CN110743620B - 一种磁性聚氮杂环卡宾钯催化剂及制备方法和应用 - Google Patents
一种磁性聚氮杂环卡宾钯催化剂及制备方法和应用 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 73
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004005 microsphere Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000005415 magnetization Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- -1 polytetrafluoroethylene Polymers 0.000 claims description 20
- 238000004108 freeze drying Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 238000007885 magnetic separation Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001555 benzenes Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 10
- 150000004693 imidazolium salts Chemical class 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 8
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 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 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims description 2
- SNHMUERNLJLMHN-IDEBNGHGSA-N iodobenzene Chemical group I[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 SNHMUERNLJLMHN-IDEBNGHGSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000009471 action Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 150000002940 palladium Chemical class 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 11
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 11
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 9
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 101150116295 CAT2 gene Proteins 0.000 description 3
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 3
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000006053 organic reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
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- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
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Abstract
本发明公开了一种磁性聚氮杂环卡宾钯催化剂及制备方法和应用,其特征在于催化剂载体为咪唑功能化的磁性聚合物微球,配体为氮杂环卡宾,活性组分为钯盐。活性组份钯盐中的钯的负载量为催化剂总质量的1.0~5.0%,咪唑功能化的磁性聚合物微球的粒径为200‑400 nm,比饱和磁化强度为20.0~50.0 emu/g,咪唑基含量为1.0~3.0 mmol/g。本发明将均相氮杂环卡宾钯催化剂负载到具有超顺磁性的聚合物微球表面,一方面氮杂环卡宾可较好地与活性粒子钯发生配位,提高钯纳米粒子在载体表面的分散性并防止钯在催化过程中发生流失,同时超顺磁性聚合物微球还具有在外加磁场作用下可以被磁化,撤去外加磁场后则磁性消失的特点。能显示出高催化活性和重复使用性能,反应条件温和。
Description
发明领域
本发明涉及一种磁性聚氮杂环卡宾钯催化剂及制备方法和应用。
背景技术
近年来,氮杂环卡宾(N-Heterocyclic Carbene,简称NHC)由于具有优良的给电子特性、与金属Pd络合可形成稳定的Pd-卡宾σ键、以及对空气、水和热稳定等众多优点目前已在钯催化的C-C偶联等有机反应中得到了广泛的应用。如本发明人主要完成人曾经提出并授权的 CN201510028685.5《一种介孔碳负载氮杂环卡宾钯催化剂及制备方法和应用》,催化剂载体为硬模板法制备的羟基化的介孔碳,配体为氮杂环卡宾,活性组分为氯化钯。
然而氮杂环卡宾钯这类催化剂本身仍是一类均相催化剂,存在分离和重复使用难等问题,这在很大程度上限制了其在有机反应中的进一步应用。均相催化剂的非均相化被认为能有效解决均相催化剂分离和重复利用问题,反应结束后通过简单的过滤、离心及外磁场作用就可将非均相催化剂从反应体系分离出来以进行下一轮的循环使用。
基于此,目前国内外关于氮杂环卡宾钯催化剂的非均相化的研究十分活跃,很多类型的材料如聚合物、碳材料、硅材料、以及磁性纳米材料都用于氮杂环卡宾钯催化剂的负载。在众多的载体材料中,磁性纳米材料由于在分离方面的巨大优势而使其在氮杂环卡宾钯催化剂的非均相化中具有广阔的应用前景。目前已有多篇关于磁性纳米材料负载型氮杂环卡宾钯催化剂的制备及催化性能的报道。
如CN201010125572.4 《金属氮杂环卡宾配合物的电化学合成方法》,在可通入惰性气体的一室型电解池中,以铜片、锰片、铁片、钴片或镍片作为阳极,以铜片、锰片、铁片、钴片、镍片、铂片或石墨片为阴极,以乙腈为溶剂,向溶剂中加入卡宾配体前驱物咪唑盐或氮杂环卡宾银配合物,在惰性气体氛围中电化学合成金属氮杂环卡宾配合物。电解完毕后过滤,蒸去溶剂就得到金属氮杂环卡宾配合物。用于催化Suzuki-Miyaura偶联等反应,在精细化工和制药工业中具有广泛的应用前景。
又如CN201410464296.2 《核壳结构贵金属氮杂环卡宾聚合物磁性催化》,包括顺磁性Fe3O4核和包裹在其表面的贵金属氮杂环卡宾聚合物。在Fe3O4纳米颗粒存在下,以N,N-二甲基甲酰胺(DMF)作为溶剂,将咪唑盐单体TIPT-Cl或TIPB-Cl与贵金属醋酸盐首先在90℃下超声反应1h,之后于油浴中在110℃下反应5h,得到贵金属氮杂环卡宾聚合物磁性催化剂。该催化剂中的活性位点高度分散,具有很好的催化活性;而磁性Fe3O4核的存在使得该催化剂在液相反应中易于分离,便于回收利用, 仅用1%的催化剂室温下1h就 可以实现Suzuki偶联反应中反应中接近100%的转化。
另外 CN201010562077.X《氮杂环卡宾-钯-咪唑络合物催化芳基氯化物室温水相铃木偶联反应》,从简单易得的咪唑盐出发,先合成相应的氮杂环卡宾-金属-咪唑络合物,再利用这些络合物,实现室温、水相条件下芳基或杂芳基硼酸与芳基氯化物的铃木(Suzuki-Miyaura)偶联反应。金属盐中所涉及的金属中心可以是铁、铜、银、镍、钯、钴、铑、钌等等。本发明中所使用的催化剂易于制备,在催化量仅为0.01mol%的条件下,也可以实现相应的偶联反应,而且收率优异。
本发明人长期从事相关技术的研发,深知现有技术发展过程和现状,应该指出的是,目前报道的磁性纳米材料负载氮杂环卡宾钯催化剂的催化性能仍然不是很高,在催化过程中钯往往发生流失,这在很大程度上影响了负载型氮杂环卡宾钯催化剂的重复使用性能。因此,研制和开发新型的磁性纳米材料负载氮杂环卡宾钯催化剂至今仍是催化领域的一项重大研究课题。
发明内容
本发明的目的之一提供了一种磁性聚氮杂环卡宾钯催化剂的制备方法及其应用,可以克服现有技术的缺点。本发明选用有别于目前常用的载体具有超顺磁性的磁性聚合物微球为载体,氮杂环卡宾为配体负载钯,磁性聚氮杂环卡宾钯催化剂用于卤代苯与芳基硼酸的C-C偶联反应显出高的催化活性,反应条件温和,且催化剂在外加磁场作用下能够实现快速回收,操作简单,实用性强。
本发明的目的之二在于提供了一种磁性聚氮杂环卡宾钯催化剂的制备方法。
本发明的目的之三在于提供了一种磁性聚氮杂环卡宾钯催化剂的应用。
本发明的目的之一是这样实现的:催化剂载体为咪唑功能化的磁性聚合物微球,配体为氮杂环卡宾,活性组分为钯盐。
所述的活性组份钯盐中的钯的负载量为催化剂总质量的1.0~5.0 %,咪唑功能化的磁性聚合物微球的粒径为200-300 nm,比饱和磁化强度为20.0~50.0 emu/g,咪唑基含量为1.0~3.0 mmol/g。
本发明的目的之二是这样实现的:所述的磁性聚氮杂环卡宾钯催化剂的制备方法包括下述步骤:
⑴ 咪唑功能化磁性聚合物微球的制备:
将1~3份的六水氯化铁溶解于50~100 份的乙二醇中,待其完全溶解后,再加入4~8份的醋酸钠和1~3份的聚乙二醇。上述混合物在50℃机械搅拌1 h后再转移至100 mL的聚四氟乙烯内衬不锈钢高压釜中,升温至200 ℃反应4~8 h,冷却至室温后,产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,经冷冻干燥后得到黑色粉体即Fe3O4微球;在三口烧瓶中加入0.1~0.3份的Fe3O4微球和80~120 mL的乙醇,机械搅拌30~60min后,再依次加入3~5 mL 的γ-甲基丙烯酰氧基丙基三甲氧基硅烷、20~40 mL的蒸馏水和3~7 mL 氨水,将上述混合物在40℃下机械搅拌12 h,冷却至室温后产物经离心分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,直至洗脱液呈中性;经冷冻干燥后得到黑色粉体即为乙烯基功能化的Fe3O4微球;在150 mL的三口烧瓶中加入0.1~0.2份的乙烯基功能化的Fe3O4微球和80 mL的乙腈,再加入0.06~0.1份的引发剂偶氮二异丁腈,再加入1.0~3.0 mL的二甲基丙烯酸乙二醇酯和1.0~3.0 mL的咪唑功能化的乙烯基化合物。将上述混合物加热到90℃反应2 h,冷却至室温后产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,经冷冻干燥后得到黄色粉体即为咪唑功能化的磁性聚合物微球;
⑵ 磁性聚合物微球负载咪唑鎓盐的制备:
将0.1~0.5 份所述的咪唑功能化的磁性聚合物微球加入到40~80 份的含有碘甲烷的化合物的二氯乙烷溶液中,其中含有碘甲烷的二氯乙烷溶液的质量百分比1.0~10.0 %,超声振荡120~240 min,在温度为25 ℃的条件下机械搅拌反应720~1440 min,冷却至室温后产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,直至洗脱液呈中性;经冷冻干燥后得到黑色粉体即为磁性聚合物微球负载咪唑鎓盐;
⑶ 磁性聚氮杂环卡宾钯催化剂的制备:
将0.1~0.5份的所述的磁性聚合物微球负载咪唑鎓盐加入到碳酸钠的50份的水和50份的氮,氮-二甲基甲酰胺中,碳酸钠的水溶液的质量百分数为1.0~5.0 %;室温反应120~360 min后再加入0.1~0.5份的醋酸钯,50 ℃反应720~1440 min后经磁分离和冷冻干燥后得到的黑色粉体即为磁性聚氮杂环卡宾钯催化剂;磁性聚氮杂环卡宾钯催化剂中的钯负载量为催化剂总质量的1.0~5.0 %;
所述的份为质量份;min为分钟。
步骤1所述的咪唑功能化的乙烯基化合物为乙烯基咪唑、烯丙基咪唑及它们的衍生物的一种或多种。
本发明的目的之三是这样实现的:本发明的催化剂用于卤代苯与芳基硼酸的Suzuki反应,反应氛围在空气中进行,反应后经离心分离回收催化剂,催化剂循环使用;卤代苯为碘代苯、溴代苯、氯苯或它们其中之一的衍生物,芳基硼酸为苯硼酸或它们其中之一的衍生物,Suzuki反应中所用的溶剂为水和乙醇的混合物,碱为碳酸钠或碳酸钾;反应温度为80~100 ℃,反应时间为0.5~3.0 h;卤代苯为3.0~7.0 mmol,卤代苯:芳基硼酸:碱=1:1.5~2.0 :2.0~5.0,催化剂为芳基卤代物的0.01~0.5 mol%,反应溶剂为3.0~8.0 mL的乙醇和水混合物,其中EtOH:H2O体积比=1: 1。
本发明将均相氮杂环卡宾钯催化剂负载到具有超顺磁性的聚合物微球表面,一方面氮杂环卡宾可较好地与活性粒子钯发生配位,提高钯纳米粒子在载体表面的分散性并防止钯在催化过程中发生流失,同时超顺磁性聚合物微球还具有在外加磁场作用下可以被磁化,撤去外加磁场后则磁性消失的特点。因此本发明的磁性聚氮杂环卡宾钯催化剂用于卤代苯与芳基硼酸的Suzuki反应显示出高的催化活性和重复使用性能,反应条件温和,且催化剂在外加磁场作用下能够实现快速回收,操作简单,实用性强。
与目前相关背景技术相比,本发明技术创造主要体现在以下方面:
(1) 本发明通过咪唑功能化的乙烯基化合物在γ-甲基丙烯酰氧基丙基三甲氧基硅烷活化的Fe3O4表面的蒸馏沉淀聚合,一步就可将高浓度的咪唑基团引入到磁性聚合物微球表面,以其为载体制备的磁性聚氮杂环卡宾钯催化剂不仅具有较高的催化活性同时还具有较好的循环使用性能。此外,通过本思路构筑的磁性钯催化剂中高浓度的活性中心还有利于催化剂活性中心的协同,可使其展现出比相应的均相氮杂环卡宾钯催化剂更快的反应速度。
(2) 通过本思路可将氮杂环卡宾前驱体高度交联在磁性聚合物骨架中,当其与钯盐络合后,单个氮杂环卡宾分子的空间位阻就变大,其较大的空间位阻效应不仅能促进Pd中间产物的形成,降低有机反应的活化能,同时还能在催化循环的多个步骤发挥作用。
具体实施方式
本发明技术方案不局限于以下所列举具体实施方式,还包括具体实施方式间的任意组合。
咪唑功能化的磁性聚合物微球的制备方法:
实施例1
将2.5份的六水氯化铁溶解于80 份的乙二醇中,待其完全溶解后,再加入7.2份的醋酸钠和2份的聚乙二醇。上述混合物在50℃机械搅拌1 h后再转移至100 mL的聚四氟乙烯内衬不锈钢高压釜中,升温至200 ℃反应6 h,冷却至室温后,产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,经冷冻干燥后得到黑色粉体即Fe3O4微球;在三口烧瓶中加入0.3份的Fe3O4微球和100 mL的乙醇,机械搅拌30 min后,再依次加入4 mL 的γ-甲基丙烯酰氧基丙基三甲氧基硅烷、36 mL蒸馏水和4 mL 氨水,将上述混合物在40℃下机械搅拌12 h,冷却至室温后产物经离心分离后,依次用10份的乙醇和10份的蒸馏水洗涤,直至洗脱液呈中性;经冷冻干燥后得到黑色粉体即为乙烯基功能化的Fe3O4微球;在150 mL的三口烧瓶中加入0.15份的乙烯基功能化的Fe3O4微球和80 mL的乙腈,再加入0.08 份的引发剂偶氮二异丁腈,再加入1 mL的二甲基丙烯酸乙二醇酯和1 mL的咪唑功能化的乙烯基化合物。将上述混合物加热到90℃反应2 h,冷却至室温后产物经磁分离后,依次用10份的乙醇和10份的蒸馏水洗涤,经冷冻干燥后得到黄色粉体即为咪唑功能化的磁性聚合物微球;
磁性聚氮杂环卡宾钯催化剂的制备方法:
实施例2
将0.1份所述的咪唑功能化的磁性聚合物微球加入到50份的含有碘甲烷的化合物的二氯乙烷溶液中,其中含有碘甲烷的二氯乙烷溶液的质量百分比5.0 %,超声振荡120min,在温度为25 ℃的条件下机械搅拌反应1440 min,冷却至室温后产物经磁分离后,依次用10份的乙醇和10份的蒸馏水洗涤,经冷冻干燥后得到黑色粉体即为磁性聚合物微球负载咪唑鎓盐。将0.2份的所述的磁性聚合物微球负载咪唑鎓盐加入到碳酸钠的50份的水和50份的氮,氮-二甲基甲酰胺中,碳酸钠的水溶液的质量百分数为1.0 %;室温反应120 min后再加入0.1份的醋酸钯,50 ℃反应720 min后经磁分离和冷冻干燥后得到的黑色粉体即为磁性聚氮杂环卡宾钯催化剂Cat 1;
实施例3
将0.1份所述的咪唑功能化的磁性聚合物微球加入到50份的含有碘甲烷的化合物的二氯乙烷溶液中,其中含有碘甲烷的二氯乙烷溶液的质量百分比5.0 %,超声振荡120min,在温度为25 ℃的条件下机械搅拌反应1440 min,冷却至室温后产物经磁分离后,依次用10份的乙醇和10份的蒸馏水洗涤,经冷冻干燥后得到黑色粉体即为磁性聚合物微球负载咪唑鎓盐。将0.1份的所述的磁性聚合物微球负载咪唑鎓盐加入到碳酸钠的50份的水和50份的氮,氮-二甲基甲酰胺中,碳酸钠的水溶液的质量百分数为2.0 %;室温反应120 min后再加入0.1份的醋酸钯,50 ℃反应720 min后经磁分离和冷冻干燥后得到的黑色粉体即为磁性聚氮杂环卡宾钯催化剂Cat 2;
磁性聚氮杂环卡宾钯催化剂的应用:
实施例4
在空气氛围中进行,以Cat 1为催化剂,反应温度为80 ℃,反应1.5 h,n (碘苯)为5.0 mmol,n(碘苯):n(芳基硼酸):n(碳酸钾)=1.0: 1.5: 2.0,Cat 1为碘苯的0.05 mol%,2.5 mL H2O和2.5 mL EtOH为反应溶剂,反应结束后,离心分离催化剂,倾出上层液。催化剂继续下一次的反应。用气相色谱分析上层液产物的产率,结果见表1。
实施例5
在空气氛围中进行,以Cat 1为催化剂,反应温度为80 ℃,反应1.5 h,n (溴苯)为5.0 mmol,n(溴苯):n(芳基硼酸):n(碳酸钾)=1.0: 1.5: 2.0,Cat 1为溴苯的0.08 mol%,2.5 mL H2O和2.5 mL EtOH为反应溶剂,反应结束后,离心分离催化剂,倾出上层液。催化剂继续下一次的反应。用气相色谱分析上层液产物的产率,结果见表1。
实施例6
在空气氛围中进行,以Cat 2为催化剂,反应温度为80 ℃,反应1.5 h,n (碘苯)为5.0 mmol,n(碘苯):n(芳基硼酸):n(碳酸钾)=1.0: 1.5: 2.0,Cat 2为碘苯的0.05 mol%,2.5 mL H2O和2.5mL EtOH为反应溶剂,反应结束后,离心分离催化剂,倾出上层液。催化剂继续下一次的反应。用气相色谱分析上层液产物的产率,结果见表1。
实施例7
在空气氛围中进行,以Cat 2为催化剂,反应温度为80 ℃,反应1.5 h,n (溴苯)为5.0 mmol,n(溴苯):n(芳基硼酸):n(碳酸钾)=1.0: 1.5: 2.0,Cat 2为溴苯的0.08 mol%,2.5mL H2O和2.5mLEtOH为反应溶剂,反应结束后,离心分离催化剂,倾出上层液。催化剂继续下一次的反应。用气相色谱分析上层液产物的产率,结果见表1。
表1 磁性聚氮杂环卡宾钯催化剂的催化活性
催化剂 | 催化剂用量 (mol%) | 卤代苯 | GC产率 (%) |
Cat 1 | 0.05 | 碘苯 | 99.9 |
Cat 1 | 0.08 | 溴苯 | 98.5 |
Cat 2 | 0.05 | 碘苯 | 99.8 |
Cat 2 | 0.08 | 溴苯 | 98.3 |
表1为Cat 1~2的催化活性数据。从表1可以看出,在较短的时间内(1.5h),较低的催化剂用量(0.05~0.1 mol%)和较低的反应温度(80℃)下,本发明专利制备的磁性聚氮杂环卡宾钯催化剂Cat 1~2催化的Suzuki反应的产物产率即可达98.3~99.9%,这说明磁性聚氮杂环卡宾钯催化剂Cat 1~2具有很高的反应活性。
实施例8
催化剂循环测试
在空气氛围中进行,以Cat 1为催化剂,反应温度为80 ℃,反应1.5 h,n (溴苯)为5.0 mmol,n(溴苯):n(芳基硼酸):n(碳酸钾)=1.0: 1.5: 2.0,Cat 1为溴苯的0.08 mol%,2.5ml 纯水和2.5ml乙醇为反应溶剂,反应结束后,离心分离出催化剂,倾出上层液,用GC分析上层液产物的产率。然后耐压管补加2.5ml纯水和2.5ml乙醇,溴苯 (5.0 mmol),芳基硼酸 (7.5 mmol),碳酸钾 (10.0 mmol),开动磁力搅拌,水浴加热到80℃反应1.5 h,离心分离催化剂,倾去上层液,用GC分析上层液产物的产率。如此循环使用5次,分别用GC测试Suzuki反应产物产率,结果表明Cat2连续使用5次后,产物产率为97.2%,这说明Cat 1具有很好的重复使用性能。
由本催化剂循环测试可知具体实施例3所得的cat 1可循环使用。其它的催化剂循环测试同理。
Claims (3)
1.一种磁性聚氮杂环卡宾钯催化剂的制备方法,其特征在于制备方法包括下述步骤:
⑴ 确定催化剂载体:
选用咪唑功能化的磁性聚合物微球为催化剂载体,其制备方法如下:
将1~3份的六水氯化铁溶解于50~100 份的乙二醇中,待其完全溶解后,再加入4~8份的醋酸钠和1~3份的聚乙二醇;上述混合物在50℃机械搅拌1 h后再转移至100 mL的聚四氟乙烯内衬不锈钢高压釜中,升温至200 ℃反应4~8 h,冷却至室温后,产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,经冷冻干燥后得到黑色粉体即Fe3O4微球;在三口烧瓶中加入0.1~0.3份的Fe3O4微球和80~120 mL的乙醇,机械搅拌30 ~60min后,再依次加入3~5 mL 的γ-甲基丙烯酰氧基丙基三甲氧基硅烷、20~40 mL的蒸馏水和3~7 mL 氨水,将上述混合物在40℃下机械搅拌12 h,冷却至室温后产物经离心分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,直至洗脱液呈中性;经冷冻干燥后得到黑色粉体即为乙烯基功能化的Fe3O4微球;在150 mL的三口烧瓶中加入0.1~0.2份的乙烯基功能化的Fe3O4微球和80 mL的乙腈,再加入0.06~0.1份的引发剂偶氮二异丁腈,再加入1.0~3.0 mL的二甲基丙烯酸乙二醇酯和1.0 ~3.0 mL的咪唑功能化的乙烯基化合物;将上述混合物加热到90℃反应2 h,冷却至室温后产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,经冷冻干燥后得到黄色粉体即为咪唑功能化的磁性聚合物微球;
⑵ 磁性聚合物微球负载咪唑鎓盐的制备:
将0.1~0.5 份所述的咪唑功能化的磁性聚合物微球加入到40~80 份的含有碘甲烷的化合物的二氯乙烷溶液中,其中含有碘甲烷的二氯乙烷溶液的质量百分比1.0~10.0 %,超声振荡120~240 min,在温度为25 ℃的条件下机械搅拌反应720~1440 min,冷却至室温后产物经磁分离后,依次用10~20份的乙醇和10~20份的蒸馏水洗涤,经冷冻干燥后得到黑色粉体即为磁性聚合物微球负载咪唑鎓盐;
⑶ 磁性聚氮杂环卡宾钯催化剂的制备:
将0.1~0.5份的所述的磁性聚合物微球负载咪唑鎓盐加入到50份的碳酸钠的水溶液和50份的氮,氮-二甲基甲酰胺混合溶液中,碳酸钠的水溶液的质量百分数为1.0~5.0 %;室温反应120~360 min后再加入0.1~0.5份的醋酸钯,50 ℃反应720~1440 min后经磁分离和冷冻干燥后得到的黑色粉体即为磁性聚氮杂环卡宾钯催化剂;其中催化剂载体为咪唑功能化的磁性聚合物微球,配体为氮杂环卡宾,活性组分为钯盐;
磁性聚氮杂环卡宾钯催化剂中的钯负载量为催化剂总质量的1.0~5.0 %,咪唑功能化的磁性聚合物微球的粒径为200-400 nm,比饱和磁化强度为20.0~50.0 emu/g,咪唑基含量为1.0~3.0 mmol/g;所述的份为质量份;min为分钟。
2.根据权利要求1所述的一种磁性聚氮杂环卡宾钯催化剂的制备方法,其特征在于所述的含有咪唑功能化的乙烯基化合物为乙烯基咪唑、烯丙基咪唑及它们的衍生物的一种或多种。
3.根据权利要求1-2任一权利要求所述方法得到的一种磁性聚氮杂环卡宾钯催化剂的应用,其特征在于所述的磁性聚氮杂环卡宾钯催化剂用于卤代苯与芳基硼酸的Suzuki反应,反应氛围在空气中进行,反应后经磁分离回收催化剂,催化剂循环使用;卤代苯为碘代苯、溴代苯、氯苯或它们其中之一的衍生物,芳基硼酸为苯硼酸,Suzuki反应中所用的溶剂为水和乙醇的混合物,碱为碳酸钠或碳酸钾;反应温度为80~100 ℃,反应时间为0.5~3.0h;卤代苯为3.0~7.0 mmol,卤代苯:芳基硼酸:碱=1: 1.5~2.0 :2.0~5.0,催化剂为卤代苯的0.01~0.5 mol%,反应溶剂为3.0~8.0 mL的乙醇和水混合物,其中EtOH:H2O体积比=1: 1。
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