CN110327973B - Crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst and preparation method and application thereof - Google Patents
Crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst and preparation method and application thereof Download PDFInfo
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- CN110327973B CN110327973B CN201910683516.3A CN201910683516A CN110327973B CN 110327973 B CN110327973 B CN 110327973B CN 201910683516 A CN201910683516 A CN 201910683516A CN 110327973 B CN110327973 B CN 110327973B
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- 239000010949 copper Substances 0.000 title claims abstract description 99
- 229920001577 copolymer Polymers 0.000 title claims abstract description 73
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 239000006229 carbon black Substances 0.000 title claims abstract description 54
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 239000012295 chemical reaction liquid Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- -1 aldehyde ketones Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011984 grubbs catalyst Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 241001424392 Lucia limbaria Species 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- ZQTYQMYDIHMKQB-UHFFFAOYSA-N exo-norborneol Chemical compound C1CC2C(O)CC1C2 ZQTYQMYDIHMKQB-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JFARWEWTPMAQHW-DHZHZOJOSA-N (e)-3-(4-bromophenyl)-1-phenylprop-2-en-1-one Chemical compound C1=CC(Br)=CC=C1\C=C\C(=O)C1=CC=CC=C1 JFARWEWTPMAQHW-DHZHZOJOSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- SGCLBIRCSTXTIU-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O SGCLBIRCSTXTIU-UHFFFAOYSA-N 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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
Abstract
The invention relates to a crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst, a preparation method and application thereof, which are characterized by comprising the following steps: the catalyst comprises a crosslinked norbornene copolymer/carbon black three-dimensional network carrier and nano copper loaded on the carrier, wherein the mass percentage of the copper in the crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst is 1.0-2.0%. According to the invention, the copper nano catalyst PNBI/CB/Cu is loaded on the crosslinked norbornene copolymer/carbon black three-dimensional network, and the nano copper is wrapped in the carrier, so that the nano copper is easy to separate and recycle after reaction, and the metal copper has small loss and small pollution; compared with bivalent copper, the heterogeneous zero-valent copper is not easy to fall off in the reaction process, the catalyst has long service life, and still has high activity after being repeatedly recycled; the metal copper exists in the PNBI/CB/Cu catalyst in the form of nano particles, and has the advantages of uniform dispersion, small copper content, high activity and low use cost; the PNBI/CB/Cu catalyst can be stored well, and is not easy to drop metal or damage a structure.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a copper nano catalyst loaded on a crosslinked norbornene copolymer/carbon black three-dimensional network, and a preparation method and application thereof.
Background
The organic boron compound is an important intermediate, widely exists in the structures of natural products and drug molecules, and is also an important synthon for organic synthesis, and C-B bonds can be further converted into C-O, C-N bonds and C-C bonds. Compared with the traditional method using equivalent reaction reagents, the strategy of direct boron addition to unsaturated carbonyl compounds under the action of a catalyst is more direct and effective, and the method has attracted much attention in recent years.
The inventor's granted Chinese patent (patent No. ZL201610271869.9) discloses a method for preparing an organic boron compound by catalysis of chitosan supported copper and application thereof. However, in the invention, the catalyst metal copper is divalent, such as copper sulfate, copper chloride, copper hydroxide and the like, copper is easy to fall off in the reaction process, so that the activity of the catalyst is reduced, the environment is polluted, and the method is not suitable for practical production, the application of the method in practical production is greatly limited, and the selection of the carrier is very important for a heterogeneous catalyst.
Disclosure of Invention
The technical problem solved by the invention is as follows: the invention provides a copper metal nano catalyst (PNBI/CB/Cu) immobilized by a crosslinked norbornene copolymer/carbon black three-dimensional network. According to the PNBI/CB/Cu catalyst, the nano copper is wrapped in a crosslinked norbornene copolymer/carbon black three-dimensional network (PNBI/CB) carrier, a crosslinked polymer is insoluble in a conventional solvent, and the effect of immobilizing the nano metal copper is good; compared with bivalent copper, the heterogeneous zero-valent copper is not easy to fall off in the reaction process; the catalyst has high activity and long service life, and still has high activity after being repeatedly recycled.
The scheme provided by the invention is as follows:
the invention provides a copper nano catalyst loaded on a crosslinked norbornene copolymer/carbon black three-dimensional network, which is characterized by comprising the following components in percentage by weight: the catalyst comprises a cross-linked norbornene copolymer/carbon black three-dimensional network (PNBI/CB) carrier and nano copper loaded on the PNBI/CB carrier, wherein the mass percentage of copper in a copper nano catalyst PNBI/CB/Cu loaded on the cross-linked norbornene copolymer/carbon black three-dimensional network is 1.0-2.0%.
According to the crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst, the nano copper is wrapped in the PNBI/CB carrier, the nano copper is easy to separate and recycle after reaction, the loss of metal copper is small, the pollution caused by the metal copper is small, heterogeneous zero-valent copper is not easy to fall off in the reaction process compared with bivalent copper, the service life of the catalyst is long, and the catalyst still has high activity after repeated recycling; the metallic copper exists in the PNBI/CB/Cu catalyst in the form of nano particles, is uniformly dispersed, has the copper content of only 1.0 to 2.0 percent, small content, high activity and low use cost; the PNBI/CB/Cu catalyst can be stored well, and is not easy to drop metal or damage a structure.
Specifically, the carbon black is commercially available activated carbon powder, is cheap and easily available, is amorphous carbon, is loose, light and extremely fine black powder, has very large surface area, can improve the immobilization stability of metal nanoparticles in the catalyst by adding the carbon black, and has high specific surface area so that metal copper on the carrier has high dispersibility.
On the basis of the scheme, the following improvements can be made:
further, the norbornene copolymer is prepared by mixing a first monomer (formula I), a second monomer (formula II) and a third monomer (formula III) according to a molar ratio of 1: (0.75-1.25): (0.75-1.25) polymerized product.
The cross-linked norbornene copolymer prepared under the condition contains a proper amount of free hydroxyl, has a proper hydrophilic-lipophilic balance (HLB), has good dispersibility in both an organic phase and a water phase, can be suitable for reaction of the organic phase and the water phase and reaction of an organic/water mixed phase, can be conveniently separated from other components in a reaction system by a conventional solid-liquid separation method (centrifugation, filtration and the like) after the reaction is finished, and is convenient to reuse.
Further, the molecular weight of the norbornene copolymer was 12000-17000.
Therefore, the PNBI/CB/Cu catalyst obtained by crosslinking the norbornene copolymer has better dispersibility and stability in an organic/water mixed phase.
The invention provides a preparation method of a copper nano catalyst loaded on a crosslinked norbornene copolymer/carbon black three-dimensional network, which is characterized by comprising the following steps:
1) reacting a reaction solution A containing the first monomer, the second monomer, the third monomer and a catalyst for 1-3h under an inert atmosphere, wherein the molar ratio of the first monomer to the second monomer to the third monomer to the catalyst is 1: (0.75-1.25): (0.75-1.25): (1% -5%).
2) Adding a quenching agent into the reaction liquid A, continuously stirring for 5-20min to obtain a reaction liquid B, and concentrating and precipitating the reaction liquid B to obtain the norbornene copolymer.
3) And dispersing a norbornene polymer and activated carbon powder mixed material in dichloromethane to obtain a mixed dispersion liquid, wherein the mass fraction of the norbornene polymer in the mixed material is 30% -70%.
4) Drying the mixed dispersion liquid to obtain a norbornene polymer/carbon black mixture;
5) and dispersing the polynorbornene polymer/carbon black and sodium borohydride in a diethylene glycol dimethyl ether/dichloromethane mixed solvent, adding copper acetate, and stirring for 2-6h to obtain a reaction liquid C, wherein the molar ratio of the sodium borohydride to the copper acetate is (3-5): 1.
6) Adding ether into the reaction solution C to precipitate a norbornene polymer/carbon black/copper primary product, washing and drying the primary product, and heating at the temperature of 150 ℃ for 4-7h under inert gas to obtain the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper catalyst PNBI/CB/Cu.
According to the method, norbornene is used as a polymer framework, under the action of a catalyst, a first monomer, a second monomer and a third monomer are subjected to ring-opening disproportionation polymerization to obtain a crosslinked norbornene copolymer, and the relative content of free hydroxyl in the catalyst can be adjusted by changing the proportion of the monomers, so that the hydrophilic-lipophilic balance value of the catalyst is regulated and controlled to adapt to different organic phase and aqueous phase reactions or organic phase/aqueous phase reactions, and higher catalytic efficiency and higher recovery rate are achieved.
On the basis of the scheme, the following improvements can be made:
further, the catalyst is selected from one of Grubbs catalyst and Schrock catalyst, and the quenching agent is vinyl ethyl ether.
The catalyst catalyzes ring-opening disproportionation polymerization to be activity-controllable polymerization, and the polymerization degree and molecular weight of the polymer can be adjusted by changing the amount of the catalyst, so that the obtained molecular weight is accurate and controllable, and the molecular weight Distribution (DPI) is narrow; the relative content of Cu (copper) in the copper nano catalyst in PNBI/CB/Cu can be adjusted by changing the volume or concentration of the copper acetate solution; and the size of the copper nanoparticles in PNBI/CB/Cu can be adjusted by changing the using amount of the sodium borohydride.
Further, the washing treatment in step 6) includes washing with deionized water, tetrahydrofuran, and dichloromethane in this order.
This enables the polar and nonpolar impurities on the catalyst surface to be removed successively and completely.
Further, the steps 1) to 5) are all carried out at room temperature.
Therefore, the reaction is carried out at normal temperature, the conditions are mild, the preparation is simple, and the industrial production is convenient.
According to the preparation method, the relative content of free hydroxyl in the catalyst is controlled by changing the monomer ratio, so that the hydrophilic-lipophilic balance (HLB) of the catalyst is regulated and controlled to adapt to different reaction systems (organic phase, water phase and organic/water mixed phase).
Specifically, the solvent in the reaction solution a in the step 1) is any one selected from dichloromethane, toluene and tetrahydrofuran.
Preferably, the solvent in the reaction solution a is dichloromethane.
The reaction raw materials and the catalyst can be sufficiently dissolved in the dichloromethane, and a norbornene copolymer with high yield and high purity can be prepared.
Preferably, the organic solvent in step 3) is dichloromethane.
Can sufficiently disperse the mixture of the norbornene polymer and the activated carbon powder and further dissolve and remove incompletely reacted reaction raw materials.
Preferably, the mixed dispersion liquid is filtered, washed and dried in the step 4) to obtain a polynorbornene polymer/carbon black mixture.
Thereby removing redundant impurities and obtaining a polynorbornene polymer/carbon black mixture with higher purity.
Specifically, the concentration of the polynorbornene polymer/carbon black in the step 5) is 15-25g/L, and the concentration of the sodium borohydride is 0.5-1.5 g/L.
The concentration of the used copper acetate solution is adjusted, the relative content of copper in the PNBI/CB/Cu nano catalyst can be adjusted, the concentration of sodium borohydride is changed, the size of copper nanoparticles in the PNBI/CB/Cu copper nano catalyst can be adjusted, and the copper nanoparticles which are uniformly distributed in the PNBI/CB carrier, small in size (the particle size is 2-8nm) and highly dispersed can be obtained under the condition.
The invention also provides an application of the crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst, and the PNBI/CB/Cu catalyst is applied to boron addition reaction of alpha, beta-unsaturated aldehyde ketone.
The PNBI/CB/Cu catalyst provided by the invention is applied to the boron addition reaction of alpha, beta-unsaturated aldehyde ketone, can obtain higher product yield, has long service life, and still has higher activity after being recycled for a plurality of times.
The application of the crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst comprises the following steps:
1) mixing alpha, beta-unsaturated aldehyde ketone, bis-pinacol borate and palladium in the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nano catalyst according to a molar ratio of 1 (1-1.2) to 0.1-0.3%, and mixing according to a volume ratio of 1: (0.5-1.5) adding tetrahydrofuran and water to obtain a mixed reaction solution;
2) and reacting the mixed reaction liquid for 8-16h to generate a boron addition product of the alpha, beta-unsaturated aldehyde ketone.
When the cross-linked norbornene copolymer is prepared by mixing the first monomer, the second monomer and the third monomer according to a molar ratio of 1: (0.75-1.25): (0.75-1.25) polymerizing and crosslinking to obtain a product, wherein the catalyst obtained under the condition has appropriate hydrophilic and lipophilic properties, has good dispersibility in the tetrahydrofuran/water system, can be fully separated and recycled after the reaction is finished, and is convenient to recycle.
Specifically, after the mixed reaction liquid reacts for 8-16h in the step 2), the mixed reaction liquid is filtered, the PNBI/CB/Cu catalyst is recovered, the solvent is removed by rotary evaporation of the filtrate, and the boron addition reaction product of the alpha, beta-unsaturated aldehyde ketone is obtained after column chromatography.
Further, the method comprises the step 3) of adding sodium perborate into the mixed reaction liquid of the boron addition product for generating the alpha, beta-unsaturated aldehyde ketone, and reacting for 1-3 hours to generate a hydroxyl compound.
Since boron compounds are less stable and are not easily separated, they can be converted into hydroxy compounds. With an excess of sodium perborate, THF and H2O is taken as a solvent, oxidized for 2 hours, extracted, dried by spinning, and separated by column chromatography to obtain the product. The conversion of the organoboron compound to the beta-hydroxy compound is an important application in industrial production, because the beta-hydroxy structure is widely existed in a drug molecular structure, if a strategy of 'one-pot method' is adopted, firstly, the boron addition of a substrate alpha, beta-unsaturated aldehyde ketone is realized, and then, the substrate alpha, beta-unsaturated aldehyde ketone is continuously converted into the beta-hydroxy compound without separation, so that the synthesis steps of the beta-hydroxy product are simplified, and the method has very important application value in the fields of drug synthesis and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a TEM image of a crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst prepared in example 1.
FIG. 2 is a gel permeation chromatography outflow chart of the norbornene copolymer prepared in example 1.
FIG. 3 is a hydrogen nuclear magnetic resonance spectrum of the norbornene copolymer prepared in example 1.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the norbornene copolymer prepared in example 2.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the norbornene copolymer prepared in example 3.
Detailed Description
For a better understanding of the present invention, the following further illustrates the present invention with reference to the accompanying fig. 1-5 and the specific embodiments, but the present invention is not limited to the following embodiments.
The specific solution provided by the invention is as follows:
example 1
(1) Preparation of norbornene copolymer: mixing a first monomer, a second monomer and a third monomer of the norborneol according to a ratio of 1:1, taking 345.44mg of first monomer, 311.38mg of second monomer, 431.53mg of third monomer and 20mg of catalyst Grubbs-I, adding 50mL of dichloromethane to dissolve to obtain reaction liquid A, stirring at room temperature for 2 hours under argon atmosphere, adding 5mL of vinyl ether, continuously stirring for 10min to obtain reaction liquid B, carrying out rotary evaporation concentration on the reaction liquid B, slowly pouring the reaction liquid B into ether to separate out precipitate, filtering, washing the separated precipitate with ether, and drying to obtain the norbornene copolymer.
(2) Preparation of norbornene copolymer/carbon black/copper: and (2) mixing 500mg of the norbornene copolymer obtained in the step (1) and 500mg of activated carbon powder, adding dichloromethane, fully dispersing, filtering, washing and drying to obtain a polynorbornene/carbon black mixture, adding the synthesized polynorbornene/carbon black into 50ml of anhydrous diethylene glycol dimethyl ether/dichloromethane mixed solvent, uniformly dispersing, adding 50.23mg of sodium borohydride, dissolving the sodium borohydride, adding 60.30mg of copper acetate, stirring at room temperature for 4 hours to obtain a reaction liquid C, dropwise adding excessive ether into the reaction liquid C, filtering, repeatedly washing with ether and removing residual solvent to obtain a black solid.
(3) Preparation of crosslinked norbornene copolymer/carbon Black three-dimensional network/copper: and heating the black solid at 160 ℃ for 6h under an argon atmosphere to obtain the PNBI/CB/Cu catalyst.
The catalyst and the intermediate product are characterized, fig. 1 is a Transmission Electron Microscope (TEM) of the crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst PNBI/CB/Cu prepared in example 1, and it can be seen from the TEM that the copper nano particles are highly dispersed in the polymer, and the average particle size is 5 ± 3 nm. The average grain diameter of copper in the PNBI/CB/Cu catalyst prepared by the method is small and the dispersity is good; FIG. 2 is a gel permeation chromatography elution curve of a sample of the norbornene copolymer prepared in the step (1), the spectrum of the norbornene copolymer is good, and Table 1 is an average molecular weight scale of the norbornene copolymer, and the number average molecular weight M of the norbornene copolymer can be knownp15425.
Table 1:
note: mnNumber average molecular weight, MwWeight average molecular weight, MpPeak molecular weight, Mz-z average molecular weight, Mz+1-z + 1 average molecular weight, Polydispersity-Polydispersity.
Example 2
(1) Preparation of norbornene copolymer: mixing a first monomer, a second monomer and a third monomer of the norborneol according to a ratio of 1: 0.75: 0.75, adding 345.44mg of the first monomer, 233.53mg of the second monomer, 323.66mg of the third monomer and 8.23mg of Grubbs-I as a catalyst into 50mL of dichloromethane for dissolution to obtain a reaction solution A, stirring at room temperature for 1h under an argon atmosphere, adding 2mL of vinyl ether, stirring for 5min to obtain a reaction solution B, carrying out rotary evaporation and concentration on the reaction solution B, slowly pouring the reaction solution B into ether to separate out a precipitate, filtering, washing the separated precipitate with ether, and drying to obtain the norbornene copolymer.
(2) Preparation of norbornene copolymer/carbon black/copper: mixing 500mg of the norbornene copolymer polymer prepared in the step (1) and 214mg of activated carbon powder, adding dichloromethane, fully dispersing, filtering, washing and drying to obtain a polynorbornene/carbon black mixture, adding the synthesized polynorbornene/carbon black into 50ml of anhydrous diethylene glycol dimethyl ether/dichloromethane mixed solvent for uniform dispersion, adding 25.82mg of sodium borohydride, adding 24.01mg of copper acetate after the sodium borohydride is dissolved, stirring at room temperature for 2 hours to obtain a reaction liquid C, dropwise adding excessive ether into the reaction liquid C, filtering, repeatedly washing with ether and removing residual solvent to obtain a black solid.
(3) Preparation of crosslinked norbornene copolymer/carbon Black three-dimensional network/copper: and heating the black solid at 150 ℃ for 7h under an argon atmosphere to obtain the PNBI/CB/Cu catalyst.
Example 3
(1) Preparation of norbornene copolymer: mixing a first monomer, a second monomer and a third monomer of the norborneol according to a ratio of 1: 1.25: 1.25, taking 345.44mg of the first monomer, 389.23mg of the second monomer, 539.41mg of the third monomer and 41.14mg of Grubbs-I as a catalyst, adding 50mL of dichloromethane to dissolve the first monomer, obtaining a reaction solution A, stirring the reaction solution A for 3 hours at room temperature under an argon atmosphere, adding 8mL of vinyl ether, stirring the reaction solution B for 20 minutes to obtain a reaction solution B, performing rotary evaporation and concentration on the reaction solution B, slowly pouring the reaction solution B into ether to separate out a precipitate, filtering the precipitate, washing the precipitate with ether, and drying the precipitate to obtain the norbornene copolymer.
(2) Preparation of norbornene copolymer/carbon black/copper: mixing 500mg of the norbornene copolymer polymer prepared in the step (1) and 1167mg of activated carbon powder, adding dichloromethane, fully dispersing, filtering, washing and drying to obtain a polynorbornene/carbon black mixture, adding the synthesized polynorbornene/carbon black into 50ml of an anhydrous diethylene glycol dimethyl ether/dichloromethane mixed solvent for dispersing, adding 75.32mg of sodium borohydride, adding 120.56mg of copper acetate after the sodium borohydride is dissolved, stirring at room temperature for 6 hours to obtain a reaction liquid C, dropwise adding excessive ether into the reaction liquid C, filtering, repeatedly washing with ether and removing residual solvent to obtain a black solid.
(3) Preparation of crosslinked norbornene copolymer/carbon Black three-dimensional network/copper: and heating the black solid at 170 ℃ for 4h under an argon atmosphere to obtain the PNBI/CB/Cu catalyst.
As shown in FIGS. 3 to 5, FIGS. 3, 4 and 5 are NMR spectra of the polymers obtained in example 1, example 2 and example 3, respectively, and the ratios of the characteristic peaks (. delta.7.26-7.41, 4.56, 4.40) are 5.64:0.99:2.00, 5.00:0.75:1.68 and 5.00:1.25:2.50, respectively, which are close to theoretical ratios of 5.00:1.00:2.00, 5.00:0.75:1.50 and 5.00:1.25:2.50, respectively, whereby the structural composition of the polymer can be adjusted by controlling the addition ratio of the three monomers, thereby controlling the hydrophilic-lipophilic balance of the crosslinked norbornene copolymer.
Examples 4 to 6
Similar to example 1, except that: the amount of Grubbs-I added was varied, 10.05mg, 30.23mg and 40.15mg for Grubbs-I in examples 4-6, respectively, and the number average molecular weights of the resulting copolymers were 16510, 14303 and 13569, respectively, i.e., the smaller the amount of catalyst used, the higher the molecular weight, and therefore, by controlling the amount of polymerization catalyst added, the molecular weight of the polymer was controlled, and copolymers of different molecular weights could be synthesized as desired.
Example 7
Adding 0.20mmol of chalcone, 0.24mmol of pinacol diboron and 0.000375mmol of catalyst into a mixed solvent of 1ml of tetrahydrofuran and 1ml of water, stirring for 12 hours at room temperature, filtering the PNBI/CB/Cu catalyst, performing rotary evaporation on the filtrate to remove the solvent, separating by column chromatography to obtain a boron addition reaction product, adding excessive sodium borate, oxidizing the boron addition reaction product into a hydroxyl compound, wherein the yield of the hydroxyl compound product is 94%, and the yield of the product in the Suzuki coupling reaction is still higher than 90% after the catalyst is recycled for 7 times.
The reaction formula is as follows:
wherein, the PNBI/CB/Cu catalyst after reaction is filtered, fully washed by ethyl acetate and ethanol for a plurality of times, and then dried, so that the PNBI/CB/Cu catalyst can be reused.
Example 8
Similar to example 7, except that the α, β -unsaturated aldehyde ketone used was 4-bromochalcone, the yield of the hydroxy compound product reached 90%, and the catalyst was recycled 7 times, the yield of the product was still higher than 85%.
The PNBI/CB/Cu catalyst provided by the embodiment of the invention has high catalytic activity, low feeding, high product yield of catalyzing boron addition reaction of alpha, beta-unsaturated aldehyde ketone and still has higher activity after repeated recycling.
Although embodiments of the present invention have been described in detail above, those of ordinary skill in the art will understand that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (7)
1. A copper nano catalyst loaded on a crosslinked norbornene copolymer/carbon black three-dimensional network is characterized by comprising:
the catalyst comprises a crosslinked norbornene copolymer/carbon black three-dimensional network carrier and nano copper loaded on the carrier, wherein the mass percentage of the copper in the crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst is 1.0-2.0%;
the norbornene copolymer is prepared by mixing a first monomer shown as a formula I, a second monomer shown as a formula II and a third monomer shown as a formula III according to a molar ratio of 1: (0.75-1.25): (0.75-1.25) polymerized product:
2. the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst as claimed in claim 1, wherein the norbornene copolymer has a molecular weight of 12000-17000.
3. A method for preparing the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst according to any one of claims 1 or 2, comprising the steps of:
1) reacting a reaction solution A containing the first monomer, the second monomer, the third monomer and a catalyst for 1-3h under an inert atmosphere, wherein the molar ratio of the first monomer to the second monomer to the third monomer to the catalyst is 1: (0.75-1.25): (0.75-1.25): (0.01-0.05);
2) adding a quenching agent into the reaction liquid A, continuously stirring for 5-20min to obtain a reaction liquid B, and concentrating and precipitating the reaction liquid B to obtain a norbornene copolymer;
3) dispersing a norbornene copolymer and activated carbon powder mixed material in an organic solvent to obtain a mixed dispersion liquid, wherein the mass fraction of the norbornene copolymer in the mixed material is 30-70%;
4) drying the mixed dispersion liquid to obtain a norbornene copolymer/carbon black mixture;
5) preparing diethylene glycol dimethyl ether dispersion liquid of the norbornene copolymer/carbon black, sequentially adding sodium borohydride and copper acetate, and stirring for 2-6 hours to obtain reaction liquid C, wherein the molar ratio of the sodium borohydride to the copper acetate is (3-5) to 1;
6) adding ether into the reaction liquid C to precipitate a norbornene copolymer/carbon black/Cu initial product, washing and drying the initial product, and heating at the temperature of 150-170 ℃ for 4-7h under inert gas to obtain the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nano catalyst.
4. The method for preparing a crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nano catalyst according to claim 3, wherein the catalyst in the step 1) is one selected from Grubbs catalyst or Schrock catalyst, and the quenching agent is vinyl ethyl ether.
5. The method for preparing a crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst as claimed in claim 3, wherein the washing treatment in step 6) comprises washing with deionized water, tetrahydrofuran and dichloromethane in sequence.
6. The method for preparing a crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst as claimed in claim 3, wherein the steps 1) to 5) are performed at room temperature.
7. The use of the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst as claimed in any one of claims 1 or 2, wherein the crosslinked norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst is used in the preparation of boron addition products of α, β -unsaturated aldehyde ketones or in the preparation of hydroxy compounds.
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Application publication date: 20191015 Assignee: Hangzhou Hongshun Pipe Industry Co.,Ltd. Assignor: HUBEI ENGINEERING University Contract record no.: X2023980048834 Denomination of invention: A cross-linked norbornene copolymer/carbon black three-dimensional network loaded copper nanocatalyst and its preparation method and application Granted publication date: 20211221 License type: Common License Record date: 20231130 |