CN113399001A - Catalyst for olefin hydrosilylation reaction, preparation method and application thereof - Google Patents
Catalyst for olefin hydrosilylation reaction, preparation method and application thereof Download PDFInfo
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- CN113399001A CN113399001A CN202110822701.3A CN202110822701A CN113399001A CN 113399001 A CN113399001 A CN 113399001A CN 202110822701 A CN202110822701 A CN 202110822701A CN 113399001 A CN113399001 A CN 113399001A
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- olefin
- hydrosilylation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 8
- -1 n-octyl Chemical group 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000008863 intramolecular interaction Effects 0.000 abstract description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- BFIDWDKYNVSHDP-UHFFFAOYSA-N triethyl(hexyl)silane Chemical compound CCCCCC[Si](CC)(CC)CC BFIDWDKYNVSHDP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2461—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as ring members in the condensed ring system or in a further ring
- B01J31/248—Bridged ring systems, e.g. 9-phosphabicyclononane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
- C07F7/0829—Hydrosilylation reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65683—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine
-
- 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
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
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- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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- 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
- B01J2531/828—Platinum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a catalyst for olefin hydrosilylation, which is a platinum complex of a phosphorus-containing tetradentate ligand 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphosphite-1, 3,5,7(1,3) -tetrabenzocyclooctane compound, and the structural formula of the platinum complex is shown as a formula (I);
in the formula, R1And R2Each independently selected from hydrogen and C1～C10Alkyl of (C)3～C10Cycloalkyl, haloalkyl, alkoxy or halogen. The catalyst is a metal catalyst assembled by using annular polydentate ligands, forms an ordered closed structure through intramolecular interaction, and is more stable than the coordination of a tridentate ligand and a bidentate ligandNot only the characteristics of a single molecule are maintained, but also unique macroscopic properties are obtained due to an ordered three-dimensional structure, the specific catalytic activity is realized, and the performance of the central metal coordination catalysis is influenced by changing the substituent groups on the phosphine ligand. The catalyst has the advantages of high reaction activity, less catalyst consumption, mild reaction conditions, high conversion rate and high selectivity of beta addition products.
Description
Technical Field
The invention relates to a catalyst for olefin hydrosilylation, a preparation method and application thereof, belonging to the field of olefin hydrosilylation catalysts.
Background
The hydrosilylation reaction of olefin is one of the most important ways for synthesizing organosilicon coupling agent, functional organosilicon compound and polymer, and plays an important role in the synthesis of organic chemistry. The hydrosilylation of olefins is usually carried out in the presence of chloroplatinic acid and its complexes (such as Speier's catalyst and Karstedt's catalyst), which, although having a high activity, produce a large number of reaction by-products (Chisso corp. jp, 8204995,1982). Later, through research on various transition metal complexes, transition metals (Pt, Rh, Ru and the like) have certain catalytic activity on hydrosilylation reaction, but the catalytic activity is not high for certain types of hydrosilylation reaction, such as the hydrosilylation reaction of olefin and hydrosilane. So far, how to improve the activity of the catalyst, reduce the amount of the catalyst used, and inhibit the occurrence of side reactions is still the focus of research on hydrosilylation reactions.
Pt(Ph3P)4The catalyst has been widely used in hydrosilylation of unsaturated organic compounds, but the problems of low catalytic activity, large amount of catalyst and low reaction selectivity still exist. Therefore, designing and synthesizing a specific catalytic function unit, constructing a catalyst with specific catalytic activity, and improving the performance of the traditional organic catalyst have become a research hotspot.
Disclosure of Invention
Aiming at the prior art, the invention provides a catalyst for olefin hydrosilylation, a preparation method thereof and application of the catalyst in olefin hydrosilylation. The catalyst is a platinum catalyst, is prepared from a tetradentate ligand 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane compound and chloroplatinic acid, does not need to separate an intermediate product during preparation, and has the advantages of low loss and high catalyst yield. The catalyst of the invention has higher reaction activity and catalytic activity in various reactions, and the beta addition product has good selectivity and wide application prospect.
The invention is realized by the following technical scheme:
a catalyst for olefin hydrosilylation is a platinum complex of a phosphorus-containing tetradentate ligand 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphosphia-1, 3,5,7(1,3) -tetrabenzocyclooctane compound, and the structural formula of the platinum complex is shown as a formula (I);
in the formula, R1And R2Each independently selected from hydrogen and C1～C10Alkyl of (C)3～C10Cycloalkyl, haloalkyl, alkoxy or halogen.
Further, said C1～C10The alkyl group of (a) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl.
Further, said C3～C10The cycloalkyl group is selected from cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
Further, the alkoxy group is selected from methoxy, ethoxy, isopropoxy.
Further, the halogen is selected from fluorine, chlorine, bromine.
The preparation method of the catalyst for the hydrosilylation reaction comprises the following steps: reacting phosphorus-containing tetradentate ligand with chloroplatinic acid under the action of a catalyst dimethyl sulfoxide, wherein the reaction temperature is 80-90 ℃, and the reaction time is 60-120 minutes; after the reaction is terminated, filtering and washing the crystal to obtain the product.
The structural formula of the phosphorus-containing tetradentate ligand is shown as the formula (II):
in the formula, R1And R2Each independently selected from hydrogen and C1～C10Alkyl of (C)3～C10Cycloalkyl, haloalkyl, alkoxy or halogen.
Further, the dosage proportioning relationship of the phosphorus-containing tetradentate ligand and chloroplatinic acid is as follows: 1.05 millimoles of phosphorus-containing tetradentate ligand are added per millimole of chloroplatinic acid.
Further, the dosage proportion relation of the chloroplatinic acid and the dimethyl sulfoxide is as follows: 10-15 mL of dimethyl sulfoxide is added to each millimole of chloroplatinic acid.
Further, hydrazine hydrate was added to the reaction system to terminate the reaction.
Further, after the reaction is terminated, cooling the reaction solution to room temperature, filtering and collecting crystals, performing suction filtration and washing on the crystals according to the sequence of ethanol washing, water washing and ethanol washing, and drying to obtain the target catalyst.
The catalyst for olefin hydrosilylation is applied to olefin hydrosilylation.
Further, the hydrosilylation reaction of the olefin is a hydrosilylation reaction of the olefin and the hydrogen-containing silane.
A catalyst system for olefin hydrosilylation reaction of olefin and hydrogen-containing silane comprises olefin, hydrogen-containing silane and the catalyst, wherein the molar ratio of the catalyst to the olefin to the hydrogen-containing silane is as follows: (1X 10)-9～1×10-8) 1 (1-1.3). The conditions of the olefin hydrosilylation reaction are as follows: reacting for 2-3 hours in a silicon oil bath at 30-50 ℃, and cooling to room temperature after the reaction is finished.
Further, the olefin is selected from hexene, heptene, octene, undecene, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene or 4-methoxystyrene.
The hydrogen-containing silane is selected from triethoxy hydrosilane, trimethoxy hydrosilane, triethyl hydrosilane, trichlorosilane, monomethyl dichlorohydrosilane or monochlorodimethyl hydrosilane.
The catalyst is a platinum complex of a phosphorus-containing tetradentate ligand 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphosphite-1, 3,5,7(1,3) -tetrabenzocyclooctaalkane compound, the complex is a metal catalyst assembled by using annular polydentate ligands, an ordered closed structure is formed by intramolecular interaction, the complex is more stable than the coordination of a tridentate ligand and a bidentate ligand, the characteristic of a single molecule is maintained, the unique macroscopic performance is obtained due to the ordered three-dimensional structure, the catalyst has specific catalytic activity, and the performance of central metal coordination catalysis is influenced by changing substituent groups on a phosphine ligand.
The catalyst of the invention takes platinum as a main catalyst, and tetradentate phosphorus-containing derivatives containing different substituents as ligands, so that the catalyst has the advantages of higher reaction activity, less catalyst usage amount, mild reaction conditions, high conversion rate and high selectivity of beta addition products.
The various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Example 1 preparation of catalyst for hydrosilylation reaction of olefin
Into a conical flask, 0.517g of chloroplatinic acid and 0.517g of chloroplatinic acid were charged736g of 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphosphaza-1, 3,5,7(1,3) -tetrabenzocyclooctane (i.e.R)1And R2Hydrogen) and 15mL of 99.9% (weight percent) dimethyl sulfoxide, heating the mixture to reflux (85 ℃), keeping the temperature for 60min, cooling the solution to 50 ℃, adding 2mL of 25% (volume percent) hydrazine hydrate solution, cooling the solution to room temperature, filtering and separating a crystal product 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphosphayl-1, 3,5,7(1,3) -tetrabenzocyclooctane compound platinum complex, filtering and washing the crystal with absolute ethyl alcohol, filtering and washing the crystal with distilled water, filtering and washing the crystal with absolute ethyl alcohol, and drying the crystal at room temperature. 0.85g of product, yield 95%.
Example 2 preparation of catalyst for hydrosilylation reaction of olefin
Into an Erlenmeyer flask were added 0.517g of chloroplatinic acid, 0.736g of 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane (i.e., R1And R2All hydrogen) and 10mL of 99.9% dimethyl sulfoxide, heating the mixture to reflux (85 ℃), keeping the temperature for 60min, cooling the solution to 50 ℃, adding 1mL of 25% hydrazine hydrate solution, cooling the solution to room temperature, filtering and separating a crystal product, namely 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzooctane compound platinum complex, filtering the crystal, washing the crystal by using absolute ethyl alcohol in a suction filtration manner, washing the crystal by using distilled water in a suction filtration manner, washing the crystal by using absolute ethyl alcohol in a suction filtration manner, and airing the crystal at room temperature. 0.83g of product, 89% yield.
Example 3 preparation of catalyst for hydrosilylation reaction of olefin
Into an Erlenmeyer flask were charged 0.517g of chloroplatinic acid, 0.792g of 1,3,5, 7-tetramethyl-2, 4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane-based compound (i.e., R1Is hydrogen, R2Methyl) and 10mL of 99.9% dimethyl sulfoxide, heating the mixture to reflux (85 ℃), maintaining the temperature for 60min, cooling the solution to 50 ℃, adding 1mL of 25% hydrazine hydrate solution, cooling the solution to room temperature, filtering and separating a crystal product 1,3,5, 7-tetramethyl-2, 4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane compound platinum complex, filtering the crystal, performing suction filtration and washing by using absolute ethyl alcohol, and performing suction filtration and washing by using distilled waterThen, the mixture is filtered and washed by absolute ethyl alcohol and dried at room temperature. 0.83g of product, 89% yield.
EXAMPLE 4 hydrosilylation reaction of olefins
In a 500 ml three-necked flask, hexene (1mol), 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane platinum complex (prepared in example 1) (1X 10)-8mol), slowly heating to 35 ℃ under the protection of nitrogen, dropwise adding triethylhydrosilane (1mol) through a dropping funnel, keeping the reaction temperature, continuously stirring for reaction for 2 hours, cooling to room temperature, replacing by reduced pressure distillation to collect corresponding fractions, measuring the conversion rate of hexene to be 99.9% through GC-MS, and measuring the beta adduct 1-triethylsilyl hexane (CH)3(CH2)5Si(CH2CH3)3) The yield of (b) was 95%.
EXAMPLE 5 hydrosilylation reaction of olefin
In a 500 ml three-necked flask, hexene (1mol), 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane platinum complex (prepared in example 1) (1X 10)-9mol), slowly heating to 45 ℃ under the protection of nitrogen, dropwise adding triethylhydrosilane (1mol) through a dropping funnel, keeping the reaction temperature, continuously stirring for reaction for 3 hours, cooling to room temperature, replacing by reduced pressure distillation to collect corresponding fractions, measuring the conversion rate of hexene to 97.8% through GC-MS, and measuring the beta adduct 1-triethylsilyl hexane (CH)3(CH2)5Si(CH2CH3)3) The yield of (b) was 93%.
EXAMPLE 6 hydrosilylation reaction of olefin
In a 500 ml three-necked flask, hexene (1mol), 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane platinum complex (prepared in example 1) (1X 10)-8mol), slowly heating to 35 ℃ under the protection of nitrogen, dropwise adding monochlorodimethylhydrogensilane (1mol) through a dropping funnel, keeping the reaction temperature, continuously stirring for reaction for 2.5 hours, cooling to room temperature, replacing by reduced pressure distillation to collect corresponding fractions, determining the conversion rate of hexene to be 99.9% through GC-MS, and determining the beta adduct 1-triethylsilyl hexane (CH)3(CH2)5Si(CH2CH3)3) The yield of (b) was 97%.
EXAMPLE 7 hydrosilylation reaction of olefins
In a 500 ml three-necked flask, hexene (1mol), and a platinum complex of 1,3,5, 7-tetramethyl-2, 4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane (prepared in example 3) (1X 10)- 8mol), slowly heating to 35 ℃ under the protection of nitrogen, dropwise adding monochlorodimethylhydrogensilane (1mol) through a dropping funnel, keeping the reaction temperature, continuously stirring for reaction for 2.5 hours, cooling to room temperature, replacing by reduced pressure distillation to collect corresponding fractions, determining the conversion rate of hexene to be 99.8% through GC-MS, and determining the beta adduct 1-triethylsilyl hexane (CH)3(CH2)5Si(CH2CH3)3) The yield of (b) was 95%.
EXAMPLE 8 hydrosilylation reaction of olefins
In a 500 ml three-necked flask, heptene (1mol), the platinum complex of 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphospham-1, 3,5,7(1,3) -tetrabenzocyclooctane (prepared in example 1) (1X 10)-8mol), slowly heating to 40 ℃ under the protection of nitrogen, dropwise adding monochlorodimethylhydrogensilane (1mol) through a dropping funnel, keeping the reaction temperature, continuously stirring for reaction for 3 hours, cooling to room temperature, replacing by reduced pressure distillation to collect corresponding fractions, determining the conversion rate of heptene to be 99.5% through GC-MS, and determining the beta adduct 1-triethylsilyl hexane (CH)3(CH2)6Si(CH2CH3)3) The yield of (b) was 96%.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. A catalyst for olefin hydrosilylation is a platinum complex of a phosphorus-containing tetradentate ligand 2,4,6, 8-tetraphenyl-2, 4,6, 8-tetraphosphia-1, 3,5,7(1,3) -tetrabenzocyclooctane compound, and the structural formula of the platinum complex is shown as a formula (I);
in the formula, R1And R2Each independently selected from hydrogen and C1～C10Alkyl of (C)3～C10Cycloalkyl, haloalkyl, alkoxy or halogen.
2. The catalyst for hydrosilylation reaction of an olefin according to claim 1, wherein: said C is1～C10The alkyl group of (a) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl;
said C is3～C10The cycloalkyl group of (a) is selected from cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl;
the alkoxy is selected from methoxy, ethoxy and isopropoxy;
the halogen is selected from fluorine, chlorine and bromine.
3. The method for producing a catalyst for hydrosilylation of olefins according to claim 1, characterized in that: reacting phosphorus-containing tetradentate ligand with chloroplatinic acid under the action of a catalyst dimethyl sulfoxide, wherein the reaction temperature is 80-90 ℃, and the reaction time is 60-120 minutes; after the reaction is terminated, filtering and washing the crystal to obtain the product;
the structural formula of the phosphorus-containing tetradentate ligand is shown as the formula (II):
in the formula, R1And R2Each independently selected from hydrogen and C1～C10Alkyl of (C)3～C10Cycloalkyl, haloalkyl, alkoxy or halogen.
4. The production method according to claim 3, characterized in that: said C is1～C10The alkyl group of (a) is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl;
said C is3～C10The cycloalkyl group of (a) is selected from cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl;
the alkoxy is selected from methoxy, ethoxy and isopropoxy;
the halogen is selected from fluorine, chlorine and bromine.
5. The production method according to claim 3, characterized in that: the dosage proportion relation of the phosphorus-containing tetradentate ligand and the chloroplatinic acid is as follows: 1.05 millimoles of a phosphorus-containing tetradentate ligand per millimole of chloroplatinic acid;
the dosage proportion relation of the chloroplatinic acid and the dimethyl sulfoxide is as follows: adding 10-15 mL of dimethyl sulfoxide into each millimole of chloroplatinic acid;
adding hydrazine hydrate into the reaction system to stop the reaction;
after the reaction is ended, cooling the reaction solution to room temperature, filtering and collecting crystals, performing suction filtration and washing on the crystals according to the sequence of ethanol washing, water washing and ethanol washing, and drying to obtain the catalyst.
6. Use of the catalyst of claim 1 or 2 as a catalytic component in a hydrosilylation reaction of an olefin.
7. Use according to claim 6, characterized in that: the olefin hydrosilylation reaction is the hydrosilylation reaction of olefin and hydrogen-containing silane.
8. A catalyst system for the hydrosilylation reaction of an olefin with a hydrosilane, comprising: comprising an olefin, a hydrosilane, and the catalyst of claim 1 or 2.
9. The catalytic system of claim 8, wherein: the molar ratio of the catalyst, the olefin and the hydrogen-containing silane is as follows: (1X 10)-9～1×10-8):1:(1～1.3)；
The conditions of the olefin hydrosilylation reaction are as follows: reacting for 2-3 hours in a silicon oil bath at 30-50 ℃, and cooling to room temperature after the reaction is finished.
10. The catalytic system according to claim 8 or 9, characterized in that: the olefin is selected from hexene, heptene, octene, undecene, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene or 4-methoxystyrene;
the hydrogen-containing silane is selected from triethoxy hydrosilane, trimethoxy hydrosilane, triethyl hydrosilane, trichlorosilane, monomethyl dichlorohydrosilane or monochlorodimethyl hydrosilane.
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