CN107686536A - The industrial process of trans 1,4 butadiene-isoprene copolymer rubber and the device for implementing this method - Google Patents
The industrial process of trans 1,4 butadiene-isoprene copolymer rubber and the device for implementing this method Download PDFInfo
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- CN107686536A CN107686536A CN201710913932.9A CN201710913932A CN107686536A CN 107686536 A CN107686536 A CN 107686536A CN 201710913932 A CN201710913932 A CN 201710913932A CN 107686536 A CN107686536 A CN 107686536A
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- Prior art keywords
- butadiene
- catalyst
- isoprene
- monomer
- polymer
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 55
- 229920001971 elastomer Polymers 0.000 title claims abstract description 51
- 239000005060 rubber Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000178 monomer Substances 0.000 claims abstract description 74
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims abstract description 46
- 239000000693 micelle Substances 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005469 granulation Methods 0.000 claims abstract description 9
- 230000003179 granulation Effects 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 238000012805 post-processing Methods 0.000 claims abstract description 6
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000012423 maintenance Methods 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 42
- 239000010936 titanium Substances 0.000 claims description 42
- 229910052719 titanium Inorganic materials 0.000 claims description 42
- 239000003292 glue Substances 0.000 claims description 36
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 wherein Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 238000005354 coacervation Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- 239000003426 co-catalyst Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000009776 industrial production Methods 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000012806 monitoring device Methods 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 4
- 229910000091 aluminium hydride Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 2
- 241001597008 Nomeidae Species 0.000 claims description 2
- 229910010386 TiI4 Inorganic materials 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 2
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 150000001361 allenes Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 2
- 235000014692 zinc oxide Nutrition 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000002329 infrared spectrum Methods 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 5
- 230000001413 cellular effect Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The present invention relates to the device of the industrial process of trans 1,4 butadiene-isoprene copolymer rubber (TBIR) and implementation this method.The production method one：Solvent, butadiene and the isoprene of scheduled volume deliver to polyplant, implement solution copolymerization in the presence of catalyst, obtain TBIR.The production method two：Solvent, butadiene and isoprene are delivered into polymer reactor according to predetermined close, implement solution copolymerization in the presence of catalyst, the mol ratio of butadiene and isoprene in maintenance system, obtains TBIR.Polymer slurries carry out drying, granulation and the packaging of micelle after terminating, condensing.Solvent and unreacted monomer through separating, it is refined after, return to polyplant or storage tank.The process units includes recovery refined unit, polymerized unit, post-processing unit and public work unit.By the production method and device, solwution method prepares TBIR and realizes industrialized production.
Description
Technical field
The present invention relates to anti-form-1 in petrochemical industry, 4- structures butadiene-isoprene copolymer glue (TBIR) system
Standby technical field, and in particular to be a kind of solwution method production anti-form-1, the work of 4- structure butadiene-isoprene copolymer glues
Industry production method and the device for implementing this method.
Background technology
Anti-form-1,4- structures butadiene-isoprene copolymer glue (TBIR) are on anti-form-1,4- polyisoprene basis
The elastomeric material of new generation of upper development, compared with common natural rubber, the maximum feature of this material is that dynamic property is good, heat
Low, wearability is good, is the good material for manufacturing high-performance energy-conserving and environment-protective tire.Its excellent fatigue performance and low-heat-generation performance,
It will be widely used on various yielding rubber materials.Patent (US 5100965, WO 9723521, US 4020115,
US5844044, UK 2029426) disclose high trans structure butadiene isoprene copolymer excellent physical mechanics
Performance, particularly fatigue durability and resistance to breach growth property can be excellent, are the preferable sizing materials for developing high-performance tire.
TBIR synthesis mainly uses coordination polymerization catalysts such as pi-allyl Raney nickel system, TiCl4/VOCl3/Al
(i-Bu)3Catalyst system, allyl chromium-silicate catalyst system, lanthanide metal compound catalyst system
[Dokl.Akad.Nauk SSSR,1976；Ger.Pat.2331921,1975；Dokl.Akad.Nauk SSSR,1973；Prom-
st Sint Kauch,1982；Unexamined Patent 2-60907,1990] etc., and anionic alkyl group lithium system [US 4020115,
1997；UK Pat 2029426,1980；US 5100965,1992].But above-mentioned system has that catalytic efficiency is low or trans knot
The problem of structure content is low.
Supported titanium System Catalyst [JP 60-42412,1985；Elastomer, 2002；Macromolecule journal, 2002；Synthesis
Rubber industry, 2002] can synthesize transconfiguration content higher than 97%, monomer composition can be adjusted in copolymer
TBIR, its catalytic efficiency is higher, can reach 30000 times.Chinese invention patent ZL201210138621.7 discloses a kind of anti-
The butadiene-isoprene copolymer glue of formula-Isosorbide-5-Nitrae-structure, its transconfiguration content are more than 90%, in copolymer butadiene and
The composition of isoprene is respectively 0.5-80% and 20-99.5%.Meanwhile the microstructure sequence distribution of its two kinds of monomers can be with
It is gradient distribution or equally distributed.But the patent uses polymerisation in bulk, the polymerization later stage can cause system viscosity to increase severely, reactor
Motor can not normal operation, therefore monomer conversion generally it is very low, no more than 20%-25%.The patent is not directed to solvent simultaneously
Recovery and refinement treatment with monomer.Solution polymerization is the polymerization commonly used in current synthetic rubber, can be solved above-mentioned
The viscosity sharp increase problem that polymerisation in bulk is brought.
In order to overcome the above-mentioned difficulty and shortcoming for referring to patented technology, present patent application provides one kind to use solution legal system
Standby anti-form-1, the industrial process of 4- structures butadiene-isoprene copolymer glue (TBIR) and the device for implementing this method.
The content of the invention
More than in view of, one of main object of the present invention is to provide a kind of solution polymerization process industrial production anti-form-1,4- knots
The production method of the butadiene-isoprene copolymer glue (TBIR) of structure.
The two of the main object of the present invention, which are to provide, implements the above-mentioned industrial device of TBIR solution polymerization process.
To achieve the above object, a kind of anti-form-1 of the invention, the butadiene-isoprene copolymer glue solution of 4- structures
Polymer industry production method, the production method can be method one or method two,
Method one：
(1) polyplant through application of vacuum and nitrogen be sufficiently displaced from remove water oxygen after, by proportioner in order successively
By refined solvent, isoprene monomer, divinylic monomer, co-catalyst, electron donor, major catalyst and molecular weight regulator
It is sent to respectively according to predetermined close in polymer reactor, the mol ratio of titanium and/or v element and monomer is 0.01 in major catalyst
~100 × 10-5:1, Al elements and the titanium in major catalyst and/or the mol ratio of v element in co-catalyst are 1~500:1,
Molecular weight regulator is 0.01~2000 with the mol ratio of titanium and/or v element in catalyst:1, in electron donor and catalyst
The mol ratio of titanium and/or v element is 0~10:1, co-polymerization temperature is 20~90 DEG C, and butadiene and feeding intake for isoprene are rubbed
That ratio 0.01~50:100, the mass ratio of monomer and solvent is 10~30:100, constant temperature polymerize 1~48 hour；
(2) polymer slurries are added into terminator by pipelined to stop device, while in the entrance of stop device；
(3) polymer after step (2) termination is transported to coacervation device, is condensed into micelle；Solvent and unreacted list
Body reclaims from coacervation device side line, separates and returns to polyplant or storage tank after refined；
(4) the micelle shaped polymer that step (3) obtains is after drying and dehydrating, then is transported to extruder, while to extrusion
Machine adds age resistor and/or rubber chemicals, extruded granulation obtain granular anti-form-1,4- butadiene-isoprene copolymer rubbers
Glue, after drying, measured and packed.
Method two：
(1) polyplant through application of vacuum and nitrogen be sufficiently displaced from remove water oxygen after, by feed proportioning system in order successively
By refined solvent, isoprene monomer, divinylic monomer, co-catalyst, electron donor, major catalyst and molecular weight regulator
It is sent to respectively according to predetermined close in polymer reactor, the mol ratio of titanium and/or v element and monomer is 0.01 in major catalyst
~100 × 10-5:1, Al elements and the titanium in major catalyst and/or the mol ratio of v element in co-catalyst are 1~500:1,
Molecular weight regulator is 0.01~2000 with the mol ratio of titanium and/or v element in catalyst:1, in electron donor and catalyst
The mol ratio of titanium and/or v element is 0~10:1, co-polymerization temperature is 20~90 DEG C, and butadiene and feeding intake for isoprene are rubbed
That ratio 0.01~50:100, the mass ratio of monomer and solvent is 10~30:100, constant temperature polymerization；
(2) liquid monomer mole in polymerization system is monitored by on-Line Monitor Device to form, and by controlling proportioner
Divinylic monomer is added to polymer reactor, keeps butadiene in step (1) and isoprene monomer mol ratio constant, holding
Temperature-resistant, the constant temperature polymerization 1~48 hour of step (1)；
(3) polymer slurries are added into terminator by pipelined to stop device, while in the entrance of stop device；
(4) polymer after step (3) termination is transported to coacervation device, solvent and unreacted monomer from coacervation device
Side line reclaims, and separates and returns to paradigmatic system or storage tank after refined；Polymer becomes micelle shape in condensing field；
(5) the micelle shaped polymer that step (4) obtains is after drying and dehydrating, is transported to extruder, while to extruder
Add age resistor and/or a certain amount of rubber chemicals, extruded granulation obtain granular anti-form-1,4- butadiene-isoprenes are total to
Poly- rubber, after drying, measured and packed.
Using technical scheme provided by the invention, for the anti-form-1 of production, the butadiene-isoprene copolymer of 4- structures
Rubber, for its copolymer composition with the extension in reaction time, copolymer rubber prepared by method one is the copolymer rubber of gradient composition,
With the increase of conversion ratio, anti-form-1 in newly-generated copolymer rubber, 4- polyisoprene blocks are increasingly longer, and content is increasingly
It is more；Copolymer rubber prepared by method two is the uniform copolymer rubber of composition, with the increase of conversion ratio, newly-generated copolymer rubber
Composition does not change substantially.
Trans Isosorbide-5-Nitrae-structure molar content is more than 85% in copolymer rubber of the present invention, and butadiene rubs in copolymer rubber
That content 0.1~50%, the Mooney viscosity (3+4 minutes at 100 DEG C) of copolymer rubber is 20~120.
In order that solution polymerization process prepares anti-form-1,4- butadiene-isoprene copolymer glues are achieved industrial production,
The invention provides a set of industrialization reaction unit, the device includes recovery refined unit, polymerized unit, post-processing unit and public affairs
With engineering unit, specifically include：
Reclaim refined unit include solvent, butadiene, the refining plant of isoprene and for recovered solvent and
Unreacted monomer is separated and refined, and is delivered to the recovery separator of polymer reactor or storage tank；
Polymerized unit includes：
Proportioner：Solvent, butadiene, the metering of isoprene and pumping installations；Major catalyst, co-catalyst, to electricity
Preparation, metering and the pumping installations of daughter；The refined and metering device of molecular weight regulator；
Polymerizing reactor：Including 1 set of autoclave, tower, annular tube type or tubular polymerization reactor that either more sets are connected；
Monitoring and control device：Including on-line temperature monitoring device, pressure on-line monitoring device, material on-line checking device and control
Device；Material on-line checking device includes in-situ infrared spectroscopy, online viscosity detector；Material on-line controller includes material electromagnetism
Valve, material flow gauge and Computer Control Unit；
Post-processing unit includes：
Stop device：Including finishing reactor and glue tank, finishing reactor is the tank reactor with stirring, glue
Tank is used for the allotment of polymer between different batches；
Coacervation device：For recycling design and unreacted monomer, while obtain the polymer of micelle shape；Include 1 set or more
The kettle of series connection is covered built with the condensing field and condenser of frame or propeller formula or anchor formula agitating paddle and steam pipe and layering tank；
Extruding pelletization device：For one in single screw extrusion machine, parallel dual-screw extruding machine, counter rotation twin screw extruder
Kind, for the mixing of polymer and age resistor and/or rubber chemicals, and it is granulated；
Terminator, age resistor and rubber chemicals configuration, conveying device；
Public work unit：It is used to carry out temperature control to polymerization system including hot water or cold water and/or steam pipework device；
Vacuum and high pure nitrogen device enter line replacement when being used for before polymerization with maintenance to paradigmatic system；Material lifting device is used for will be dry
Polymer after dry sends to metering and packaging.
The method according to the invention, further solvent, butadiene and isoprene monomer are entered respectively before step (1)
Row is refined.
The method according to the invention, the solvent in step (3) and method two in step (4) and unreacted list in method one
Body recovery after, by separation and refining plant separation and purification, after can by proportioner return polymer reactor be polymerize or
Solvent or single storage tank are pumped to respectively.
The method according to the invention, polymer is being transported to terminator simultaneously, terminator can passed through pipelined
To terminator.
Polymer reactor of the present invention is optionally the polymer reactor using one or more sets series connection, and described is poly-
It is either tubular reactor or the tower reactor or annular tube type of the tank reactor with ribbon impeller to close reactor
Reactor.
Described major catalyst of the present invention is supported titanium and/or vanadium catalyst, wherein, titanium and/or v element account for
The 1%~5% of catalyst gross mass, internal electron donor account for the 0%~20% of the gross mass of catalyst；The carrier of catalyst is selected from
MgCl2、MgBr2、MgI2、SiO2In one kind；Titanium compound is selected from TiCl4、TiBr4Or TiI4In one kind；Vfanadium compound selects
From VCl3、VBr3、VOCl3、VOBr3、VCl4、VBr4、V2O5In one or more；Internal electron donor be esters, ethers, ketone,
One or more in anhydrides compound.
Co-catalyst of the present invention is triethyl aluminum, triisobutyl aluminium, dimethyl monochlor(in)ate aluminium, monomethyl dichloride
Aluminium, diethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium, an isobutyl aluminium dichloride, alkyl aluminium hydride
It is the one or more of diethyl aluminium hydride, ethyl hydride aluminium, hydrogenation aluminium isobutyl or diisobutylaluminium hydride.
Molecular weight regulator of the present invention be hydrogen, ethene, propylene, allene, 1,2- butadiene, cyclo-octadiene or
It is more than one or both of alcohol, mercaptan, amine, phenol and its salt.Electron donor of the present invention is phosphoric acid ester, ethers, ketone
One or more in class, anhydrides, phenols, silane compound.
Solvent of the present invention is inert hydrocarbon solvent, selected from pentane, isopentane, hexane, hexamethylene, methyl cyclohexane
Alkane, normal heptane, normal octane, benzene, toluene, paraxylene, meta-xylene, isopropylbenzene, hydrogasoline and raffinate oil；Solvent and monomer
Mass ratio be 10~30:100.
Stop device in apparatus of the present invention includes finishing reactor, the preparation of glue tank and terminator and metering device,
Finishing reactor is the tank reactor with stirring, and glue tank is used for the allotment of polymer between different batches；In terminating reaction
Device entrance can add terminator to polymer slurries；Described terminator be carbon monoxide, carbon dioxide, nitrogen, empty gas and water and
One or both of alcohol, acid, ketone, amine, phenol containing 4~8 carbon atoms are mixed above, terminator and titanium in major catalyst
And/or the mol ratio of v element is 1~100:1.
The purpose of coacervation device in apparatus of the present invention is for recycling design and unreacted monomer, while obtains micelle shape
Polymer, comprising 1 set or the condensing field of more set series connection and condenser and layering tank, condensing field is built with frame or propeller
Formula or anchor formula agitating paddle and steam pipe；
Described extruding pelletization device is in single screw extrusion machine, parallel dual-screw extruding machine, counter rotation twin screw extruder
One kind.Polymer can add age resistor and/or rubber chemicals while extruding pelletization.
Age resistor of the present invention be 4010NA, MB, 2264,264, MBZ, 800A, 1010A, 1010,168, DSTP,
626th, the one or more in 4020 and 1076, age resistor are 0.01~1 with TBIR weight ratio:100；The rubber chemicals are stone
Wax, aromatic naphtha, naphthenic oil, light dydrocarbon resin, stearic acid, calcium stearate, magnesium stearate, zinc oxide, silica, carbon black or on
The one or more in modification derivant are stated, rubber chemicals are 10~50 with TBIR weight ratio:100.
The mol ratio of titanium and/or v element and monomer is 0.01~100 × 10 in major catalyst of the present invention-5:1,
Molecular weight regulator is 0.01~2000 with the mol ratio of titanium and/or v element in catalyst：1, in electron donor and catalyst
The mol ratio of titanium and/or v element is 0-10：1, co-polymerization temperature is 20~90 DEG C, and butadiene and isoprene feed intake mole
Than 0.01~50：100, the mass ratio of monomer and solvent is 10~30:100, polymerization time is 1~48 hour.
Described extruder can be that single order or two rank above serial or parallel connections use, be used in series can obtain it is lower
Solvent and content of monomer；It is used in parallel to improve yield.
The polymerization technique of the present invention can be intermittence type polymerization mode either continous way polymerization methodses.
The present invention can realize TBIR solution polymerization process industrial production by above method.
Brief description of the drawings
Describe the present invention in detail with reference to the accompanying drawings and detailed description.
Accompanying drawing 1 is the workflow diagram of the process units of the present invention
In figure, polymerized unit is polymerizing reactor；Recovery refined unit includes solvent refining, and butadiene refines, isoamyl
Diene refines, and reclaims the separation of monomer and solvent and refined, catalyst, the configuration of molecular weight regulator and electron donor and meter
Amount, the configuration and metering of monomer and solvent after refining；Post-processing unit includes termination, coacervation device and granulation, drying, packaging dress
Put.
Embodiment
In order to preferably explain the technological process of production and process units workflow of the present invention, to describe the present invention in detail
Technological means, feature and the purpose reached of realization, with reference to embodiment, the present invention is furture elucidated.
Following examples raw materials of the present invention are：
Butadiene, Qilu Petrochemical, polymer grade, purity>99.0%；Isoprene, Kingsoft petrochemical industry, polymer grade, purity>
99.0%；Normal heptane, Qilu Petrochemical, purity>99.0%；Heterogeneous supported titanium catalyst, self-control, MgCl2Load TiCl4Catalysis
Agent, it is 3.2% to carry titanium amount；Heterogeneous load vanadium catalyst, self-control, MgCl2Supported V OCl3Catalyst, it is 3.5% to carry vanadium amount；Three
Aluminium isobutyl, self-control, purity 98%；Hydrogen, the production of Linzhou City auxiliary reagent factory, purity 99.99%；Antioxidant 264,2264,1010A, work
Industry level, Shanghai addition Chemical Co., Ltd.；Ethanol, hexamethylene diamine, acetone, technical grade, Laiyang chemical plant.Other molecular-weight adjustings
Agent, electron donor, rubber chemicals and age resistor are commercially available industrial goods.
Embodiment 1
By 20 cubic metres of polymeric kettles after vacuum nitrogen is handled, solvent is disposably passed through into polymeric kettle by proportioner
6 tons of normal heptane, 0.382 ton of divinylic monomer, 1.4 tons of isoprene monomer, by public work unit by polymeric kettle temperature liter
To after 60 DEG C, triisobutyl aluminium 3.2Kg is sequentially added, carries the TiCl that titanium amount is 3.2wt%4/MgCl2Heterogeneous supported titanium catalysis
Agent 0.424Kg, add hydrogen 120mol.48h is reacted on this condition, now detects condensate through in-situ infrared spectroscopy monitor
Divinylic monomer concentration in system will be 0.After reaction terminates, polymeric kettle interpolymer slurries are filled by pipelined to termination
Put, 32g terminator butanol is passed through into stop device, polymerisation is terminated, be then transferred to the storage of glue tank and adjust
Match somebody with somebody.Terminate the polymer slurries after allotment and be delivered to coacervation device, be condensed into the polymer of micelle shape.Carry out unreacted list simultaneously
The separation of body and polymer, the monomer isolated is by successively after MONOMER RECOVERY tower, monomer separation treating column, into storage tank
It is standby.Resulting micelle shaped polymer is transported to double screw extruder, while adds 1.5Kg age resistor in charge door position
2264 and 280Kg aromatic naphtha, 2Kg stearic acid, 1Kg zinc oxide and 110Kg improved silica rubber chemicals, through squeezing
Go out to be granulated and obtain granular anti-form-1,4- butadiene-isoprene copolymer glues, weighed and packed after being further dried.
Products weight is obtained as 1.465 tons, is computed polymer weight as 1.07 tons, conversion ratio is about 60%.After tested
The cellular construction content of butadiene is 36% in TBIR, and transconfiguration content is 92%, Mooney viscosity (ML100 3+4) it is 65.
Embodiment 2
Operation does not add hydrogen simply, while add electron donor fourth diether 0.145Kg, polymerization temperature 65 with embodiment 1
℃。
Products weight is obtained as 1.8 tons, is computed polymer weight as 1.406 tons, conversion ratio is about 79%.After tested
The cellular construction content of butadiene is 27% in TBIR, and transconfiguration content is 96%, Mooney viscosity (ML100 3+4) it is 120.
Embodiment 3
By 20 cubic metres of polymeric kettles after vacuum nitrogen is handled, normal heptane 6.5 is passed through into polymeric kettle by proportioner
Ton, 0.12 ton of divinylic monomer, 1.0 tons of isoprene monomer, after polymeric kettle temperature is risen into 90 DEG C by public work unit,
Triisobutyl aluminium 2.8kg is sequentially added, electron donor 1,3- dimethoxy propane 53g, carries the TiCl that titanium amount is 3.2%4/MgCl2
Heterogeneous supported titanium catalyst 0.078kg, hydrogen 48mol is added, carry out polymerisation.Supervised by the online infrared and viscosity of material
The butadiene content surveyed in device detection architecture, and divinylic monomer is persistently added to polymeric kettle by material on-line controller, tie up
The concentration ratio for holding the butadiene in polymerization system and isoprene monomer is initial rate of charge scope.React 48h.Reaction terminates
Afterwards, polymeric kettle interpolymer slurries are passed through 92g terminator water into stop device by pipelined to stop device, it is right
Polymerisation is terminated, and is then transferred to the storage of glue tank and allotment.Terminate the polymer slurries after allotment and be delivered to cohesion
Device, it is condensed into the polymer of micelle shape.Carry out the separation of unreacted monomer and polymer simultaneously, the monomer isolated pass through according to
It is secondary after MONOMER RECOVERY tower, monomer separation treating column, it is standby into storage tank.Resulting micelle shaped polymer is transported to double spiral shells
Bar extruder, while add 13Kg age resistor (264 in charge door position:1010 mass ratioes:2:1) and 260Kg naphthenic oils,
8Kg stearic acid, 4Kg zinc oxide and 120Kg carbon blacks, extruded granulation obtain granular anti-form-1, and 4- butadiene-isoprenes are total to
Poly- rubber, weighed and packed after being further dried.
Product is obtained as 1.705 tons, is computed about 1.3 tons of polymer weight in product.Butadiene in TBIR after tested
Cellular construction content is 50%, and transconfiguration content is 95%, Mooney viscosity (ML100 3+4) it is 78.
Embodiment 4
By 40 cubic metres of polymeric kettles 1 of two series connection and polymeric kettle 2 after vacuum nitrogen is handled, by proportioner to poly-
Close and 11 tons of normal heptane is passed through in kettle 1,0.12 ton of divinylic monomer, 1.0 tons of isoprene monomer will be poly- by public work unit
After conjunction kettle temperature degree rises to 60 DEG C, triethyl aluminum 28Kg, electron donor 2,2-dimethoxypropane are added to polymeric kettle 1 successively
0.92Kg, carry the VOCl that vanadium amount is 3.5%3/MgCl2Heterogeneous load vanadium catalyst 1.3Kg, hydrogen 20mol is added, is gathered
Close reaction 1-10h.The polymerization system of polymeric kettle 1 continues to react through pipelined to the polymeric kettle 2 of series connection, polymerization temperature 80
DEG C, polymerization time 1-24h.By the butadiene content in the online infrared and Viscosity Monitoring device detection architecture of material, and pass through thing
Material on-line controller persistently adds divinylic monomer to polymeric kettle 1 and polymeric kettle 2, maintains butadiene and isoamyl in polymerization system
The concentration ratio of diene monomers is initial rate of charge scope.After reaction terminates, polymeric kettle interpolymer slurries are passed through into pipelined
To stop device, 1.5Kg terminator water is passed through into stop device, polymerisation is terminated, is then transferred to glue tank
Storage and allotment.Terminate the polymer slurries after allotment and be delivered to coacervation device, be condensed into the polymer of micelle shape.Carry out simultaneously
The separation of unreacted monomer and polymer, the monomer isolated by successively after MONOMER RECOVERY tower, monomer separation treating column,
It is standby into storage tank.Resulting micelle shaped polymer is transported to double screw extruder, while adds and prevented always in charge door position
The 1100g of agent 2264, extruded granulation obtain granular anti-form-1,4- butadiene-isoprene copolymer glues, are further dried
After weighed and packed.
1.1 tons of products therefrom.The cellular construction content of butadiene is 42% in TBIR after tested, and transconfiguration content is
95%, Mooney viscosity (ML100 3+4) it is 86.
Embodiment 5
With embodiment 1, the triisobutyl aluminium that 10% is simply substituted by the use of aluminum hydride is used as co-catalyst for operation.
Products therefrom weight is 1.48 tons, and it is 1.085 tons that polymer weight, which is calculated, conversion ratio 61%.After tested
The cellular construction content of butadiene is 28% in TBIR, and transconfiguration content is 86%, Mooney viscosity (ML100 3+4) it is 85.
Embodiment 6
Polymerizing condition and scheme simply change polymerization tank reactor into annular-pipe reactor with embodiment 4.Finally give grain
The anti-form-1 of shape, 1.23 tons of 4- structures butadiene-isoprene copolymer glue (TBIR).After tested, butadiene in gained TBIR
The molar content of unit is 41%, anti-form-1, and 4- structural contents are 94%, Mooney viscosity (ML100 3+4) it is 85.
Embodiment 7
In the reactor with stirring, the TiCl that titanium amount is 3.2% will be carried4/MgCl2Heterogeneous supported titanium catalyst is used
It is standby that white oil is diluted to suspension.The white oil that the proportioning of supported titanium catalyst and white oil is 350g catalyst/10L.In stirring
The lower keeping body of effect is tied to form well dispersed suspension.
Using continuous polymerization.10 10 cubic metres of the tank reactor series connection with double ribbon stirrings is anti-as polymerization
Device is answered, whole reaction unit and its pipeline are subjected to the nitrogen vacuum displacement removing water oxygen harmful to catalyst.Solvent and fourth
Diene, isoprene monomer are refined in advance before paradigmatic system is entered.Stirring is opened, rotating speed is 100 turns/min；By solvent
Normal heptane, divinylic monomer, isoprene monomer, triisobutyl aluminium, supported titanium catalyst and hydrogen are defeated by feed controller
Enter into the first reactor, polymerization temperature is 40 DEG C, and polymerisation is carried out in the presence of stirring.Control the stream of solvent n-heptane
Measure as 1.5m3/ h, the flow of butadiene is 0.065m3/ h, the flow of isoprene is 0.435m3/ h, triisobutyl aluminum flux are
250mL/h, supported titanium catalyst flow are 0.875L/h, hydrogen flowing quantity 12g/h.Polymeric system is by plunger pump through carrying
The pipeline of insulation is fed sequentially into the 2nd~10 polymeric kettle, and the polymerization temperature of the 2nd~10 reactor is 80 DEG C, controls total stop
Time is 48h.Be transported to finishing reactor from the polymeric system of the 10th reactor outflow, at the same by terminator ethanol according to
5g/h flow carries out terminating reaction through pipelined to finishing reactor.Polymeric system after termination conveys through metering screw
To polymer agglomerates device, solvent, unreacted monomer are reclaimed by steam stripped method.Recovered solvent and monomer warp
After crossing separation, respectively enter refining plant and carry out after refining, it is standby to return to corresponding storage tank.Polymer after cohesion is transported to double
Screw extruder, while add age resistor (2264 according to 0.18Kg/h speed in charge door position：4010NA=1:2), pass through
Extruding pelletization obtains granular anti-form-1,4- butadiene-isoprene copolymer glues, is weighed and is wrapped after being further dried
Dress.After tested, the molar content of the butadiene structural units of gained copolymer rubber is 24.6%, anti-form-1, and 4- structural contents are
More than 98%, (100 degree, 3+4 minutes) of Mooney viscosity is 65.Prepared copolymer rubber have heat is low, wearability is good, it is resistance to bend
Excelling in fatigue property feature is scratched, rubber is used suitable for the dynamic such as tire, shock absorber part, damping material.
Embodiment 8~10
In the reactor with stirring, the TiCl that titanium amount is 3.2% will be carried4/MgCl2Heterogeneous supported titanium catalyst is used
It is standby that white oil is diluted to suspension.The white oil that the proportioning of supported titanium catalyst and white oil is 350g catalyst/10L.In stirring
The lower keeping body of effect is tied to form well dispersed suspension.
Polymerizing reactor is used as using 2 tank reactors with double ribbon stirrings and 2 annular-pipe reactor series connection,
Whole reaction unit and its pipeline are subjected to the nitrogen vacuum displacement removing water oxygen harmful to catalyst.It is solvent and butadiene, different
Pentadiene monomer is refined in advance before paradigmatic system is entered.By 1# tank reactors temperature control at 45 DEG C, 2# still reactions
Device temperature control is at 60 DEG C, and annular-pipe reactor temperature control is at 80 DEG C.The stirring of tank reactor is opened, rotating speed is 200 turns/min；By solvent
Hydrogasoline, divinylic monomer, isoprene monomer, triisobutyl aluminium, supported titanium catalyst and hydrogen are inputted by inlet valve
Into 1# reactors, polymerisation is carried out in the presence of stirring.Polymeric acceptor is tied up in reactors at different levels and passed through by plunger pump
Pipeline with insulation conveys successively.There are online infrared monitoring and Viscosity Monitoring at the middle part of stirred tank and annular-pipe reactor
Device, butadiene and isoprene content in detection architecture, and monoblock pump is controlled from trend device by material on-line controller
Butadiene is injected, to control the mol ratio of butadiene and isoprene in reaction system.From the polymerization of annular-pipe reactor outflow
Objects system is pumped into terminator by measuring, while terminator ethanol is carried out into terminating reaction through pipelined to terminator.Eventually
Polymeric system after only is transported to polymer agglomerates device through metering screw, by steam stripped method by solvent, unreacted
Monomer is reclaimed.Recovered solvent and monomer respectively enter refining plant and carried out after refining, return corresponding after separation
Storage tank is standby.Polymer after cohesion is transported to double screw extruder, while adds age resistor 2264 in charge door position and prevent
Old agent 4010NA, extruded granulation obtain granular anti-form-1,4- butadiene-isoprene copolymer glues, after being further dried
Weighed and packed.The physical property of all material flows, residence time and gained copolymer rubber is shown in Table 1.Prepared is total to
Poly- rubber has that heat is low, wearability is good, flex fatigue property excellent characteristics, suitable for tire, shock absorber part, damping material etc.
Dynamic uses rubber.
The embodiment 8-10 of table 1 main technologic parameters and prepared polymer physics performance
| Parameter | Unit | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Solvent | m3/h | 1.6 | 3.2 | 0.75 |
| Butadiene | m3/h | 0.08 | 0.12 | 0.03 |
| Isoprene | m3/h | 0.32 | 0.68 | 0.22 |
| Triisobutyl aluminium | L/h | 0.85 | 2 | 1.24 |
| Supported titanium catalyst | L/h | 1.7 | 3.4 | 2.1 |
| Hydrogen | m3/h | 12 | 0 | 12 |
| Butadiene content in TBIR | % | 21.4 | 19.2 | 16.8 |
| Transconfiguration content in TBIR | % | >98 | >98 | >98 |
| Mooney, 100 DEG C | ML3+4 | 62 | 96 | 64 |
Claims (9)
1. a kind of anti-form-1, the industrial process of the butadiene-isoprene copolymer glue of 4- structures, the production method can
Implemented by method one or method two,
Method one：
(1) polyplant is after application of vacuum and nitrogen are sufficiently displaced from removing water oxygen, by proportioner in order successively by essence
Solvent, isoprene monomer, divinylic monomer, co-catalyst, electron donor, major catalyst and the molecular weight regulator difference of system
It is sent to according to predetermined close in polymer reactor, the mol ratio of titanium and/or v element and monomer is 0.01~100 in major catalyst
×10-5:1, Al elements and the titanium in major catalyst and/or the mol ratio of v element in co-catalyst are 1~500:1, molecule
It is 0.01~2000 that conditioning agent, which is measured, with the mol ratio of titanium and/or v element in catalyst:1, in electron donor and catalyst titanium and/
Or the mol ratio of v element is 0~10:1, co-polymerization temperature is 20~90 DEG C, the molar ratio of butadiene and isoprene
0.01~50:100, the mass ratio of monomer and solvent is 10~30:100, constant temperature polymerize 1~48 hour；
(2) polymer slurries are added into terminator by pipelined to stop device, while in the entrance of stop device；
(3) polymer after step (2) termination is transported to coacervation device, is condensed into micelle；Solvent and unreacted monomer from
Coacervation device side line reclaims, and separates and returns to polyplant or storage tank after refined；
(4) the micelle shaped polymer that step (3) obtains is after drying and dehydrating, then is transported to extruder, while adds to extruder
Enter age resistor and/or rubber chemicals, extruded granulation obtains granular anti-form-1,4- butadiene-isoprene copolymer glues, warp
Cross after drying, measured and packed；
Method two：
(1) polyplant is after application of vacuum and nitrogen are sufficiently displaced from removing water oxygen, by feed proportioning system in order successively by essence
Solvent, isoprene monomer, divinylic monomer, co-catalyst, electron donor, major catalyst and the molecular weight regulator difference of system
It is sent to according to predetermined close in polymer reactor, the mol ratio of titanium and/or v element and monomer is 0.01~100 in major catalyst
×10-5:1, Al elements and the titanium in major catalyst and/or the mol ratio of v element in co-catalyst are 1~500:1, molecular weight
Conditioning agent is 0.01~2000 with the mol ratio of titanium and/or v element in catalyst:1, in electron donor and catalyst titanium and/or
The mol ratio of v element is 0~10:1, co-polymerization temperature is 20~90 DEG C, the molar ratio 0.01 of butadiene and isoprene
~50:100, the mass ratio of monomer and solvent is 10~30:100, constant temperature polymerization；
(2) liquid monomer mole in polymerization system is monitored by on-Line Monitor Device to form, and by controlling proportioner to poly-
Close reactor and add divinylic monomer, keep butadiene in step (1) and isoprene monomer mol ratio constant, holding step
(1) temperature-resistant, constant temperature polymerization 1~48 hour；
(3) polymer slurries are added into terminator by pipelined to stop device, while in the entrance of stop device；
(4) polymer after step (3) termination is transported to coacervation device, solvent and unreacted monomer from coacervation device side line
Recovery, separate and return to paradigmatic system or storage tank after refined；Polymer becomes micelle shape in condensing field；
(5) the micelle shaped polymer that step (4) obtains is transported to extruder, while add to extruder after drying and dehydrating
Age resistor and/or a certain amount of rubber chemicals, extruded granulation obtain granular anti-form-1,4- butadiene-isoprene copolymer rubbers
Glue, after drying, measured and packed.
2. a kind of anti-form-1, the industrial process of the butadiene-isoprene copolymer glue of 4- structures, it is characterised in that institute
Stating industrial manufacture process includes recovery refined unit, polymerized unit, post-processing unit and public work unit, specifically includes：
(1) recovery refined unit includes：Solvent, butadiene, the refining plant of isoprene；Reclaim separator：To recovery
Solvent and unreacted monomer are separated and refined, and are delivered to polymer reactor or storage tank；
(2) polymerized unit includes：Proportioner：Solvent, butadiene, the metering of isoprene and pumping installations；Major catalyst, help
Catalyst, the preparation of electron donor, metering and pumping installations；The refined and metering device of molecular weight regulator；Polymerisation fills
Put：Including 1 set of autoclave, tower, annular tube type or tubular polymerization reactor that either more sets are connected；Monitoring and control device：Bag
Include on-line temperature monitoring device, pressure on-line monitoring device, material on-line checking device and controller；Material on-line checking device includes online
Infrared spectrum, online viscosity detector；Material on-line controller includes material magnetic valve, material flow gauge and computer control dress
Put；
(3) post-processing unit：Stop device：Including finishing reactor and glue tank, finishing reactor is the autoclave with stirring
Reactor, glue tank are used for the allotment of polymer between different batches；Coacervation device：For recycling design and unreacted monomer, together
When obtain the polymer of micelle shape；Comprising 1 set or more set series connection kettle built with frame or propeller formula or anchor formula agitating paddle and
The condensing field and condenser and layering tank of steam pipe；Extruding pelletization device：For single screw extrusion machine, Co rotating Twin Screw Extrusion
One kind in machine, counter rotation twin screw extruder, for the mixing of polymer and age resistor and/or rubber chemicals, and it is granulated；Terminate
Agent, age resistor and rubber chemicals configuration, conveying device；
(4) public work unit：It is used to carry out temperature control to polymerization system including hot water or cold water and/or steam pipework device；Very
Empty and high pure nitrogen device enters line replacement when being used for before polymerization with maintenance to paradigmatic system；Material lifting device is used for drying
Polymer afterwards sends to metering and packaging.
3. anti-form-1 according to claim 1 or 2, the industrial production of the butadiene-isoprene copolymer glue of 4- structures
Method, it is characterised in that anti-form-1 in described copolymer rubber, 4- structures molar content is more than 85%, fourth two in copolymer rubber
Alkene molar content 0.1~50%, 100 DEG C of copolymer rubber, 3+4 minutes Mooney viscosity is 20~120.
4. anti-form-1 according to claim 1 or 2, the industrial production of the butadiene-isoprene copolymer glue of 4- structures
Method, it is characterised in that described major catalyst is supported titanium and/or vanadium catalyst, wherein, titanium and/or v element account for catalysis
The 1%~5% of agent gross mass, internal electron donor account for the 0%~20% of the gross mass of catalyst；The carrier of catalyst is selected from
MgCl2、MgBr2、MgI2、SiO2In one kind；Titanium compound is selected from TiCl4、TiBr4Or TiI4In one kind；Vfanadium compound selects
From VCl3、VBr3、VOCl3、VOBr3、VCl4、VBr4、V2O5In one or more；Internal electron donor be esters, ethers, ketone,
One or more in anhydrides compound.
5. anti-form-1 according to claim 1 or 2, the industrial production of the butadiene-isoprene copolymer glue of 4- structures
Method, it is characterized in that：Described co-catalyst is triethyl aluminum, triisobutyl aluminium, dimethyl monochlor(in)ate aluminium, monomethyl dichloride
Aluminium, diethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium, an isobutyl aluminium dichloride, alkyl aluminium hydride
It is the one or more of diethyl aluminium hydride, ethyl hydride aluminium, hydrogenation aluminium isobutyl or diisobutylaluminium hydride；Described molecule
Amount conditioning agent is in hydrogen, ethene, propylene, allene, 1,2- butadiene, cyclo-octadiene or alcohol, mercaptan, amine, phenol and its salt
It is one or more kinds of；Described electron donor is one kind in phosphoric acid ester, ethers, ketone, anhydrides, phenols, silanes
It is or a variety of.
6. anti-form-1 according to claim 1 or 2, the industrial production of the butadiene-isoprene copolymer glue of 4- structures
Method, it is characterized in that：Described solvent is inert hydrocarbon solvent, selected from pentane, isopentane, hexane, hexamethylene, methyl cyclohexane
Alkane, normal heptane, normal octane, benzene, toluene, paraxylene, meta-xylene, isopropylbenzene, hydrogasoline and one kind in raffinating oil or
It is a variety of.
7. anti-form-1 according to claim 1 or 2, the industrial production of the butadiene-isoprene copolymer glue of 4- structures
Method, it is characterised in that intermittence type polymerization mode or continous way polymerization methodses can be used.
8. anti-form-1 according to claim 1 or 2, the industrial production of the butadiene-isoprene copolymer glue of 4- structures
Method, it is characterised in that described terminator is carbon monoxide, carbon dioxide, nitrogen, empty gas and water and contains 4~8 carbon originals
Alcohol, acid, ketone, amine, one or both of the phenol of son are mixed above, and terminator and titanium in major catalyst and/or v element rub
You are than being 1~100:1；The age resistor be 4010NA, MB, 2264,264, MBZ, 800A, 1010A, 1010,168, DSTP,
626th, the weight ratio of the one or more in 4020 and 1076, age resistor and copolymer rubber is 0.01~1:100；The rubber helps
Agent is paraffin, aromatic naphtha, naphthenic oil, light dydrocarbon resin, stearic acid, calcium stearate, magnesium stearate, zinc oxide, silica, charcoal
The weight ratio of one or more in black or above-mentioned modification derivant, rubber chemicals and copolymer rubber is 1~50:100.
9. anti-form-1 according to claim 1 or 2, the industrial production of 4- structure butadiene-isoprene copolymer glue
Method, it is characterised in that copolymer rubber prepared by method one is the copolymer rubber of gradient composition, newborn with the increase of conversion ratio
Into copolymer rubber in anti-form-1,4- polyisoprene blocks are increasingly longer, and content is more and more；Copolymerization rubber prepared by method two
Glue is forms uniform copolymer rubber, and with the increase of conversion ratio, newly-generated copolymer rubber composition does not change substantially.
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| CN113087829A (en) * | 2021-04-07 | 2021-07-09 | 青岛科技大学 | End group functionalized synthetic rubber and preparation method and application thereof |
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