CN116410389A - Organic phosphine ligand polymer and preparation method and application thereof - Google Patents
Organic phosphine ligand polymer and preparation method and application thereof Download PDFInfo
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- CN116410389A CN116410389A CN202111674374.8A CN202111674374A CN116410389A CN 116410389 A CN116410389 A CN 116410389A CN 202111674374 A CN202111674374 A CN 202111674374A CN 116410389 A CN116410389 A CN 116410389A
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000003446 ligand Substances 0.000 title claims abstract description 101
- 229920000642 polymer Polymers 0.000 title claims abstract description 85
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000007037 hydroformylation reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 229940125782 compound 2 Drugs 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 239000010948 rhodium Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000006886 vinylation reaction Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 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
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- 229940126214 compound 3 Drugs 0.000 description 13
- 229940015043 glyoxal Drugs 0.000 description 13
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DJLBVUYUIACDIU-UHFFFAOYSA-N tris(4-ethenylphenyl)phosphane Chemical compound C1=CC(C=C)=CC=C1P(C=1C=CC(C=C)=CC=1)C1=CC=C(C=C)C=C1 DJLBVUYUIACDIU-UHFFFAOYSA-N 0.000 description 4
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- KMJZIGLLNWFDIG-UHFFFAOYSA-N buta-1,3-diene;toluene Chemical compound C=CC=C.CC1=CC=CC=C1 KMJZIGLLNWFDIG-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 150000008301 phosphite esters Chemical group 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- -1 J.mol.Catal.A: chem. Chemical compound 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 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 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 238000011925 1,2-addition Methods 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HEOKFDGOFROELJ-UHFFFAOYSA-N diacetal Natural products COc1ccc(C=C/c2cc(O)cc(OC3OC(COC(=O)c4cc(O)c(O)c(O)c4)C(O)C(O)C3O)c2)cc1O HEOKFDGOFROELJ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QIWRFOJWQSSRJZ-UHFFFAOYSA-N tributyl(ethenyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C=C QIWRFOJWQSSRJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Health & Medical Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides an organic phosphine ligand polymer, a preparation method and application thereof, wherein the structure of the organic phosphine ligand polymer is shown as a general formula (I),
wherein R is 1 And R is 2 Selected from the same or different phosphorus-containing groups, m is 35-45, n is 35-1350. The organophosphine ligand polymers of the present invention are prepared by forming heterogeneous rhodiumThe catalyst system not only has high activity and high selectivity of a homogeneous catalyst, but also has the convenience in separating the catalyst from products, and can greatly reduce the production cost.
Description
Technical Field
The invention relates to the technical field of olefin hydroformylation, in particular to an organic phosphine ligand polymer, a preparation method and application thereof.
Background
The hydroformylation of olefins is a reaction for converting olefins, hydrogen and carbon monoxide into aldehydes using a transition metal catalyst, and has been developed as one of the most important industrial homogeneous catalytic reactions. The ability to produce aldehydes and alcohols by hydroformylation has been statistically more than 1000 ten thousand t/a worldwide.
The hydroformylation reaction process has the characteristics of strong atom economy, wide product application and the like, but olefin substrates are mainly concentrated on a-olefin and internal olefin in industrial production so far, but the hydroformylation reaction of butadiene is challenging, and mainly because the hydroformylation reaction process of butadiene is relatively complex, multiple reaction paths such as 1, 4-addition carbonylation, 1, 2-addition carbonylation, carbon-carbon double bond isomerization and the like can occur, and meanwhile, the reaction rate is slow, the regioselectivity is difficult to control, and more than ten isomerization products and byproducts are simultaneously generated. Butadiene is therefore a very challenging substrate in hydroformylation reactions, where the design synthesis of phosphine ligands of different structural types is critical to the development of this technology.
Based on the current situation, researchers design and synthesize phosphine ligands and ligand polymers with novel structures, apply the phosphine ligands and ligand polymers to hydroformylation reaction, and realize the recycling of ligands and catalysts through heterogeneous catalysis. EP33554A2 discloses a process for the carbonylation of conjugated dienes, the product being predominantly valeraldehyde with little formation of dialdehydes; US4769498A discloses that polyphosphite ligand polymers with rhodium catalysts can be used in the hydroformylation of 1, 4-hexadiene and 1, 7-octadiene; WO9740003a discloses a class of phosphite bidentate ligands and their use in the hydroformylation of 1, 3-butadiene with a glyoxal selectivity of 22%; CN1087078A discloses a class of polyphosphite ligands, wherein the optimal ligand is 110 ℃, the conversion of 1, 3-butadiene reaches 99% at 900psig, and the glyoxal selectivity is 30%; CN108137451a discloses a class of bidentate phosphine ligands for hydroformylation of 1, 3-butadiene, diacetal of 1, 6-glyoxal accounting for 73% of the total product at 3MPa, 120 ℃ for 18 h; CN110343209a and CN109942750a disclose a phosphoramidite bidentate phosphine ligand copolymer with a conversion of approximately 100%, a linear aldehyde selectivity of 90%, and an l/b value of about 150; CN109836318A discloses an organic phosphine ligand polymer containing Xantphos, and the ligand is applied to a fixed bed catalytic hydroformylation reaction of 1-octene, the TOF value of the optimal condition can be more than 700, and the l/b value can also be about 30.
In addition, many publications report on the preparation of 1, 6-hexanedial by hydroformylation of 1, 3-butadiene, such as J.mol.Catal.A: chem.,1998,133,289 screened a series of phosphine ligands, found that DIOP was most selective for hydroformylation of 1, 3-butadiene, and that 1, 6-hexanedial could reach 37%; organometallics,2015,34,841; ACS catalyst.2016, 6,2802; mol.catalyst, 2020,484,110721 also gives similar results, 1, 6-hexanedial selectivity can be increased to 40% by condition optimization; organometallics,2011,30,3643-3651; ACS catalyst, 2014,4,3593-3604; the optimal structural glyoxal selectivity in phosphonite ligands reported in the literature for Organometallics,2015,34,4102-4108, et al, is close to 50%.
Among them, WO9740003a and CN1087078A disclose a class of phosphite bidentate ligands and polyphosphite ligands, and apply them to the hydroformylation of 1, 3-butadiene with a glyoxal selectivity of less than 30%, a disadvantage of this technique or a disadvantage relative to the present invention: the ligand has low catalytic efficiency for the hydroformylation of butadiene; CN110343209A, CN109942750a and CN109836318A disclose a bidentate phosphine ligand copolymer polymerized with an organophosphine ligand to form a catalytic system with transition metal salts for hydroformylation of terminal olefins or isomerization-hydroformylation of internal olefins; the disadvantages of this technique or the shortcomings with respect to the present invention are: the ligand is used for terminal olefin hydroformylation or isomerization-hydroformylation of internal olefins.
Through research and study for many years, the technology for preparing glyoxal by hydroformylation of butadiene still has the problems of low reaction rate, poor regioselectivity and difficult product separation, industrial production is not realized yet, and the technology is still in a laboratory stage at present. Based on the current situation, the novel heterogeneous catalytic system is developed, so that the heterogeneous catalyst has high activity and high selectivity, and simultaneously has the convenience in separating the catalyst from a product, and is a research key point and a main development direction for realizing the directional preparation of the glyoxal by the hydroformylation of butadiene in the future.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an organic phosphine ligand polymer, a preparation method and application thereof, and a heterogeneous rhodium catalyst system is formed, so that the heterogeneous rhodium catalyst system has high activity and high selectivity of a homogeneous catalyst, and simultaneously has the convenience in separating the catalyst from a product, and the production cost can be greatly reduced.
In order to achieve the aim, the invention provides an organic phosphine ligand polymer, the structure of which is shown as a general formula (I),
wherein R is 1 And R is 2 Selected from the same or different phosphorus-containing groups, R 1 And R is 2 Each independently selected from the following structures, wherein "," means the attachment location, and the same applies below.
R 3 Selected from the group consisting of
m is 35-45, n is 35-1350.
According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, R 1 And R is 2 Each independently selected from
According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, R 3 Selected from the group consisting of
According to an embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, the organophosphine ligand polymer is formed by copolymerizing a bidentate phosphine monomer having a structure represented by the general formula (II) and a vinyl monomer having a structure of
According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, the vinyl monomer is selected from one or more of the following structures.
According to an embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, the molar ratio of the bidentate phosphine monomer to the vinyl monomer is 1 (1-30).
According to a specific embodiment of the present invention, in the above-mentioned organophosphine ligand polymer, preferably, m: n is 1 (1-30), more preferably, 1:10.
According to a specific embodiment of the present invention, preferably, the molecular weight of the organophosphine ligand polymer ranges from 50000 to 200000g/mol.
According to a specific embodiment of the present invention, preferably, the polymerization degree of the organophosphine ligand polymer is 35 to 55.
According to a particular embodiment of the invention, preferably the organophosphine ligand polymer is selected from the group consisting of L 1 Or L 2 The structural formula is as follows.
Wherein m is 35-45, n is 35-1350.
The invention also provides a preparation method of the organic phosphine ligand polymer, which comprises the following steps:
s1: under the condition of inert gas atmosphere and triethylamine, R is reacted with the mixture 1 -Cl and/or R 2 -Cl, compound 2, in a first solvent, to perform a reaction, quenching the reaction, collecting and purifying the reaction product, obtaining the bidentate phosphine monomer;
s2: under the condition of inert gas atmosphere and the existence of azodiisobutyronitrile, enabling the bidentate phosphine monomer and the vinyl monomer to fully contact in a second solvent for copolymerization reaction, terminating the reaction, and collecting and purifying a reaction product to obtain the organic phosphine ligand polymer;
wherein the structure of the compound 2 is
According to a specific embodiment of the present invention, in the above preparation method, preferably, in S2, the copolymerization reaction temperature is 60-100 ℃ and the reaction time is 2-6h.
According to a specific embodiment of the present invention, in the above preparation method, preferably, in S2, the second solvent is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, and toluene.
According to a specific embodiment of the present invention, in the above preparation method, preferably, in S1, the reaction temperature is 0 to 30 ℃ and the reaction time is 5 to 10 hours.
According to a specific embodiment of the present invention, in the above preparation method, preferably, in S1, the first solvent is one or more selected from tetrahydrofuran, toluene, and N, N-dimethylformamide.
According to a specific embodiment of the present invention, preferably, the above preparation method further includes a step of preparing the compound 2, and the preparation method of the compound 2 includes: and (3) under the action of nitrogen atmosphere and a catalyst, enabling the compound 1 and an vinylation reagent to be fully contacted in a third solvent for performing vinylation reaction, and collecting and purifying a reaction product to obtain the compound 2.
According to a specific embodiment of the present invention, in the preparation method of the compound 2, preferably, the vinylation reaction temperature is 10-60 ℃ and the reaction time is 5-10h.
According to a specific embodiment of the present invention, in the method for producing compound 2, preferably, the vinylating agent is selected from the group consisting of
One or more of the following.
According to a specific embodiment of the present invention, in the preparation method of the compound 2, preferably, the catalyst is selected from tetra (triphenylphosphine) palladium, pdCl 2 (dppf) or PdCl 2 (PPh3) 2 One or more of the following.
According to a specific embodiment of the present invention, in the preparation method of the compound 2, preferably, the third solvent is selected from one or more of toluene, tetrahydrofuran, and 1, 4-dioxane.
According to a specific embodiment of the present invention, preferably, as shown in reaction formula 1, the above preparation method includes the steps of:
(1) Adding the compound 1 and a solvent into a reactor, then adding an vinylation reagent and a catalyst, carrying out reflux reaction under the protection of nitrogen for overnight, cooling to room temperature, distilling under reduced pressure to remove the solvent, purifying by column chromatography, and separating to obtain a compound 2;
(2) Adding phosphine chloride compound (R) into a reactor under the protection of nitrogen 1 -Cl and/or R 2 -Cl) and a solvent, cooling to 0 ℃, additionally taking the compound 2 and triethylamine to dissolve in the solvent, dripping the mixture into the reactor at 0 ℃, naturally heating to room temperature for reaction, adding water for quenching reaction, adding ethyl acetate for extraction, drying an organic phase by using anhydrous sodium sulfate, and separating by column chromatography to obtain a bidentate phosphine monomer shown in the general formula (II);
(3) Adding bidentate phosphine monomer and comonomer into reactor
AIBN and solvent react under the protection of nitrogen, after the reaction is finished, the reaction is cooled to room temperature, methanol is added for precipitation, filtration, methanol washing and vacuum drying are carried out, and the organic phosphine ligand polymer shown in the general formula (I) is obtained.
The invention also provides application of the organic phosphine ligand polymer in olefin hydroformylation reaction.
In accordance with a specific embodiment of the present invention, in the above application, preferably, the olefin is selected from C 4 -C 10 The olefin is more preferably butadiene.
In accordance with a specific embodiment of the present invention, in the above application, preferably, the organophosphine ligand polymer forms a heterogeneous rhodium catalyst system.
The organic phosphine ligand polymer is applied to the hydroformylation of low-carbon olefin by forming a heterogeneous rhodium catalyst system, replaces the current widely used rhodium low-pressure oxo synthesis liquid-phase circulation process in industry, simplifies the process flow and greatly reduces the production cost.
The organic phosphine ligand polymer is applied to the hydroformylation of high-carbon olefin by forming a heterogeneous rhodium catalyst system, so that the technical problem that the catalyst is difficult to separate in the hydroformylation process of the high-carbon olefin by using a homogeneous catalyst is thoroughly solved.
(1) The preparation process of the organic phosphine polymer ligand is simple, raw materials are easy to obtain, the phosphine ligand used in the method for synthesizing the copolymer ligand can be directly purchased or synthesized, and the copolymer bidentate phosphine ligand monomer can be copolymerized with a cheap and commercially available vinyl-containing compound, so that the copolymer ligand is cheap and easy to obtain. The raw materials directly react in one step to generate a bidentate phosphine ligand copolymer containing phosphite ester structures;
(2) The preparation method has high yield and good product quality. The bidentate phosphine ligand copolymer containing phosphite ester structure prepared by the method provided by the invention has the advantages that the product yield and purity are higher than 95%, and recrystallization is not needed, so that the level which cannot be achieved by the prior preparation technology is reached;
(3) The preparation method of the invention can realize the preparation of copolymer ligands in various scales. The method provided by the invention can prepare several to hundreds of grams of bidentate phosphine ligand copolymer containing phosphite ester structure at one time;
(4) The application of the organic phosphine ligand polymer simplifies the oxo process flow and reduces the production cost. The industrial device for oxo synthesis generally adopts rhodium low-pressure oxo synthesis liquid-phase circulation process, which has very wide application, but has the problems of complex flow and high production and operation cost. The organic phosphine ligand polymer developed by the invention is used as a carrier and a ligand, and the traditional oxo synthesis process is changed from the aspects of a reaction system, a separation system, a circulation system and the like, so that the production cost is greatly reduced;
(5) The application of the organic phosphine ligand polymer solves the stability problems of separation, recycling and the like of a homogeneous catalyst. In order to overcome the technical problem that a homogeneous catalyst is difficult to separate, a water-oil two-phase catalyst is usually adopted in the hydroformylation reaction of the high-carbon olefin, but in order to improve the intersolubility of the water and the oil, the reaction efficiency of the catalyst is improved, and a certain amount of surfactant is usually added into a reaction system, so that the emulsification of the reaction system is caused, and the difficulty of separating subsequent products is further increased. The organic phosphine ligand polymer developed by the invention is used as a carrier and a ligand to form single-point coordination structure catalysis, so that the activity is improved, and the problems of catalyst separation, recycling and the like are solved.
Drawings
FIG. 1 is a liquid nuclear magnetic resonance hydrogen spectrum of compound 2 in example 2;
FIG. 2 is a liquid nuclear magnetic resonance hydrogen spectrum of compound 3 in example 3;
FIG. 3 is a liquid nuclear magnetic resonance phosphorus spectrum of compound 3 of example 3;
FIG. 4 is an organic phosphine ligand polymer L of example 4 1 Hydrogen nuclear magnetic resonance spectrum of (2);
FIG. 5 is an organic phosphine ligand polymer L of example 4 1 Nuclear magnetic resonance phosphorus spectrum of (2);
FIG. 6 is an organic phosphine ligand polymer L of example 8 2 Nuclear magnetic resonance phosphorus spectrum of (2).
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The present examples provide two organophosphine ligand polymers L 1 、L 2 The chemical structure of the preparation method is as follows,
wherein m is 35-45, n is 35-1350.
Organic phosphine ligand polymer L 1 The synthetic route of (2) is shown as the reaction scheme 2, the organic phosphine ligand polymer L 2 The synthetic route of (2) is shown in the reaction formula 3; wherein, the compound 3 is a bidentate phosphine monomer.
Example 1
This example synthesizes compound 1, for its synthesis, see document CN113004326a.
Example 2:
compound 2 was synthesized in this example as follows:
5g of Compound 1 was charged into a reactor, 100ml of toluene was added, and then 12g of vinyl tri-n-butyltin and 0.73g of tetrakis (triphenylphosphine) palladium were added, and the reaction was refluxed under nitrogen protection overnight. Cooling to room temperature, distilling under reduced pressure to remove solvent, purifying by column chromatography, eluting with petroleum ether: ethyl acetate=2:1, isolated to give compound 2.
As shown in fig. 1, the nuclear magnetic data thereof are as follows: 1 H NMR(400MHz,DMSO)δ9.39(s,1H),7.16(dt,J＝11.2,8.2Hz,2H),6.60(d,J＝8.5Hz,1H),5.56(d,J＝1.4Hz,1H),5.18(dd,J＝11.0,1.4Hz,1H),5.10(d,J＝1.7Hz,1H),1.51(s,2H)。
example 3
Compound 3 was synthesized in this example as follows:
1.27g of the phosphine chloride in the above step 3 was taken
Adding the mixture into a reactor, adding 6ml of ultra-dry tetrahydrofuran under the protection of nitrogen, and cooling to 0 ℃. Another 400mg of Compound 2 and 418mg of triethylamine were dissolved in 2ml of ultra-dry tetrahydrofuran, and the mixture was added dropwise to the above-mentioned reactor at 0 ℃Naturally heating to room temperature, and reacting for 1h. Quenched by adding 20ml of water, extracted by adding 20ml of ethyl acetate, and the organic phase is dried over anhydrous sodium sulfate and separated by column chromatography to obtain the compound 3.
As shown in fig. 2 and 3, the nuclear magnetic data thereof are as follows: 1 H NMR(400MHz,CDCl 3 )δ7.22(d,J＝8.5Hz,2H),7.14(dd,J＝17.4,11.0Hz,2H),7.03(d,J＝3.8Hz,5H),6.97(d,J＝8.5Hz,2H),6.92(d,J＝8.3Hz,5H),5.61(dd,J＝17.4,1.2Hz,2H),5.42(s,1H),5.34(dd,J＝11.0,1.2Hz,2H),5.15(s,0H),2.31(d,J＝7.2Hz,12H),2.21(d,J＝3.6Hz,12H),1.67(q,J＝9.1Hz,4H)。
example 4
This example Synthesis of an organophosphine ligand Polymer L 1 The method comprises the following steps:
400mg of Compound 3 was charged into a reactor, 450mg of styrene, 50mg of AIBN,9ml of ultra-dry tetrahydrofuran was added, and the mixture was reacted at 100℃for 4 hours under the protection of nitrogen. Cooling to room temperature, adding 20ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine polymer L 1 The nuclear magnetic hydrogen spectrum and the nuclear magnetic phosphorus spectrum are shown in fig. 4 and 5 respectively.
Wherein, m is n=1:6, the molecular weight of the polymer is 70000g/mol, the product yield is 97.8%, and the purity is 98.2%.
Example 5
This example Synthesis of an organophosphine ligand Polymer L 1 The method comprises the following steps:
400mg of Compound 3 was charged into a reactor, 500mg of styrene, 45mg of AIBN,9ml of ultra-dry tetrahydrofuran were added, and reacted at 100℃for 4 hours under the protection of nitrogen. Cooling to room temperature, adding 20ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine polymer L 1 。
Wherein, m is n=1:10, the molecular weight of the polymer is 95000g/mol, the product yield is 97.6 percent, and the purity is 99.3 percent.
Example 6
This example Synthesis of an organophosphine ligand Polymer L 1 The method comprises the following steps:
400mg of Compound 3 was added to a reactor, 600mg of styrene, 45mg of AIBN,9ml of ultra-dry tetrahydrofuran was added under nitrogenThe reaction was carried out at 100℃for 4 hours. Cooling to room temperature, adding 20ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine polymer L 1 。
Wherein, m is n=1:20, the molecular weight of the polymer is 140000g/mol, the product yield is 97.3 percent, and the purity is 98.8 percent.
Example 7
This example Synthesis of an organophosphine ligand Polymer L 1 The method comprises the following steps:
400mg of Compound 3 was charged into a reactor, 600mg of styrene, 40mg of AIBN,9ml of ultra-dry tetrahydrofuran were added and reacted at 90℃for 4 hours under the protection of nitrogen. Cooling to room temperature, adding 20ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine polymer L 1 。
Wherein, m is n=1:30, the molecular weight of the polymer is 180000g/mol, the product yield is 97.5%, and the purity is 99.0%.
Example 8
This example Synthesis of an organophosphine ligand Polymer L 2 The method comprises the following steps:
300mg of Compound 3 was charged into a reactor, and 1.0g of tris (4-vinylphenyl) phosphine, 35mg of AIBN,15ml of ultra-dry tetrahydrofuran were added and reacted at 100℃for 4 hours under nitrogen. Cooling to room temperature, adding 30ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine ligand polymer L 2 The nuclear magnetic phosphorus spectrum is shown in FIG. 6.
Wherein, m is n=1:6, the molecular weight of the polymer is 85000g/mol, the product yield is 96.8 percent, and the purity is 98.9 percent.
Example 9
This example Synthesis of an organophosphine ligand Polymer L 2 The method comprises the following steps:
300mg of Compound 3 was charged into a reactor, and 1.22g of tris (4-vinylphenyl) phosphine, 35mg of AIBN,15ml of ultra-dry tetrahydrofuran were added and reacted at 100℃for 4 hours under nitrogen. Cooling to room temperature, adding 30ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine ligand polymer L 2 。
Wherein, m is n=1:10, the molecular weight of the polymer is 11000g/mol, the product yield is 97.1 percent, and the purity is 99.1 percent.
Example 10
This example Synthesis of an organophosphine ligand Polymer L 2 The method comprises the following steps:
300mg of Compound 3 was charged into a reactor, and 1.50g of tris (4-vinylphenyl) phosphine, 35mg of AIBN,15ml of ultra-dry tetrahydrofuran were added and reacted at 95℃for 4 hours under nitrogen. Cooling to room temperature, adding 30ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine ligand polymer L 2 。
Wherein, m is n=1:20, the molecular weight of the polymer is 165000g/mol, the product yield is 96.8 percent, and the purity is 98.8 percent.
Example 11
This example Synthesis of an organophosphine ligand Polymer L 2 The method comprises the following steps:
300mg of Compound 3 was charged into a reactor, and 1.80g of tris (4-vinylphenyl) phosphine, 30mg of AIBN,15ml of ultra-dry tetrahydrofuran were added and reacted at 85℃for 4 hours under nitrogen. Cooling to room temperature, adding 30ml of methanol for precipitation, filtering, washing with methanol, and drying in vacuum to obtain an organic phosphine ligand polymer L 2 。
Wherein, m is n=1:30, the molecular weight of the polymer is 195000g/mol, the product yield is 96.2 percent, and the purity is 98.6 percent.
Example 12
This example provides an organophosphine ligand polymer L 2 Use of (m=36, n=52, m: n=1:1.44) in the hydroformylation of butadiene, in particular as follows:
in a glove box, 20mg of the organophosphine ligand polymer L was taken separately 2 And 1mg of rhodium metal precursor Rh (acac) (CO) 2 Adding into autoclave, adding 3ml toluene, sealing the autoclave, and introducing H with pressure of 2MPa and volume ratio of 1:1 2 Mixing with CO gas, stirring at 80deg.C for 2 hr to obtain catalyst; cooling, adding 1ml of 1, 3-butadiene toluene solution with the concentration of 3mol/L, pressurizing to 4MPa, and stirring at 80 ℃ for reaction for 12 hours to prepare the 1, 6-glyoxal.
The conversion of 1, 3-butadiene was 99.5% and the selectivity of 1, 6-glyoxal was 53.4% as measured by gas chromatography internal standard method.
Example 13
As in example 12, this example provides an organophosphine ligand polymer L 2 The only difference in the use in olefin polymerization is the organophosphine ligand polymer L of the present example 2 M=25, n=52, m:n=0.48. The method comprises the following steps:
20mg of the organophosphine ligand polymer L2 and 1mg of the rhodium metal precursor Rh (acac) (CO) were taken, respectively, in a glove box 2 Adding into autoclave, adding 3ml toluene, sealing the autoclave, and introducing H with pressure of 2MPa and volume ratio of 1:1 2 Mixing with CO gas, stirring at 80deg.C for 2 hr to obtain catalyst; cooling, adding 1ml of 1, 3-butadiene toluene solution with the concentration of 3mol/L, pressurizing to 4MPa, and stirring at 80 ℃ for reaction for 12 hours to prepare the 1, 6-glyoxal.
The conversion of 1, 3-butadiene was 93.2% and the selectivity of 1, 6-glyoxal was 40.2% as measured by gas chromatography internal standard method.
Comparative example 1
As in example 12, this comparative example provides an organophosphine ligand polymer L 3 Use in olefin polymerization of the organophosphine ligand polymer L of this comparative example 3 With an organophosphine ligand polymer L 2 The only difference in comparison is that where m=36, n=1440, m: n=1:40, the other structures are identical. The method comprises the following steps:
in a glove box, 20mg of the organophosphine ligand polymer L was taken separately 3 And 1mg of rhodium metal precursor Rh (acac) (CO) 2 Adding into autoclave, adding 3ml toluene, sealing the autoclave, and introducing H with pressure of 2MPa and volume ratio of 1:1 2 Mixing with CO gas, stirring at 80deg.C for 2 hr to obtain catalyst; cooling, adding 1ml of 1, 3-butadiene toluene solution with the concentration of 3mol/L, pressurizing to 4MPa, and stirring at 80 ℃ for reaction for 12 hours to prepare the 1, 6-glyoxal.
The conversion of 1, 3-butadiene was 50.5% and the selectivity of 1, 6-glyoxal was 13.7% as measured by gas chromatography internal standard method. The organophosphine ligand polymer L of this comparative example 3 M: the value of n is too small, and the application effect in the hydroformylation of olefinPoor.
Claims (10)
1. An organic phosphine ligand polymer is characterized in that the structure is shown as a general formula (I),
wherein R is 1 And R is 2 Selected from the same or different phosphorus-containing groups, R 1 And R is 2 Each independently selected from the following structures:
R 3 selected from the group consisting of
m is 35-45, n is 35-1350.
2. The organophosphine ligand polymer according to claim 1, wherein R 1 And R is 2 Each independently selected from
Preferably, R 3 Selected from the group consisting of
3. The polymer of an organic phosphine ligand according to claim 1 or 2, wherein the polymer of an organic phosphine ligand is formed by copolymerizing a bidentate phosphine monomer and a vinyl monomer, the structure of the bidentate phosphine monomer is shown as a general formula (II), and the structure of the vinyl monomer is that
4. An organophosphine ligand polymer according to claim 1 or 2, wherein m: n is 1 (1-30);
preferably, the molecular weight range of the organic phosphine ligand polymer is 50000-200000g/mol;
preferably, the organophosphine ligand polymer has a degree of polymerization of 35 to 55.
5. A process for the preparation of an organophosphine ligand polymer according to any one of claims 1 to 4, comprising the steps of:
s1: under the condition of inert gas atmosphere and triethylamine, R is reacted with the mixture 1 -Cl and/or R 2 The Cl and the compound 2 are fully contacted in a first solvent for reaction, the reaction is quenched, and the reaction product is collected and purified to obtain a bidentate phosphine monomer;
s2: under the condition of inert gas atmosphere and the existence of azodiisobutyronitrile, enabling the bidentate phosphine monomer and the vinyl monomer to fully contact in a second solvent for copolymerization reaction, terminating the reaction, and collecting and purifying a reaction product to obtain the organic phosphine ligand polymer;
wherein the structure of the compound 2 is
6. The process according to claim 5, wherein in S2, the copolymerization reaction temperature is 60 to 100℃and the reaction time is 2 to 6 hours;
preferably, the second solvent is selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran and toluene;
preferably, in S1, the reaction temperature is 60-100 ℃ and the reaction time is 2-6h;
preferably, in S1, the first solvent is selected from one or more of tetrahydrofuran, toluene, N-dimethylformamide.
7. The production method according to claim 5, characterized in that the production method further comprises a step of producing the compound 2, the production method of the compound 2 comprising: and (3) under the action of nitrogen atmosphere and a catalyst, enabling the compound 1 and an vinylation reagent to be fully contacted in a third solvent for performing vinylation reaction, and collecting and purifying a reaction product to obtain the compound 2.
8. The process according to claim 7, wherein the vinylation reaction temperature is 10-60 ℃ and the reaction time is 5-10 hours;
preferably, the vinylating agent is selected from
One or more of the following;
preferably, the catalyst is selected from tetrakis (triphenylphosphine) palladium, pdCl 2 (dppf) or PdCl 2 (PPh3) 2 One or more of the following;
preferably, the third solvent is selected from one or more of toluene, tetrahydrofuran, 1, 4-dioxane.
9. Use of an organophosphine ligand polymer according to any one of claims 1 to 4, in an olefin hydroformylation reaction.
10. The use according to claim 9, wherein the olefin is selected from C 4 -C 10 Olefins, preferably butadiene;
preferably, the organophosphine ligand polymer forms a heterogeneous rhodium catalyst system.
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