melting point were obtained by the methods of examples 7 to 8 of the present invention, but the propylene-butene random copolymers obtained by the methods had a high n-hexane extract content.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A process for preparing a propylene-butene random copolymer comprising the steps of:
a. refining raw material propylene and raw material butene to obtain refined propylene and refined butene respectively, and dividing the refined butene into A-strand butene and B-strand butene;
b. in the presence of a main catalyst, a cocatalyst, hydrogen, an external electron donor and an optional antistatic agent, carrying out first gas phase random copolymerization on refined propylene and A-strand butene to obtain a first random copolymerization product;
c. contacting the first random copolymerization product with B-strand butene and optional hydrogen to carry out a second gas-phase random copolymerization reaction to obtain a product containing propylene-butene random copolymer;
d. compressing and separating gas in a product containing the propylene-butene random copolymer to obtain propylene and butene, and returning the propylene and the butene to the step a for refining respectively;
wherein the mass ratio of the A-strand butene to the B-strand butene is 1:0.1-0.6.
2. The process according to claim 1, wherein in step b, the amount of the a-butene is 8 to 10 parts by weight, the amount of the main catalyst is 0.004 to 0.01 part by weight, the amount of the cocatalyst is 0.02 to 0.03 part by weight, the amount of the hydrogen is 0.001 to 0.004 part by weight, and the amount of the external electron donor is 0.005 to 0.01 part by weight, relative to 100 parts by weight of the refined propylene.
3. The process according to claim 1 or 2, wherein in step b, the conditions of the first gas-phase random copolymerization reaction comprise: 70-76 ℃, preferably 73-75 ℃, 2-3MPa, preferably 2.5-2.8MPa, and residence time of 1-2h, preferably 1-1.5h.
4. A process according to any one of claims 1 to 3, wherein in step c the conditions of the second gas phase random copolymerization reaction comprise: the temperature is 65-75deg.C, preferably 70-75deg.C, the pressure is 1.3-2MPa, preferably 1.5-1.8MPa, and the residence time is 0.5-1.5 hr, preferably 0.5-1 hr.
5. The process according to any one of claims 1 to 4, wherein the pressure of the first gas phase random copolymerization is 0.5 to 1MPa, preferably 0.5 to 0.8MPa, higher than the pressure of the second gas phase random copolymerization.
6. The process of any of claims 1-5, wherein the temperature of the first gas phase random copolymerization is 1-5 ℃ higher than the temperature of the second gas phase random copolymerization.
7. The process according to any one of claims 1 to 6, wherein the active components of the procatalyst comprise Ti, mg, cl and an internal donor, which is phthalate, preferably phthalate;
and/or the cocatalyst is an alkylaluminum, preferably at least one of triethylaluminum, diethylaluminum chloride and triisobutylaluminum, more preferably triethylaluminum;
and/or the external electron donor is non-phenyl siloxane, preferably cyclohexyl methyl dimethoxy silane, dicyclopentyl methyl dimethoxy silane, diisopropyl dimethoxy silane and diisobutyl dimethoxy silane, and more preferably dicyclopentyl methyl dimethoxy silane.
8. The method of any of claims 1-7, wherein the antistatic agent is glycerol monostearate and/or ethoxylated alkylamine;
and/or the weight ratio of the antistatic agent to the external electron donor is 1:1-2;
preferably, the antistatic agent is an ethoxylated alkylamine.
9. The method according to any one of claims 1-8, wherein the method further comprises step e: and granulating the propylene-butene random copolymer powder in the product containing the propylene-butene random copolymer, wherein the granulating process comprises the steps of mixing the propylene-butene random copolymer powder with a composite auxiliary agent and granulating.
10. A system for producing a propylene-butene random copolymer, the system comprising: a raw material refining unit, a copolymerization unit and a separation recovery unit, wherein,
the raw material refining unit comprises a propylene refining unit and a butene refining unit which are respectively used for refining raw material propylene and raw material butene to obtain refined propylene and refined butene;
the copolymerization unit comprises a first vertical gas-phase stirring kettle (31) and a second vertical gas-phase stirring kettle (32) which are connected in series, wherein the first vertical gas-phase stirring kettle (31) is used for carrying out first gas-phase random copolymerization on refined propylene and refined butene, and the second vertical gas-phase stirring kettle (32) is used for carrying out second gas-phase random copolymerization on a product of the first gas-phase random copolymerization and the refined butene to obtain a product containing propylene-butene random copolymer;
the separation and recovery unit is used for separating unreacted propylene and butene in the product from the copolymerization unit, returning the separated propylene to the propylene refining unit, and returning the separated butene to the butene refining unit.
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