CN115739184B - Diisobutylene hydroformylation catalyst composition and application thereof - Google Patents
Diisobutylene hydroformylation catalyst composition and application thereof Download PDFInfo
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- CN115739184B CN115739184B CN202211181624.9A CN202211181624A CN115739184B CN 115739184 B CN115739184 B CN 115739184B CN 202211181624 A CN202211181624 A CN 202211181624A CN 115739184 B CN115739184 B CN 115739184B
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- diisobutylene
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- phosphine ligand
- rhodium
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 239000010948 rhodium Substances 0.000 claims abstract description 73
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 50
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 164
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 82
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- WTPYRCJDOZVZON-UHFFFAOYSA-N 3,5,5-Trimethylhexanal Chemical compound O=CCC(C)CC(C)(C)C WTPYRCJDOZVZON-UHFFFAOYSA-N 0.000 claims description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- SYBXSZMNKDOUCA-UHFFFAOYSA-J rhodium(2+);tetraacetate Chemical compound [Rh+2].[Rh+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O SYBXSZMNKDOUCA-UHFFFAOYSA-J 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 abstract description 19
- SZFRZEBLZFTODC-UHFFFAOYSA-N 2,3,4-trimethylpent-2-ene Chemical compound CC(C)C(C)=C(C)C SZFRZEBLZFTODC-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 125000004122 cyclic group Chemical group 0.000 abstract description 10
- 238000006317 isomerization reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 abstract description 3
- BOBIVTKCBMKFJH-UHFFFAOYSA-N P.P(O)O Chemical compound P.P(O)O BOBIVTKCBMKFJH-UHFFFAOYSA-N 0.000 abstract description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- -1 phosphoranylidene amide diphosphine Chemical compound 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 9
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 4
- KDPSKENBCWJPHJ-UHFFFAOYSA-N P.NP(O)O Chemical compound P.NP(O)O KDPSKENBCWJPHJ-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004439 Isononyl alcohol Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- WHWBTOCNUBAGRL-UHFFFAOYSA-N cobalt;formaldehyde Chemical compound [Co].O=C WHWBTOCNUBAGRL-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- DWAQDRSOVMLGRQ-UHFFFAOYSA-N 5-methoxyindole Chemical compound COC1=CC=C2NC=CC2=C1 DWAQDRSOVMLGRQ-UHFFFAOYSA-N 0.000 description 2
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 239000005968 1-Decanol Substances 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WTZKWQAWKOMJLL-UHFFFAOYSA-N P.[PH3]=N Chemical compound P.[PH3]=N WTZKWQAWKOMJLL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004806 diisononylester Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ZOGYOOUMDVKYLM-UHFFFAOYSA-N phosphane phosphorous acid Chemical compound P.OP(O)O ZOGYOOUMDVKYLM-UHFFFAOYSA-N 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- URTNLODHVVYAQT-UHFFFAOYSA-N tris(1H-indol-2-yl)phosphane Chemical compound N1C(=CC2=CC=CC=C12)P(C=1NC2=CC=CC=C2C=1)C=1NC2=CC=CC=C2C=1 URTNLODHVVYAQT-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The diisobutylene hydroformylation catalyst composition comprises a phosphonite monophosphine ligand and a phosphonite biphosphine ligand which are combined specifically, wherein the first ligand and the second ligand of a P-N structural model with strong pi electron receiving capability enhance the rhodium electron receiving capability of a catalyst active species and the space effect around rhodium, accelerate the coordination of diisobutylene and rhodium metal, further improve the reaction rate of 2, 4-trimethyl-2-pentene isomerization, improve the yield of isononaldehyde, strengthen the stability and the catalytic activity of rhodium of the catalyst active species in a cyclic catalysis process, keep higher conversion rate and isononaldehyde selectivity in a multiple cyclic catalysis process, solve the problem of poor hydroformylation reactivity of trisubstituted olefins, and simultaneously provide a novel catalysis method for solving the problem of low isomerization-hydroformylation reaction rate of intermediate olefins, wherein the conversion rate of diisobutylene hydroformylation reaction is more than 95 percent and the isononaldehyde selectivity is more than 97 percent.
Description
Technical Field
The invention relates to the technical field of diisobutylene hydroformylation, in particular to a catalyst composition based on a combination of a phosphoranylidene amide diphosphine ligand and a phosphoranylidene amide monophosphine ligand, and application of the catalyst composition in diisobutylene hydroformylation.
Background
Since the first discovery of the hydroformylation reaction by Ruhrchemie AG in the work of the Fischer-Tropsch synthesis study, the German scientist Otto Roelen teaches that the reaction is one of the most successful homogeneous catalytic reactions for industrial applications due to the important use of the product aldehyde and high added value due to 100% atomic economy.
The byproduct isobutene of ethylene refinery is dimerized to obtain oligomerization diisobutylene, and the oligomerization diisobutylene mainly comprises 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene. Isononal generated by hydroformylation reaction of diisobutylene and synthesis gas under the catalysis of transition metal, namely 3, 5-trimethylhexanal, is an important chemical product, and generates isononyl alcohol (INA) after hydrogenation reduction reaction, the isononyl alcohol is mainly used for producing advanced plasticizers such as diisononyl phthalate (DINP), cyclohexane 1, 2-dicarboxylic acid diisononyl ester (DINCH), diisononyl adipate (DINA), and the like, and the novel plasticizer which has excellent performance, is safe and environment-friendly has no reproduction toxicity, can be used as a novel environment-friendly substitute of dioctyl phthalate (DOP) which is a traditional plasticizer, and is added into plastic products of children toys and contact products.
The diisobutylene is subjected to hydroformylation reaction to prepare isononanal, and hydrogenation reduction is carried out to prepare isononanol, wherein the reaction path is as follows:
The prior art relates to a diisobutylene hydroformylation reaction technology for preparing isononyl aldehyde, wherein the adopted catalytic system mainly comprises a traditional cobalt catalytic system, a phosphine ligand modified cobalt catalytic system, a supported cobalt catalytic system, a porous phosphine ligand polymer supported rhodium catalytic system and a phosphine ligand modified rhodium catalytic system.
However, in the cobalt catalyst system, cobalt carbonyl hydride is used as a catalyst, after the reaction is finished, strong alkali or strong oxidant with organic acid is needed to treat the reaction to generate sodium tetracarbonylcobaltate solution or organic cobalt (bivalent cobalt) carboxylate solution, the aqueous solution is separated, and after being treated by strong acid or reducing agent, the catalyst is regenerated into cobalt carbonyl hydride, and the cobalt carbonyl hydride is put into the reaction for continuous use. The greatest disadvantage of the process is that a large amount of wastewater is generated, which causes serious pollution to the environment. Phosphite monophosphine ligand modified rhodium is used as a catalyst, and can show high catalyst activity under mild conditions, especially under low synthesis pressure, but the ligand has poor thermal stability, and byproducts after thermal decomposition can poison rhodium catalysts. The triphenylphosphine oxide modified rhodium catalyst has the problems of harsh reaction conditions and lower reaction activity, and the triphenylphosphine oxide has weak coordination capacity, so that the rhodium catalyst has poor stability.
In addition, diisobutylene generally comprises 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene in any ratio, and the reaction rate of the isomerisation-hydroformylation of 2, 4-trimethyl-2-pentene is more affected by such factors as rhodium electron receiving capacity, steric effects around rhodium and the like. However, the existing catalytic system is difficult to effectively improve the isomerization-hydroformylation reaction rate of 2, 4-trimethyl-2-pentene, so that the problems of low isononaldehyde yield, low conversion rate and the like are caused, and particularly, diisobutylene with larger proportion of 2, 4-trimethyl-2-pentene is solved.
In summary, the existing catalytic system for diisobutylene hydroformylation has the defects of harsh reaction conditions, high equipment requirements, high energy consumption, low reaction activity, poor catalyst stability, large loss and the like.
Disclosure of Invention
The invention aims to provide a diisobutylene hydroformylation catalyst composition, which comprises a phosphoramidite diphosphine ligand and a phosphoramidite monophosphine ligand which are mixed in a certain proportion, can effectively enhance pi electron receiving capacity of rhodium which is a catalyst active species and space effect around rhodium, accelerates coordination of diisobutylene and rhodium metal to improve the reaction rate of 2, 4-trimethyl-2-pentene isomerization-hydroformylation, further improves the conversion rate of olefin hydroformylation reaction and the yield of isononanal, and has the advantages of high stability, easy separation after reaction, capability of recycling on the premise of keeping higher yield and conversion rate, and remarkably reduced catalyst investment cost.
The aim of the invention is achieved by the following technical scheme:
A diisobutylene hydroformylation catalyst composition comprising a first phosphine ligand having a structure represented by formula I and a second phosphine ligand having a structure represented by formula II:
In formula I, formula II, R 1、R2 and R 3 are each independently selected from hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, halogen, acyl, ester, acyloxy, nitro, cyano.
In this embodiment, the phosphine ligand of the catalyst composition comprises a first phosphine ligand and a second phosphine ligand mixed in a certain ratio. The first phosphine ligand with the structural formula shown in the formula I is a phosphoranylidene amide diphosphine ligand, has stronger chelating capacity, can better protect catalyst active species, namely rhodium phosphine complex for catalyzing double bond isomerization-hydroformylation tandem reaction of intermediate olefin, enhances the stability of rhodium catalyst, and is further beneficial to improving the circulating catalytic capacity of the catalytic system. However, such phosphoramidite bisphosphine ligands, when used alone to catalyze diisobutylene hydroformylation, have a slow diisobutylene hydroformylation rate due to crowding of the steric structure around the rhodium metal under the rhodium/bisphosphine catalyst system, resulting in a slow rate of isomerisation of the double bond of the more sterically hindered 2, 4-trimethyl-2-pentene (one of the diisobutylene feed components) to 2, 4-trimethyl-1-pentene.
The second phosphine ligand with the structural formula shown in the formula II is a phosphoramidite monophosphine ligand which has an isomerization function and strong pi electron receiving capacity, and can effectively improve the reaction rate of olefin isomerization-hydroformylation in the diisobutylene reaction process, but when the second phosphine ligand is independently used in a diisobutylene hydroformylation catalytic system, the isononaldehyde selectivity of the phosphoramidite monophosphine ligand is not high, the stability of a rhodium phosphine catalyst is poor, the catalytic system is difficult to recycle, and the industrialized application cost is high.
In the process of catalyzing diisobutylene hydroformylation reaction, 2, 4-trimethyl-2-pentene in diisobutylene is isomerized under the action of rhodium-phosphine composite catalyst to generate 2, 4-trimethyl-1-pentene, and then the hydroformylation reaction is carried out to generate isononyl aldehyde.
The inventor finds that when the combination of the phosphonite monophosphine ligand and the phosphonite biphosphine ligand with specific combination is applied to the diisobutylene hydroformylation reaction, the strategy that a rhodium catalyst precursor and a first ligand and a second ligand of a P-N structure model with strong pi electron receiving capability are adopted to form the specific combination catalyst enhances the rhodium electron receiving capability of a catalyst active species and the space effect around rhodium, accelerates the coordination of diisobutylene and rhodium metal, further improves the reaction rate of 2, 4-trimethyl-2-pentene isomerization, improves the yield of isononaldehyde, and can enhance the stability and the catalytic activity of rhodium of the catalyst active species in the cyclic catalysis process, and the catalyst combination can maintain higher conversion rate and isononaldehyde selectivity in the cyclic catalysis process.
As a preferred embodiment of the first phosphine ligand in the present invention, the first phosphine ligand has any one of the following structural formulas:
as a preferred embodiment of the second phosphine ligand in the present invention, the second phosphine ligand has any one of the following structural formulas:
Further, the molar ratio of the first phosphine ligand to the second phosphine ligand is 1:10-1:80. Experiments show that when the mole ratio of the first phosphine ligand to the second phosphine ligand is 1:10-1:80, the catalyst solution containing the catalyst composition can ensure the conversion rate of more than 80%, the isononaldehyde selectivity is as high as 98%, and the higher conversion rate and isononaldehyde selectivity can be maintained in the process of multiple cycles. When the first phosphine ligand is too little or the second phosphine ligand is too much, the conversion of the diisobutylene hydroformylation reaction will decrease, and the number of recycle catalysis to maintain high conversion and high selectivity will also decrease. Preferably, the molar ratio of the first phosphine ligand to the second phosphine ligand is from 1:20 to 1:80, and more preferably, the molar ratio of the first phosphine ligand to the second phosphine ligand is from 1:20 to 1:40.
Further, the catalyst further comprises a rhodium catalyst precursor, the molar ratio of the first ligand to the rhodium catalyst precursor is 0.5-10, and the molar ratio of the second ligand to the rhodium catalyst precursor is 20-80. The catalyst composition also comprises a rhodium catalyst precursor, wherein the molar ratio of the first ligand to the rhodium catalyst precursor is 0.5-10, preferably 0.5-4, and more preferably 1-2; the molar ratio of the second ligand to the rhodium catalyst precursor is 20 to 80, preferably 20 to 40, and more preferably 30 to 40.
Further, the rhodium catalyst precursor is at least one of Rh(acac)(CO)2、[Rh(CO)2]2Cl2、Rh(COD)2BF4、Rh(nbd)2BF4、Rh(COD)(acac)、HRh(CO)(TPP)3、RhCl3、[Rh(COD)Cl]2、Rh(C2H4)(acac)、[Rh(C2H4)Cl]2、Rh(OAc)3、Rh2(OAc)4、Rh(NO3)3、[Rh(C7H15COO)2]2, wherein acac is acetyl acetonyl, COD is 1, 5-cyclooctadiene, nbd is norbornadiene, TPP is triphenylphosphine, and OAc is acetate ion. Preferably, the rhodium catalyst precursor is Rh (acac) (CO) 2.
The invention further aims to provide the application of the catalyst composition in diisobutylene hydroformylation based on any diisobutylene hydroformylation catalyst composition, so that the reaction rate of 2, 4-trimethyl-2-pentene isomerization-hydroformylation can be improved, the service life of the catalyst is prolonged, the yield and the conversion rate are increased in multiple cycles, and the reaction condition is mild, thereby meeting the industrial mass production.
The aim of the invention is achieved by the following technical scheme:
based on the use of any of the foregoing catalyst compositions in a diisobutylene hydroformylation reaction, the use comprising the steps of:
Uniformly mixing the catalyst composition, diisobutylene and a solvent to form a reaction solution, wherein the reaction solution reacts with synthesis gas formed by carbon monoxide and hydrogen at high temperature and high pressure;
after the reaction is completed, the product is separated from the catalyst solution by distillation under reduced pressure, which can be reused for catalyzing the newly added diisobutylene.
In the technical scheme, a catalyst composition formed by rhodium catalyst precursor, a first phosphine ligand and a second phosphine ligand, diisobutylene prepared by mixing 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene according to any proportion and a solvent are added into a high-pressure reaction kettle. After the reactor is closed, the air in the reactor is replaced by a synthesizer formed by carbon monoxide and hydrogen for a plurality of times, and then a proper amount of synthesis gas is filled to keep a certain pressure in the reactor, after the reaction is carried out for a period of time at high temperature and high pressure, the product aldehyde is obtained by distillation and separation, and at the moment, the catalyst solution at the bottom of the reactor still has higher activity and stability and can be used for cyclic catalytic reaction. The steps of the cyclic catalytic reaction are the same as the steps of the cyclic catalytic reaction, the catalyst composition is not required to be added in each cyclic reaction, and the catalyst composition remained in the kettle after distillation separation is utilized to catalyze the newly added diisobutylene hydroformylation reaction.
In one or more embodiments, the solvent is at least one of 3, 5-trimethylhexanal, 3, 5-trimethylhexanol, xylene, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, 1-octanol, 1-nonanol, 1-decanol, diethylene glycol, triethylene glycol, tetraethylene glycol.
In one or more embodiments, the catalytic reaction is in the form of a batch or continuous reaction for a period of time ranging from 3 hours to 10 hours, preferably from 6 hours to 8 hours.
In one or more embodiments, after the reaction is finished, a stepwise separation method is adopted, unreacted diisobutylene is firstly distilled under the condition of 45-50 ℃ per-0.09 MPa, and then isononanal is distilled under the condition of 80-90 ℃ per-0.09 MPa to-0.095 MPa. The separated diisobutylene can be used as a raw material to be continuously put into reaction, and the catalyst solution separated from the product is continuously reused after the raw material diisobutylene is added.
In one or more embodiments, the composition of the syngas is from 1:0.9 to 1.5:1, preferably from 1:1 to 1.2:1, by volume of H 2 to CO.
Further, the molar ratio of rhodium catalyst precursor to diisobutylene in the catalyst composition is from 1:500 to 1:10000. Preferably, the rhodium concentration in the catalyst solution is from 50ppm to 600ppm, preferably from 200ppm to 400ppm.
Further, the reaction temperature is 70-100 ℃, and the reaction pressure is 2-5 MPa. The reaction temperature of the diisobutylene hydroformylation reaction using the catalyst composition may be between 60 and 120 ℃, preferably between 70 and 100 ℃, and more preferably between 80 and 90 ℃. The pressure of the constant pressure reaction may be 1 to 8MPa, preferably 2 to 5MPa, and more preferably 3 to 5MPa.
Further, the catalyst solution is capable of repeatedly cycling the catalytic diisobutylene at least 5 times, with an olefin conversion greater than 95% and isononanal selectivity greater than 97% per cycle of catalytic reaction.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. The catalyst composition provided by the invention comprises a specific combination of a phosphoramidite monophosphine ligand and a phosphoramidite biphosphine ligand, when the catalyst composition is used in diisobutylene hydroformylation, the first ligand and the second ligand of a P-N structure model with strong pi electron receiving capability enhance the rhodium electron receiving capability of a catalyst active species and the space effect around rhodium, so that the coordination of diisobutylene and rhodium metal is accelerated, the reaction rate of 2, 4-trimethyl-2-pentene isomerization is further improved, the yield of isononaldehyde is improved, in addition, in the cyclic catalysis process, the catalyst combination can strengthen the stability and the catalytic activity of rhodium of the catalyst active species, can keep higher conversion rate and isononaldehyde selectivity in the repeated cyclic catalysis process, solve the problem of poor hydroformylation reaction activity of trisubstituted olefins, and simultaneously provide a novel catalysis method for solving the problem of low intermediate olefin isomerization-hydroformylation reaction rate, wherein the conversion rate of diisobutylene is more than 95%, and the isononaldehyde selectivity is more than 97%;
2. When the first phosphine ligand is too little or the second phosphine ligand is too much, the conversion rate of diisobutylene hydroformylation reaction is reduced, and the recycling times of the catalyst which keeps high conversion rate and high selectivity are also reduced, so that when the molar ratio of the first phosphine ligand to the second phosphine ligand is 1:10-1:80, the catalyst solution containing the catalyst composition can ensure the conversion rate of olefin with more than 80 percent, the selectivity of isononaldehyde is up to 98 percent, and the higher conversion rate and isononaldehyde selectivity can be kept in the process of multiple times of recycling;
3. the application of the catalyst composition in diisobutylene hydroformylation reaction can improve the reaction rate of 2, 4-trimethyl-2-pentene isomerization-hydroformylation, keep longer service life of the catalyst, keep higher yield and conversion rate in multiple cycles, and has mild reaction conditions, thus being suitable for industrial scale production.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
All the raw materials of the present invention are not particularly limited in their sources, and can be commercially available or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in terms of purity, and the invention preferably employs the purity requirements customary in the art of analytically pure or diisobutylene hydroformylation.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
The expression of the substituents is not particularly limited in the present invention, and all of them are well known to those skilled in the art, and those skilled in the art can correctly understand the meaning based on the general knowledge.
The use of "first", "second", etc. (e.g., first phosphine ligand, second phosphine ligand, etc.) in the present invention is merely for clarity of description to distinguish the corresponding components/materials/compounds, and is not intended to limit any order or emphasize importance, etc.
1. Synthesis of the first phosphine ligand:
[ example 1]
First phosphine ligand a: preparation of 2,2 '-bis (diindolylphosphinoxy) -1,1' -biphenyl:
To a 250mL three necked flask under N 2 protection were added sequentially 50mL of water-dehydrated deoxygenated THF, 3.0mL of PCl 3 (34.4 mmol) and 10.5mL (2.2 eq.,75.7 mmol) of anhydrous anaerobic Et 3 N, and cooled to 0℃in an ice-water bath. To a 100mL dried constant pressure dropping funnel were added 8.06g indole (2.0 eq.,68.8 mmol) and 40mL anhydrous and oxygen free THF in this order. The mixed solution in the constant pressure dropping funnel was slowly dropped into a three-necked flask at 0℃with vigorous stirring, and a white Et 3 N. HCl solid was immediately seen to be generated at the bottom of the flask upon dropping. After the dripping is completed, the temperature is raised by adopting a program, the strong stirring is carried out for 0.5h under the condition of maintaining the temperature at 0 ℃, and then the ice bath is removed, so that the reaction liquid is naturally heated to the ambient temperature. The reaction solution was used directly for the next reaction without any treatment.
To the above 100mL constant pressure dropping funnel were added 2.7g of 2,2', -dihydroxy-1, 1', -biphenyl and 30mL of anhydrous and anaerobic THF, respectively, and then 4.5mL of anhydrous and anaerobic Et 3 N (2.2 eq.,32.2 mmol) was added to the three-necked flask, the solution was cooled to 0deg.C, and the 2,2' -dihydroxybiphenyl solution in the constant pressure dropping funnel was added dropwise to the above diindole chlorophosphine-containing solution over 30min. After the dropwise addition was completed, the vigorous stirring was continued at 0℃for 0.5h, then the ice bath was removed to slowly and naturally raise it to ambient temperature, and then slowly heated to 40 ℃. The stirring was continued vigorously for 12h while maintaining 40 ℃. After the reaction was completed, the heating of the reaction solution was stopped, and the reaction solution was slowly cooled to ambient temperature. The mixture was filtered to obtain a pale yellow filtrate, and 30mL of absolute ethanol was slowly added dropwise to obtain 8.9g of a crude product by recrystallization. After a second recrystallization 7.4g of crystalline solid are obtained, namely the first phosphine ligand A:
Nuclear magnetic characterization data ：1H NMR(400MHz,CDCl3)δ7.56(d,J＝7.8Hz,4H),7.33(d,J＝8.2Hz,4H),7.26(dd,J＝7.1,1.6Hz,2H),7.16-7.00(m,16H),6.78(d,J＝8.0Hz,2H),6.50(d,J＝3.4Hz,4H).
31P NMR(162MHz,CDCl3)δ104.29.
[ Example 2]
First phosphine ligand B: preparation of 2,2 '-bis (diindolylphosphinoxy) -1,1' -binaphthyl:
To a 250mL three necked flask under N 2 protection were added sequentially 50mL of water-dehydrated deoxygenated THF, 3.0mL of PCl 3 (34.4 mmol) and 10.5mL (2.2 eq.,75.7 mmol) of anhydrous anaerobic Et 3 N, and cooled to 0℃in an ice-water bath. To a 100mL dried constant pressure dropping funnel were added 8.06g indole (2.0 eq.,68.8 mmol) and 40mL anhydrous and oxygen free THF in this order. The mixed solution in the constant pressure dropping funnel was slowly dropped into a three-necked flask at 0℃with vigorous stirring, and a white Et 3 N. HCl solid was immediately seen to be generated at the bottom of the flask upon dropping. After the dripping is completed, the temperature is raised by adopting a program, the reaction solution is firstly stirred for 0.5h under the condition of maintaining the temperature of 0 ℃, and then the ice bath is removed, so that the reaction solution is naturally heated to the ambient temperature. The reaction solution was used directly for the next reaction without any treatment.
3.2G of 2,2', -dihydroxy-1, 1', -binaphthyl and 30mL of anhydrous and anaerobic THF were added to the 100mL constant pressure dropping funnel, 4.5mL of anhydrous and anaerobic Et 3 N (2.2 eq.,32.2 mmol) was added to the three-necked flask, the solution was cooled to 0℃and the 2,2', -dihydroxy-1, 1' -binaphthyl solution in the constant pressure dropping funnel was slowly added dropwise to the solution containing diindole chlorophosphine over 30 min. After the dropwise addition was completed, the vigorous stirring was continued at 0℃for 0.5h, then the ice bath was removed to slowly and naturally raise it to ambient temperature, and then slowly heated to 40 ℃. The stirring was continued vigorously for 12h while maintaining 40 ℃. After the reaction was completed, the heating of the reaction solution was stopped, and the reaction solution was slowly cooled to ambient temperature. The mixture was filtered to obtain a pale yellow filtrate, and 30mL of absolute ethanol was slowly added dropwise to obtain 9.2g of a crude product by recrystallization. After a second recrystallization 6.6g of crystalline solid was obtained, namely the first phosphine ligand B:
nuclear magnetic characterization data ：1H NMR(400MHz,CDCl3)δ7.81(d,J＝8.2Hz,2H),7.71(d,J＝8.9Hz,2H),7.54(d,J＝7.8Hz,2H),7.47(d,J＝7.8Hz,2H),7.40(ddd,J＝8.1,6.3,1.6Hz,2H),7.29-7.21(m,6H),7.19(d,J＝8.2Hz,2H),7.10(qd,J＝7.9,0.7Hz,6H),7.03-6.92(m,4H),6.80-6.70(m,4H),6.39(d,J＝3.3Hz,2H),6.33(d,J＝3.4Hz,2H).
31P NMR(162MHz,CDCl3)δ104.71.
2. Synthesis of second phosphine ligand
Wherein,Is pyrrole structural derivative, R is selected from aromatic ring, aromatic heterocycle, aryl, alkyl, cycloalkyl, cycloheteroalkyl, hydrogen, etc., including pyrrole, indole, carbazole, derivatives thereof, etc.
[ Example 3]
Second phosphine ligand 1: synthesis of tris (5-methoxyindolyl) phosphine ligand:
600mL of molecular sieve dried tetrahydrofuran, 120.9g of 5-methoxyindole (1031.5 mmol) and 170mL (1237.8 mmol) of molecular sieve dried triethylamine solution were added sequentially to a 1000mL three-necked round bottom flask at 0deg.C under N 2. 30mL of phosphorus trichloride (343.8 mmol) was added in portions to the above solution containing 5-methoxyindole and triethylamine using a syringe with vigorous stirring to give a large amount of white triethylamine hydrochloride solid immediately upon dropwise addition, forming a suspension. After phosphorus trichloride is completely added into the reaction system, continuously maintaining the temperature at 0 ℃ for half an hour, removing the ice bath, and naturally heating the reaction solution to the ambient temperature. And then stirring the mixture strongly overnight to finally obtain a slightly yellowish reaction solution. Filtering, washing, removing the solvent, adding a poor solvent for recrystallization to obtain a slightly yellowish white solid, and finally obtaining 129.1g of white solid after filtering and drying, wherein the yield is 80%, namely the second phosphine ligand 1:
Nuclear magnetic characterization data ：1H NMR(400MHz,CDCl3)δ7.38(d,J＝8.9Hz,3H),7.09(d,J＝1.1Hz,3H),6.94(t,J＝3.2Hz,3H),6.84(dd,J＝9.0,2.5Hz,3H),6.62(d,J＝3.4Hz,3H),3.84(s,9H).
31P NMR(162MHz,CDCl3)δ68.35.
[ Example 4]
Second phosphine ligand 2: synthesis of the tri-indolylphosphine ligand:
600mL of molecular sieve dried tetrahydrofuran, 120.6g of indole (1031.5 mmol) and 170mL (1.2X105 mmol) of molecular sieve dried triethylamine (acid binding agent, typically organic base) were added sequentially to a 1000mL three neck round bottom flask at 0deg.C under N 2. 30mL of phosphorus trichloride (343.8 mmol) was added to the above solution containing indole and triethylamine in portions with vigorous stirring using a syringe, yielding a large amount of white triethylamine hydrochloride solid immediately upon dropwise addition, forming a suspension. And after the phosphorus trichloride is completely added into the reaction system, continuously maintaining the temperature at 0 ℃ for half an hour, removing the ice bath, and naturally heating the reaction liquid to the ambient temperature. And then stirring the mixture strongly overnight to finally obtain a slightly yellowish reaction solution. Filtering, washing, removing the solvent, adding a poor solvent for recrystallization to obtain a slightly yellowish white solid, and finally obtaining 97.8g of white solid after filtering and drying, wherein the yield is 75%, namely the second phosphine ligand 2:
Nuclear magnetic characterization data:
1H NMR(400MHz,CDCl3)δ7.79-7.62(m,6H),7.37-7.26(m,6H),7.10-7.01(m,3H),6.78(d,J＝3.4Hz,3H).
31P NMR(162MHz,CDCl3)δ66.82.
[ example 5]
Second phosphine ligand 3: the tri (6-chloroindolyl) phosphine ligand is synthesized:
600mL of molecular sieve dried tetrahydrofuran, 156.4g of indole (1031.5 mmol) and 170mL (1.2 x 1031.5 mmol) of molecular sieve dried triethylamine (acid-binding agent, typically organic base) were added sequentially to a 1000mL three neck round bottom flask under protection of 0, N 2 to form a solution. 30mL of phosphorus trichloride (343.8 mmol) was added to the above solution containing indole and triethylamine in portions with vigorous stirring using a syringe, yielding a large amount of white triethylamine hydrochloride solid immediately upon dropwise addition, forming a suspension. And after the phosphorus trichloride is completely added into the reaction system, continuously maintaining the temperature at 0 ℃ for half an hour, removing the ice bath, and naturally heating the reaction liquid to the ambient temperature. And then stirring the mixture strongly overnight to finally obtain a slightly yellowish reaction solution. Filtering, washing, removing the solvent, adding a poor solvent for recrystallization to obtain a slightly yellowish white solid, and finally obtaining 117.8g of tris (6-chloroindolyl) phosphine ligand with the yield of 71%, namely a second phosphine ligand 3:
nuclear magnetic characterization data ：1H NMR(400MHz,CDCl3)δ7.61–7.51(m,6H),7.22(dd,J＝8.5,1.7Hz,3H),6.92–6.86(m,3H),6.70(d,J＝3.4Hz,3H).
31P NMR(162MHz,CDCl3)δ66.25.
[ Example 6]
Second phosphine ligand 4: tris (5-fluoroindolyl) phosphine ligands
600ML of molecular sieve dried tetrahydrofuran, 139.2g of indole (1031.5 mmol) and 170mL (1.2 x 1031.5 mmol) of molecular sieve dried triethylamine (acid-binding agent, typically organic base) were added sequentially to a 1000mL three neck round bottom flask under protection of 0, N 2 to form a solution. 30mL of phosphorus trichloride (343.8 mmol) was added to the above solution containing indole and triethylamine in portions with vigorous stirring using a syringe, yielding a large amount of white triethylamine hydrochloride solid immediately upon dropwise addition, forming a suspension. And after the phosphorus trichloride is completely added into the reaction system, continuously maintaining the temperature at 0 ℃ for half an hour, removing the ice bath, and naturally heating the reaction liquid to the ambient temperature. And then stirring the mixture strongly overnight to finally obtain a slightly yellowish reaction solution. Filtering, washing, removing the solvent, adding a poor solvent for recrystallization to obtain a slightly yellowish white solid, and finally obtaining 112.0g of tris (5-fluoroindolyl) phosphine ligand with the yield of 78%, namely a second phosphine ligand 4:
nuclear magnetic characterization data ：1H NMR(400MHz,CDCl3)δ8.08(d,J＝7.4Hz,6H),7.29–7.24(m,6H),7.15(ddd,J＝12.4,9.5,4.6Hz,12H).
31P NMR(162MHz,CDCl3)δ67.63.
3. Dipolyisobutene hydroformylation
Examples 7 to 17
Adding Rh (acac) (CO) 2, a first phosphine ligand and a second phosphine ligand into a 50mL high-pressure reaction kettle respectively to form a combined catalyst, wherein rhodium concentration=200-300 ppm, the molar ratio of the first phosphine ligand to Rh is 0.5-10, the molar ratio of the second phosphine ligand to Rh is 20-80, and 40mL diisobutylene (S/C=8200), and closing the kettle. After the synthesis gas is replaced by air in the reaction kettle for three times, a proper amount of synthesis gas is filled, after the synthesis gas is heated to the reaction temperature, the reaction is carried out at constant pressure and constant pressure for 6 hours, and the experimental results are shown in table 1:
table 1:
as can be seen from Table 1, the catalyst combination provided by the invention effectively improves the reaction rate of diisobutylene hydroformylation and the selectivity of aldehyde, and particularly provides the best mole ratio of the first phosphine ligand to the second phosphine ligand, the catalyst formed by the catalyst combination and rhodium precursor has the highest catalytic activity, and the diisobutylene conversion rate reaches more than 96%. Further, under the preferred condition that the molar ratio of the first phosphine ligand to the second phosphine ligand is 2:40, after different first phosphine ligands (A, B) and second phosphine ligands (1, 2,3 and 4) are combined in a crossing way, the catalyst can keep high catalytic activity in the diisobutylene hydroformylation reaction, wherein the diisobutylene conversion rate reaches 96%, and the isononyl aldehyde selectivity reaches 98%.
Example 18
The catalyst composition composed of the first phosphine ligand A and the second phosphine ligands 1 and Rh (acac) (CO) 2 is used for circulating catalytic reaction of diisobutylene. After the first catalytic reaction is finished, separating the obtained product aldehyde, continuously recycling the catalyst solution at the bottom of the kettle for 5 times, and obtaining experimental results shown in table 2:
Table 2:
As can be seen from Table 2, the combination of the first phosphine ligand A and the second phosphine ligand 1 adopted and the rhodium catalyst precursor catalyze diisobutylene to carry out hydroformylation reaction, after the catalyst is recycled for 5 times, the conversion rate and the selectivity are not obviously changed, the conversion rate of olefin in each recycling catalytic reaction is more than 95%, and the selectivity of isononyl aldehyde is more than 97%, because the combination of the first phosphine ligand A and the second phosphine ligand 1 jointly regulates and controls the electron receiving capacity of rhodium and the space effect around rhodium of the catalyst active species, and the rhodium catalyst active species can be effectively stabilized.
As can be seen from comparative example 1, when the first phosphine ligand A is singly used for catalyzing the diisobutylene hydroformylation reaction with rhodium precursor, the conversion rate of olefin is basically stabilized at about 75% in the process of recycling 5 times, and the catalytic effect is obviously lower than that of the catalyst composition taking the combination of the first phosphine ligand A and the second phosphine ligand 1 as the catalyst composition; meanwhile, as is clear from comparative example 2, the catalyst activity is drastically reduced in the course of circulation by catalyzing diisobutylene hydroformylation reaction with the second phosphine ligand 1 and rhodium precursor, and after the catalyst is recycled for 5 times, the catalyst has basically no catalytic activity, and it is presumed that the chelating ability of the second phosphine ligand 1 and rhodium is poor, so that the rhodium phosphine catalytic active species cannot be effectively stabilized, resulting in conversion of the lao catalytic active species into rhodium phosphine compounds of inactive species.
[ Example 19]
After the catalytic reaction is finished, the unreacted olefin raw material is distilled and separated, the separation temperature is 40-45 ℃, the separation vacuum degree is-0.09 MPa to-0.095 MPa, and the obtained olefin is put into a reaction kettle again for reaction under the reaction conditions: [ Rh ] =300 ppm, first phosphine ligand a and second phosphine ligand 1, first phosphine ligand a/rh=2, second phosphine ligand 1/rh=40, 40mL diisobutylene (81% 2, 4-trimethyl-1-pentene and 19%2, 4-trimethyl-2-pentene mixture, S/c=8200), heated to 90 ℃, synthesis gas maintained at a constant pressure of 5MPa, and reaction time of 6h. The experimental results are shown in table 3:
TABLE 3 Table 3
As can be seen from Table 3, in the hydroformylation reaction of diisobutylene catalyzed by the rhodium catalyst precursor, the combination of the first phosphine ligand A and the second phosphine ligand 1 adopted in the invention isomerizes 2, 4-trimethyl-2-pentene to form 2, 4-trimethyl-1-pentene under the action of the rhodium phosphine catalyst, and the hydroformylation reaction is carried out to generate isononaldehyde.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. Use of a catalyst composition in a diisobutylene hydroformylation reaction, said use comprising the steps of:
uniformly mixing a catalyst composition, diisobutylene and a solvent to form a reaction solution, wherein the reaction solution reacts with synthesis gas formed by carbon monoxide and hydrogen at high temperature and high pressure;
after the reaction is finished, separating a product from a catalyst solution in a reduced pressure distillation mode, wherein the catalyst solution can be repeatedly used for catalyzing newly added diisobutylene;
Wherein the catalyst composition comprises a first phosphine ligand having a structure shown in formula I and a second phosphine ligand having a structure shown in formula II:
In formula I, formula II, R 1、R2 and R 3 are each independently selected from hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, alkoxy, halogen, acyl, ester, acyloxy, nitro, cyano;
wherein the molar ratio of the first phosphine ligand to the second phosphine ligand is 1:10-1:80;
Wherein the diisobutylene hydroformylation catalyst composition further comprises a rhodium catalyst precursor, the molar ratio of the first phosphine ligand to the rhodium catalyst precursor is 0.5-10, and the molar ratio of the second phosphine ligand to the rhodium catalyst precursor is 20-80.
2. The use according to claim 1, wherein the first phosphine ligand has any one of the following structural formulas:
3. The use according to claim 1, wherein the second phosphine ligand has any one of the following structural formulas:
4. The use according to claim 1, wherein the rhodium catalyst precursor is at least one of Rh(acac)(CO)2、[Rh(CO)2]2Cl2、Rh(COD)2BF4、Rh(nbd)2BF4、Rh(COD)(acac)、HRh(CO)(TPP)3、RhCl3、[Rh(COD)Cl]2、Rh(C2H4)(acac)、[Rh(C2H4)Cl]2、Rh(OAc)3、Rh2(OAc)4、Rh(NO3)3、[Rh(C7H15COO)2]2, wherein acac is acetyl, COD is 1, 5-cyclooctadiene, nbd is norbornadiene, TPP is triphenylphosphine, OAc is acetate ion.
5. The use according to claim 1, wherein the molar ratio of rhodium catalyst precursor to diisobutylene in the catalyst composition is from 1:500 to 1:10000.
6. The use according to claim 1, wherein the reaction temperature is 70-100 ℃ and the reaction pressure is 2-5 MPa.
7. The use according to claim 1, wherein the catalyst solution is capable of repeatedly cycling the catalytic diisobutylene at least 5 times, and the conversion of olefins per cycle of catalytic reaction is greater than 95% and the isononyl aldehyde selectivity is greater than 97%.
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