CN104959164A - Polymer-nano metallic particle catalyst and preparation method - Google Patents
Polymer-nano metallic particle catalyst and preparation method Download PDFInfo
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- CN104959164A CN104959164A CN201510386626.5A CN201510386626A CN104959164A CN 104959164 A CN104959164 A CN 104959164A CN 201510386626 A CN201510386626 A CN 201510386626A CN 104959164 A CN104959164 A CN 104959164A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013528 metallic particle Substances 0.000 title abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229920001519 homopolymer Polymers 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 27
- 150000003624 transition metals Chemical class 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 19
- 239000002923 metal particle Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- MCXLQFOCWZMFHV-UHFFFAOYSA-N 4-ethenyl-2h-triazole Chemical compound C=CC1=CNN=N1 MCXLQFOCWZMFHV-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 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 9
- 238000000034 method Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- YMPBAEMKFZQPRA-UHFFFAOYSA-N [Cl].[Hf] Chemical compound [Cl].[Hf] YMPBAEMKFZQPRA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 3
- 239000012989 trithiocarbonate Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 229910003603 H2PdCl4 Inorganic materials 0.000 abstract 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 allyl halide Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a polymer-nano metallic particle catalyst, and particularly relates to a polymer-nano palladium catalyst and a preparation method thereof. The preparation method of the polymer-nano palladium catalyst comprises: homopolymerizing a prepared vinyl monomer containing a triarylated imidazole group 1-(4-(4,5-diphenyl-1H-imidazole-2-group) phenyl)-4-vinyl-1,2,3-triazole (DVT) or copolymerizing the prepared vinyl monomer (DVT) with other vinyl monomers to obtain DVT homopolymer or copolymer, dissolving the homopolymer or copolymer in DMF, charging an appropriate amount of H2PdCl4 aqueous solution, rapidly stirring and facilitating the reaction under 80 DEG C to obtain black precipitates, i.e. polymer-nano palladium catalyst. The catalyst can be used for catalyzing organic coupling reaction such as Suzuki, Heck, Stille and the like and is high in catalytic activity, good in selectivity, moderate in reaction condition and good in repeatability.
Description
Technical field
The present invention relates to a kind of polymer-nanometer metal particle catalyst, especially polymer-nano Pd catalyst and preparation method thereof, belong to metal nano material catalyst technical field.
Background technology
Metal Palladium (Pd) solid catalyst occupies an important position in catalytic field, and can organic coupling reaction such as catalysis Suzuki, Heck and Stille.Research shows, when metal Pd catalyst exists with nanoscale form, can show higher reactivity and selective, and the size and shape of nano particle has significant impact to its catalytic performance.Based on this, domestic and international worker is devoted for years in research Pd nano particle shape characteristic the mechanism of action of its catalytic performance.The nanocatalyst of noble metal has less particle diameter, higher surface-active and larger specific area, and along with the reduction of grain diameter, its specific area significantly increases, and surface atom number proportion in whole Particle Cluster also greatly increases.The increase of surface atom number causes the increase of surface atom coordination unsaturation, thus create a large amount of outstanding keys and unsaturated bond etc., surface kink, gauffer and defect also increase thereupon, and the defect of these nano-particle surfaces just becomes the avtive spot in catalytic reaction.
Suzuki reacts (suzuki reaction), also referred to as Suzuki coupling reaction, Suzuki-Miyaura reaction (Suzuki-Pu, palace reaction), is a newer organometallic coupling reaction.Heck reaction is also called Mizoroki-Heck reaction, is the reaction being generated substituted olefine by a unsaturated halogenated hydrocarbons (or fluoroform sulphonate) and alkene under highly basic and palladium chtalyst.Stille reaction is aryl or alkenylstannane and aryl, thiazolinyl, benzyl, allyl halide or the cross-coupling reaction of its trichloromethane sulfonic acid ester under palladium chtalyst.The catalytic site that polymer-nano Pd catalyst prepared by the present invention provides is far above traditional catalyst, for having higher catalytic activity and better repeatability in above-mentioned three coupling reactions, this polymer-nano Pd catalyst can be predicted in serial coupling reaction, have good development prospect.
Summary of the invention
For the problems referred to above, the invention provides strong, selective good, a kind of polymer-nano Pd catalyst that reusability is good of a kind of catalytic activity and preparation method thereof.
According to the first embodiment of the present invention, a kind of polymer-nanometer metal particle catalyst is provided, described catalyst comprises vinyl triazole polymer containing triarylimidazoles group and nano grade transition metal particle, and the particle diameter of transition metal particles is 2 ~ 100nm, preferably 3 ~ 50nm, more preferably 3 ~ 10nm; Preferably, this transition metal is palladium, platinum, zirconium, hafnium, scandium or titanium.
Preferably, described polymer is containing triarylimidazoles base vinyl triazole monomer 1-(4-(4,5-diphenyl-1H-imidazoles-2-base) phenyl)-4-vinyl-1, the random copolymer of the homopolymers of 2,3-triazole (be called for short DVT) or itself and other ethylenically unsaturated monomer (especially vinyl monomer); This monomer DVT has following general formula I:
Preferably, the homopolymers of DVT or random copolymer have following structural formula (II) or (III) respectively:
Generally, in general formula (III), A-c-d-B is the unit of other ethylenically unsaturated monomer.Generally, A is H or methyl.Preferably, B has 2-10 carbon atom and 0-3 heteroatomic organic substituent.
Preferably, ethylenically unsaturated monomer is selected from one or more vinyl monomers in these monomers following: (methyl) acrylic compounds, (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) phenylethylene, acrylonitrile, vinyl carboxylates class, vinyl pyrrolidone, vinylpyridine, VCz or vinyl triazole type.
According to the second embodiment of the present invention, provide the preparation method of polymer-nanometer metal particle catalyst, the method comprises the following steps:
(1) the vinyl triazole monomer containing triarylimidazoles group carried out radically homo reaction or carry out random copolymerization reaction with other ethylenically unsaturated monomer (especially vinyl monomer), obtaining the vinyl triazole homopolymers containing triarylimidazoles group or copolymer;
(2) gained homopolymers or copolymer are dissolved in forming reactions mixture in solvent (as DMF), transistion metal compound or transition metal precursor is added in this reactant mixture, then occur to decompose or be reduced to allow reactant mixture react under separating out the reaction condition of transition metal simple substance at this transistion metal compound or transition metal precursor, thus allow transition metal be carried on described polymer.Then from reactant mixture, isolate solids and its is washed, dry, obtain polymer-nanometer metal particle catalyst, the transition metal wherein in transistion metal compound or transition metal precursor is palladium, platinum, zirconium, hafnium, scandium or titanium.
Preferably, transistion metal compound or transition metal precursor are chlorine palladium acid H in the above-mentioned methods
2pdCl
4or ammonium chloropalladate salt (NH
4)
2pdCl
4, chloroplatinic acid H
2ptCl
6or chloroplatinic acid ammonium salt (NH
4)
2ptCl
6, the acid of chlorine hafnium or chlorine hafnium acid ammonium salt.
Preferably, the step (1) of said method is carried out as follows:
It is the DVT monomer of 1 by molar part, molar part is the initator azodiisobutyronitrile (AIBN) of 0.02 ~ 0.08, molar part is the chain-transferring agent S-ethyl group-S'-(α of 0.005 ~ 0.02, α '-dimethyl-α "-propionyloxy) trithiocarbonate (EMP), molar part is the solvent N of 20 ~ 200, dinethylformamide (DMF) is placed in single necked round bottom flask, drum nitrogen deoxygenation (namely, blast nitrogen and discharge oxygen or discharge oxygenous air) remove oxygen in reaction system, in 55 ~ 85 DEG C (such as 60 ~ 80 DEG C, as 70 DEG C) insulation reaction (such as 15 ~ 40h in oil bath pan, as 24h), homopolymers poly (DVT) can be obtained.Generally, yield is 65 ~ 85%.
Or the step (1) of said method is carried out as follows:
It is the DVT monomer of 1 by molar part, molar part is the ethylenically unsaturated monomer (monomer as containing vinyl) of 2 ~ 20, molar part is the initiator A IBN of 0.02 ~ 0.08, molar part is the chain-transferring agent EMP of 0.005 ~ 0.02, molar part be 20 ~ 200 solvent DMF be placed in flask, oxygen in drum nitrogen deoxygenation removing reaction system, in 55 ~ 85 DEG C (such as 60 ~ 80 DEG C, as 70 DEG C) insulation reaction (such as 15 ~ 40h in oil bath pan, as 24h), the copolymer of DVT and ethylenically unsaturated monomer (as vinyl-containing monomers) can be obtained.Generally, yield is 70 ~ 88%.
Citing, the reaction equation obtaining homopolymers is as follows:
Citing, the reaction equation obtaining copolymer is as follows:
As can be seen from polymerization process, what be obtained by reacting is random copolymer.
Preferably, the step (2) of said method is carried out as follows:
The homopolymers obtain step (1) or copolymer are dissolved in forming reactions mixture in solvent (as DMF), slowly drip transistion metal compound or transition metal precursor (H as sour in chlorine palladium in this reactant mixture
2pdCl
4or ammonium chloropalladate salt (NH
4)
2pdCl
4, chloroplatinic acid H
2ptCl
6or chloroplatinic acid ammonium salt (NH
4)
2ptCl
6, chlorine hafnium acid or chlorine hafnium acid ammonium salt) the aqueous solution (in right amount), optionally add reducing agent (as Sn, SnCl
2, ascorbic acid, tartaric acid or citric acid), in 65 ~ 95 DEG C (such as 70 ~ 90 DEG C, as 80 DEG C) under condensing reflux reaction (such as 5-20h, as 8-12h), there is black precipitate to separate out, stoste centrifugal treating will be reacted so that collecting precipitation thing (such as centrifugal collecting precipitate under 8000rpm rotating speed), the drying precipitate of then will collect, obtains polymer-nano Pd catalyst.Such as, the sediment of collection is carried out washing [such as using DMF, H
2o many times (such as 2 times-4 times) is washing alternately], be centrifugally placed on air drying in vacuum drying chamber, namely obtain polymer-nano Pd catalyst.Generally, yield is higher than 99%.
In this application, " optionally " expression is carried out or is not carried out, or expression is with or without.
Preferably, ethylenically unsaturated monomer is selected from one or more vinyl monomers in these monomers following: (methyl) acrylic compounds, (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) phenylethylene, acrylonitrile, vinyl carboxylates class, vinyl pyrrolidone, vinylpyridine, VCz or vinyl triazole type.
Preferably, transistion metal compound or transition metal precursor are H
2pdCl
4, and its consumption is 2 ~ 5 times of nitrogen atom content in polymer, calculates by mol.
The number-average molecular weight of the homopolymers that the present invention obtains or copolymer is 5000 ~ 40000g/mol, preferably, and 10000 ~ 30000g/mol.Their glass transition temperature T
gfor 90-120 DEG C.
Polymer-nanometer metal particle catalyst provided by the invention (especially polymer-nano Pd catalyst) has the following advantages:
Vinyl monomer 1-(the 4-(4 containing triarylimidazoles group that the present invention is used, 5-diphenyl-1H-imidazoles-2-base) phenyl)-4-vinyl-1,2,3-triazole (DVT) is containing multiple nitrogen heterocyclic ring, nitrogen content is higher, contributes to the load capacity improving transition metal (as palladium).The transition metal (as palladium) of load is nanoscale, is uniformly dispersed, and Size Distribution little (can control to and be low to moderate about 2 ~ 10nm), adds the avtive spot of catalyst.Polymer provided by the invention-nano transition metal particle (as palladium particle) catalyst activity strong, selective good, reaction condition is gentle, reusability good, has good market using value.
Accompanying drawing explanation
Fig. 1 is the nuclear-magnetism figure of the homopolymers poly (DVT) of embodiment 1.
Fig. 2 is the TEM figure of the polymer-Technique of Nano Pd nano material of embodiment 2.
Fig. 3 is the nuclear-magnetism figure of the copolymer poly (DVT-co-DMAA) of embodiment 2.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.
Anhydrous potassium carbonate: Xilong Chemical Co., Ltd, AR.
Azodiisobutyronitrile (AIBN): Shanghai City Hai Qu Chemical Co., Ltd., recrystallizing methanol twice.
Chlorine palladium acid: Aladdin chemical reagents corporation, AR.
Iodobenzene: Sa En chemical technology Co., Ltd, AR.
Biphenyl: Aladdin chemical reagents corporation, AR.
Phenyl boric acid: Aladdin chemical reagents corporation, AR.
Absolute ether: Tianjin Fu Yu Fine Chemical Co., Ltd, AR.
DMF (DMF): Tianjin Kermel Chemical Reagent Co., Ltd., with the dry 12h decompression distillation of calcium hydride.
Absolute ethyl alcohol: Tianjin great Mao chemical reagent factory, AR.
Acetonitrile: Chemical Reagent Co., Ltd., Sinopharm Group, HPLC.
S-ethyl group-S'-(α, α '-dimethyl-α "-propionyloxy) trithiocarbonate (EMP): Aladdin chemical reagents corporation, AR.
Embodiment 1
Vinyl monomer 1-(4-(4,5-diphenyl-1H-imidazoles-2-base) phenyl)-4-vinyl-1,2,3-triazoles (DVT) containing triarylimidazoles group is carried out radically homo.Take DVT monomer 1.3g, AIBN 11mg, EMP 75mg, DMF 16.7mL, be placed in single necked round bottom flask, the oxygen in drum nitrogen deoxygenation removing reaction system, insulation reaction 24h in 70 DEG C of oil bath pans, then by its sedimentation in sudden cold, ether in frozen water, suction filtration can obtain 1.07g poly (DVT).
The poly obtained (DVT) is dissolved in 172mL DMF solution, adds 171mL H
2pdCl
4the aqueous solution (concentration is 0.04mol/L), condensing reflux at 80 DEG C, reaction 12h, can obtain 1.8gpoly (DVT)-Pd catalyst.
The characterization parameter of homopolymers: number-average molecular weight is 11000g/mol, glass transition temperature T
gbe 108 DEG C, its nuclear-magnetism figure as shown in Figure 1.
Embodiment 2
DVT and N,N-DMAA (DMAA) are carried out free-radical polymerized.Take DVT 1.3g, N, N-DMAA (DMAA) 2.97g, AIBN 11mg, EMP 75mg, DMF solution 21.1mL, be placed in single necked round bottom flask, drum nitrogen deoxygenation eliminates the oxygen in reaction system, insulation reaction 24h in 70 DEG C of oil bath pans, then by its sedimentation in sudden cold, ether in frozen water, suction filtration can obtain 3.5g poly (DVT-co-DMAA).
The poly obtained (DVT-co-DMAA) is dissolved in 171mL DMF solution, adds 171mLH
2pdCl
4the aqueous solution (concentration is 0.04mol/L), condensing reflux at 80 DEG C, reaction 12h, can obtain 4.23g poly (DVT-co-DMAA)-Pd catalyst, its pattern as shown in Figure 2.
The characterization parameter of copolymer: number-average molecular weight is 11700g/mol, glass transition temperature T
gbe 98 DEG C, its nuclear-magnetism figure as shown in Figure 3.
Embodiment 3
DVT and methyl methacrylate (MMA) are carried out free-radical polymerized.Take DVT 1.3g, methyl acrylate (MMA) 3.0g, AIBN 11mg, EMP 75mg, DMF solution 22.6mL, is placed in single necked round bottom flask, drum nitrogen deoxygenation eliminates the oxygen in reaction system, insulation reaction 24h in 70 DEG C of oil bath pans, then by its sedimentation in sudden cold, ether in frozen water, suction filtration can obtain 3.7gpoly (DVT-co-MMA).
The poly obtained (DVT-co-MMA) is dissolved in 179mL DMF solution, adds 179mLH
2pdCl
4the aqueous solution (concentration is 0.04mol/L), condensing reflux at 80 DEG C, reaction 12h, can obtain 4.46g poly (DVT-co-MMA)-Pd catalyst.
Embodiment 4 (Application Example 1)
Get iodobenzene 0.28mL (2.5mmol), phenyl boric acid 460mg (3.77mmol), potash 3g (21.7mmol), the polymer-nano Pd catalyst 0.2mol% of embodiment 1, solvent DMF 40mL, H
2o 10mL, is placed in centrifuge tube, reacts 20h at 100 DEG C.Centrifugal with 8000rpm rotating speed after reaction, supernatant liquor is collected, and determines reaction yield by high performance liquid chromatography (HPLC).By the lower sediment in centrifuge tube by ethanol washing, centrifugal repetition more than 5 times with eliminate remnants phenyl boric acid and product biphenyl; And then with distilled water washing, centrifugal repetition more than 5 times, remove the potash in centrifuge tube, to realize the recovery to polymer-nano Pd catalyst.Polymer-nano Pd catalyst that recovery obtains is reused for the coupling reaction of catalysis iodobenzene and phenyl boric acid, repeats above operation.Find that the polymer-nano Pd catalyst prepared by us still keeps very high catalytic activity after reusing 5 times by HPLC test, above-mentioned reaction yield still reaches more than 99%.
Embodiment 5 (Application Example 2)
Repeat embodiment 4, just use the homopolymers in the copolymer replacement embodiment 1 of embodiment 2.Same discovery, find that the copolymer-nano Pd catalyst prepared by us still keeps very high catalytic activity after reusing 5 times by HPLC test, above-mentioned reaction yield still reaches more than 99%.
Claims (10)
1. polymer-nanometer metal particle catalyst, it is characterized in that: described catalyst comprises vinyl triazole polymer containing triarylimidazoles group and nano grade transition metal particle, and the particle diameter of transition metal particles is 2 ~ 100nm, preferably 3 ~ 50nm, more preferably 3 ~ 10nm; Preferably, this transition metal is palladium, platinum, zirconium, hafnium, scandium or titanium.
2. polymer-nanometer metal particle catalyst according to claim 1, it is characterized in that: described polymer is the vinyl triazole monomer 1-(4-(4 containing triarylimidazoles group, 5-diphenyl-1H-imidazoles-2-base) phenyl)-4-vinyl-1, the radically homo thing of 2,3-triazole (DVT) or the copolymer with other ethylenically unsaturated monomer (especially vinyl monomer); This monomer DVT has following general formula I:
3. polymer-nanometer metal particle catalyst according to claim 2, is characterized in that: homopolymers or copolymer have following structural formula (II) or (III) respectively:
In general formula (III), A-c-d-B is the unit of other ethylenically unsaturated monomer; Preferably, wherein A is H or methyl, and B has 2-10 carbon atom and 0-3 heteroatomic organic substituent.
4. polymer-the nanometer metal particle catalyst according to Claims 2 or 3, is characterized in that ethylenically unsaturated monomer is selected from one or more vinyl monomers in these monomers following: (methyl) acrylic compounds, (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) phenylethylene, acrylonitrile, vinyl carboxylates class, vinyl pyrrolidone, vinylpyridine, VCz or vinyl triazole type.
5. the preparation method of polymer-nanometer metal particle catalyst, the method comprises the following steps:
(1) the vinyl triazole monomer containing triarylimidazoles group is carried out radically homo reaction or carries out free radicals copolymerization reaction with other ethylenically unsaturated monomer (especially vinyl monomer), obtain the vinyl triazole homopolymers containing triarylimidazoles group or copolymer;
(2) gained homopolymers or copolymer are dissolved in forming reactions mixture in solvent (as DMF), transistion metal compound or transition metal precursor is added in this reactant mixture, then occur decompose or be reduced to allow reactant mixture react under separating out the reaction condition of transition metal simple substance at this transistion metal compound or transition metal precursor, thus allow transition metal be carried on described polymer, then from reactant mixture, isolate solids and it is washed, dry, obtain polymer-nanometer metal particle catalyst, transition metal wherein in transistion metal compound or transition metal precursor is palladium, platinum, zirconium, hafnium, scandium or titanium.
6. method according to claim 5, wherein transistion metal compound or transition metal precursor are chlorine palladium acid H
2pdCl
4or ammonium chloropalladate salt (NH
4)
2pdCl
4, chloroplatinic acid H
2ptCl
6or chloroplatinic acid ammonium salt (NH
4)
2ptCl
6, the acid of chlorine hafnium or chlorine hafnium acid ammonium salt.
7. the method according to claim 5 or 6, wherein step (1) is carried out as follows:
It is the DVT monomer of 1 by molar part, molar part is the initator azodiisobutyronitrile (AIBN) of 0.02 ~ 0.08, molar part is the chain-transferring agent S-ethyl group-S'-(α of 0.005 ~ 0.02, α '-dimethyl-α "-propionyloxy) trithiocarbonate (EMP), molar part is the solvent N of 20 ~ 200, dinethylformamide (DMF) is placed in single necked round bottom flask, oxygen in drum nitrogen deoxygenation removing reaction system, insulation reaction (such as 15 ~ 40h in 55 ~ 85 DEG C of (such as 60 ~ 80 DEG C) oil bath pans, as 24h), homopolymers poly (DVT) can be obtained, preferably, the yield of homopolymers is 65 ~ 85%,
Or be the DVT monomer of 1 by molar part, molar part is the ethylenically unsaturated monomer (monomer as containing vinyl) of 2 ~ 20, molar part is the initiator A IBN of 0.02 ~ 0.08, molar part is the chain-transferring agent EMP of 0.005 ~ 0.02, molar part be 20 ~ 200 solvent DMF be placed in flask, oxygen in drum nitrogen deoxygenation removing reaction system, insulation reaction (such as 15 ~ 40h in 55 ~ 85 DEG C of (such as 60 ~ 80 DEG C) oil bath pans, as 24h), the copolymer of DVT and ethylenically unsaturated monomer (monomer as containing vinyl) can be obtained; Preferably, the yield of copolymer is 70 ~ 88%.
8., according to the preparation method in claim 5-7 described in any one, wherein step (2) is carried out as follows:
The homopolymers obtain step (1) or copolymer are dissolved in forming reactions mixture in solvent (as DMF), slowly drip transistion metal compound or transition metal precursor (H as sour in chlorine palladium in this reactant mixture
2pdCl
4or ammonium chloropalladate salt (NH
4)
2pdCl
4, chloroplatinic acid H
2ptCl
6or chloroplatinic acid ammonium salt (NH
4)
2ptCl
6chlorine hafnium acid or chlorine hafnium acid ammonium salt) the aqueous solution, optionally add reducing agent, condensing reflux reaction (such as 5-20h under 65 ~ 95 DEG C (such as 70 ~ 90 DEG C), as 8-12h), there is black precipitate to separate out, stoste centrifugal treating will be reacted so that collecting precipitation thing, the drying precipitate of then will collect, obtains polymer-nano Pd catalyst.
9. according to the preparation method in claim 5-8 described in any one, wherein ethylenically unsaturated monomer is selected from one or more vinyl monomers in these monomers following: (methyl) acrylic compounds, (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) phenylethylene, acrylonitrile, vinyl carboxylates class, vinyl pyrrolidone, vinylpyridine, VCz or vinyl triazole type.
10., according to the preparation method in claim 5-9 described in any one, wherein transistion metal compound or transition metal precursor are H
2pdCl
4, and its consumption is 2 ~ 5 times of nitrogen atom content in polymer, calculates by mol.
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| CN114632551B (en) * | 2022-02-22 | 2023-10-27 | 东南大学 | Difunctional chiral catalyst and preparation method and application thereof |
| CN114797984A (en) * | 2022-03-24 | 2022-07-29 | 东南大学 | Heterogeneous chiral dual-function catalyst and preparation method and application thereof |
| CN114797984B (en) * | 2022-03-24 | 2023-08-25 | 东南大学 | Heterogeneous chiral bifunctional catalyst and preparation method and application thereof |
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