CN101928394B - Activated carbon-supported nitrile group ionic liquid-palladium catalyst for synthesizing polyketone and preparation method thereof - Google Patents
Activated carbon-supported nitrile group ionic liquid-palladium catalyst for synthesizing polyketone and preparation method thereof Download PDFInfo
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- CN101928394B CN101928394B CN2010102318909A CN201010231890A CN101928394B CN 101928394 B CN101928394 B CN 101928394B CN 2010102318909 A CN2010102318909 A CN 2010102318909A CN 201010231890 A CN201010231890 A CN 201010231890A CN 101928394 B CN101928394 B CN 101928394B
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Abstract
The invention discloses an activated carbon-supported nitrile group ionic liquid-palladium (Pd) catalyst for synthesizing polyketone and a preparation method thereof, wherein the homogeneous membrane of palladium acetate and N-valeronitrile-N'-methylimidazolium hexafluorophosphate ionic liquid are supported on pretreated activated carbon. The preparation method comprises the following steps: dissolving palladium acetate and N-valeronitrile-N'-methylimidazolium hexafluorophosphate ionic liquid in solvent acetone to stir, then adding pretreated activated carbon in the solution, continuously stirring, distilling, and drying to obtain the activated carbon-supported nitrile group ionic liquid-Pd catalyst. The invention has the advantages that polar group nitrile groups can increase the binding force between ionic liquid and activated carbon, the nitrile group ionic liquid membrane coating activated carbon can increase the dispersivity of Pd<2+>, reduce the loss of Pd<2+>, prevent the product polyketone from blocking the pores of activated carbon, prevent Pd<2+> from being embedded and increase the reactivity of the copolymerization of carbon monoxide and styrene for preparing polyketone.
Description
Technical field
The present invention relates to a kind of activated carbon-supported nitrile group ionic liquid phase-palladium catalyst and preparation method of polyketone synthesis, belong to the catalyst technology of polyketone synthesis.
Background technology
In recent years, loaded catalyst has obtained continuous application in carbon monoxide and styrene copolymerized preparation polyketone.Existing research shows that the mode of loading that is used for polyketone synthesis mainly contains the chemical bond supported active kind Pd of resin surface
2+With gac physical adsorption Pd
2+Laboratory research work in earlier stage shows, under the same terms, uses the mode of gac physical adsorption to have higher catalytic activity, easier operating method and lower cost.This is because gac has flourishing internal void and huge specific surface area, with respect to resin-carried, has higher adsorption efficiency, and catalytic activity is 1255.17gSTCO/gPdh～1495.67gSTCO/gPdh.Yet the immobilized mode when utilizing gac to do carrier belongs to physical adsorption, catalytic activity kind Pd
2+Crystallite generally only is distributed in the micropore near carbon surface, causes any particulate direct friction all can cause wearing and tearing, also can cause metals ion Pd
2+Loss, and the product polyketone that generates can cover the hole of gac, embedding spike Pd
2+, reduce catalytic activity.So,, and make spike Pd if can wrap up a skim at carrier surface
2+Homodisperse wherein so both can have been avoided the loss of spike, improved the dispersiveness and the selectivity of spike, can also prevent that product from covering carrier hole, embedding spike.Nitrile group ionic liquid just can form a kind of like this film, and polar group itrile group and carrier have strong bonding force, makes spike Pd
2+Homodisperse has wherein prevented Pd
2+Reunite, improved selectivity, thereby improved catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of activated carbon-supported nitrile group ionic liquid phase-palladium catalyst and preparation method of polyketone synthesis.Described catalyzer is used for the catalysis carbon monoxide and vinylbenzene prepares polyketone reactive behavior height, and its preparation method process is simple.
The present invention realizes through following technical scheme; A kind of activated carbon-supported nitrile group ionic liquid phase-palladium catalyst of polyketone synthesis; It is characterized in that; Acid chloride and N-penta cyanic acid-N '-ion liquid homogeneous membrane of Methylimidazole hexafluorophosphate in load on gac, and wherein, the charge capacity of acid chloride is pressed Pd
2+Meter is 1%～10% of quality of activated carbon, N-penta cyanic acid-N '-Methylimidazole hexafluorophosphate ionic liquid ([C
4CNmim]
+PF
6 -) charge capacity be 5%～20% of quality of activated carbon.
Above-mentioned Preparation of catalysts method is characterized in that may further comprise the steps:
1) with the gac of 50～60 order numbers with the hydrochloric acid soln of mass concentration 10%～30% in 40 ℃～60 ℃ immersion treatment 2～4h of temperature; The ammonia soln that the gained gac adds mass concentration 2%～10% again behind the suction filtration is heated to 90 ℃～100 ℃ and keeps 10min～20min; And then the gac behind the suction filtration used the deionized water heated scrub, remove Cl
-, NH
4 +Add deionized water, per 10 gram gacs again with the ydrogen peroxide 50 15mL～25mL of mass concentration 10%～30% and with mass concentration 5%～15% chlorine bleach liquor 5mL～10mL; Soaking at room temperature 4h～6h; Through filtering, washing; In 40 ℃～50 ℃ following vacuum-drying 12h～14h of temperature, obtain pretreated gac;
2) by pretreated gac and Pd
2+Mass ratio and with N-penta cyanic acid-N '-ion liquid mass ratio of Methylimidazole hexafluorophosphate be 1: (0.01～0.10): (0.05～0.20); Acid chloride and N-penta cyanic acid-N '-Methylimidazole hexafluorophosphate ionic liquid are dissolved in the solvent acetone; Under 25 ℃～35 ℃ of temperature, stir 2h～4h, in solution, add pretreated gac again; Continue to stir 12h～14h; Acetone solvent is removed in distillation, in 40 ℃～50 ℃ following vacuum-drying 12h～14h of temperature, obtains the activated carbon-supported nitrile group ionic liquid phase-palladium catalyst of polyketone synthesis.
Compare with the activated carbon supported catalyzer that existing polyketone synthesis is used, the substantive distinguishing features that the present invention has is: during the pre-treatment gac, use chlorine bleach liquor's washing of strong oxidizing property, Pd in the time of can effectively preventing to adsorb
2+Directly be reduced to palladium metal, use the ydrogen peroxide 50 washing, help the uniform distribution of palladium, the two is used, and can improve activity of such catalysts.This catalyzer is dissolved in the spike acid chloride after the nitrile group ionic liquid formation homogeneous membrane, is dispersed on the absorbent charcoal carrier.Owing to the existence of polar group itrile group, increased the bonding force of ionic liquid and gac, avoided surfactivity kind Pd
2+Reunion.And the nitrile group ionic liquid film that is wrapped in makes spike Pd
2+Better disperseed, for polyreaction provides bigger contact area.The nitrile group ionic liquid rete also plays protection carrier surface spike Pd simultaneously
2+Effect, it has reduced spike Pd
2+The loss that causes because of factors such as frictions.In addition, the product polyketone that this nitrile group ionic liquid rete can also prevent to generate is stopped up the hole of carrier active carbon, avoids spike by embedding.Thereby this catalystsystem can increase the reactive behavior of carbon monoxide and styrene copolymerized preparation polyketone.
Description of drawings
The gained catalyzer is used for the surperficial sem photograph of polyketone building-up reactions procatalyst to Fig. 1 on the gac for acid chloride directly loads to.Find out that by figure activated carbon surface is coarse, hole is big.
The gained catalyzer is used for the surperficial sem photograph of polyketone building-up reactions rear catalyst to Fig. 2 on the gac for acid chloride directly loads to.After finding out that by figure this catalyzer is used for polyreaction, the surface pore is covered by product in a large number, spike Pd
2+By embedding.
Fig. 3 is used for the sem photograph on polyketone building-up reactions procatalyst surface for activated carbon-supported nitrile group ionic liquid phase-palladium catalyst of the present invention.Find out that by figure the carrier surface that is covered by the nitrile group ionic liquid film is smooth.
Fig. 4 is used for the sem photograph on polyketone building-up reactions rear catalyst surface for activated carbon-supported nitrile group ionic liquid phase-palladium catalyst of the present invention.Find out do not have product to cover the activated carbon surface hole by figure, avoided spike Pd
2+By embedding.
Embodiment
Embodiment 1
Take by weighing 50～60 order gac 10g; The hydrochloric acid soln 50mL that adds mass concentration 20% soaks 2h down for 50 ℃ in temperature; The gained gac adds and is heated to 100 ℃ in the ammonia soln of mass concentration 2% and keeps 10min behind the suction filtration, and then the gac behind the suction filtration is added the 100mL deionized water is heated to 100 ℃ and keeps 10min, suction filtration; Triplicate is removed Cl
-, NH
4 +, add again among the chlorine bleach liquor 5mL of ydrogen peroxide 50 15ml and mass concentration 10% of 100ml deionized water, mass concentration 30%, behind the room temperature treatment 4h; Through filtering, washing; In 40 ℃ of following vacuum-drying 12h of temperature, obtain pretreated gac, sealing is preserved subsequent use.
Taking by weighing 0.2gN-valeronitrile base-N '-Methylimidazole hexafluorophosphate ionic liquid and 0.211g acid chloride is dissolved in the 15ml acetone; Stir 2h down for 30 ℃ in temperature, in solution, add the 1g pretreated active carbon again, continue to stir 12h; Acetone is removed in distillation; In 40 ℃ of following vacuum-drying 12h of temperature, obtain the activated carbon-supported nitrile group ionic liquid catalyzer, the theoretical duty quality 10%Pd-20% [C4CNmim] of this catalyzer
+PF
6 --1gC (a), the actual negative carrying capacity that adopts the 180-80 of HIT polarization Zeeman AAS appearance to measure palladium is 7.74%.
Embodiment 2
The step of present embodiment is with embodiment 1; Different is, N-valeronitrile base-N '-Methylimidazole hexafluorophosphate ionic liquid consumption is 0.15g, and the acid chloride consumption is 0.1477g; Obtain the activated carbon-supported nitrile group ionic liquid catalyzer, the theoretical duty quality 7%Pd-15% [C of this catalyzer
4CNmim]
+PF
6 --1gC (b).The actual negative carrying capacity that adopts the 180-80 of HIT polarization Zeeman AAS appearance to measure palladium is 5.23%.
Embodiment 3
The step of present embodiment is with embodiment 1; Different is, N-valeronitrile base-N '-Methylimidazole hexafluorophosphate ionic liquid consumption is 0.1g, and the acid chloride consumption is 0.1055g; Obtain the activated carbon-supported nitrile group ionic liquid catalyzer, the theoretical duty quality 5%Pd-10% [C of this catalyzer
4CNmim]
+PF
6 --1gC (c).The actual negative carrying capacity that adopts the 180-80 of HIT polarization Zeeman AAS appearance to measure palladium is 3.46%.
Embodiment 4
The step of present embodiment is with embodiment 1; Different is, N-valeronitrile base-N '-Methylimidazole hexafluorophosphate ionic liquid consumption is 0.05g, and the acid chloride consumption is 0.0633g; Obtain the activated carbon-supported nitrile group ionic liquid catalyzer, the theoretical duty quality 3%Pd-5% [C of this catalyzer
4CNmim]
+PF
6 --1gC (d).The actual negative carrying capacity that adopts the 180-80 of HIT polarization Zeeman AAS appearance to measure palladium is 2.26%.
Comparative Examples 1
Acid chloride directly loads to gained Preparation of catalysts on the gac: take by weighing the 0.2110g acid chloride and be dissolved in the 15ml anhydrous methanol; Stir 0.5h, add 1g pretreated active carbon carrier, continue to stir 12h; Distillation for removing methanol, 40 ℃ of following vacuum-drying 12h.Obtain acid chloride and directly load on the catalyzer on the gac, the theoretical negative carrying capacity 10%Pd-1gC (e) of this catalyzer.The actual negative carrying capacity that adopts the 180-80 of HIT polarization Zeeman AAS appearance to measure palladium is 5.78%.
Comparative Examples 2
The preparation of the nonpolar ionic-liquid catalyst of load: the step of this Comparative Examples is with embodiment 1, and different is to use nonpolar ionic liquid 1-butyl-4 Methylimidazole hexafluorophosphate ([bmim]
+PF
6 -) 0.2g, obtain activated carbon supported nonpolar ionic liquid, the theoretical negative carrying capacity 10%Pd-20% [bmim] of this catalyzer
+PF
6 --1gC (f).The actual negative carrying capacity that adopts the 180-80 of HIT polarization Zeeman AAS appearance to measure palladium is 6.35%.
The foregoing description and six kinds of prepared catalyzer of Comparative Examples are applied to the synthetic of polyketone respectively
Application examples 1
The catalyzer of embodiment 1 preparation is used for preparing polyketone: at the stainless steel autoclave of the charged magnetic stirring of 100mL; Add catalyzer (a) 0.02mmol (in theoretical palladium content), 2,2 '-dipyridyl 0.06mmol; Para benzoquinone 2mmol, tosic acid 0.06mmol.Add methyl alcohol 1ml then, vinylbenzene 15ml, ortho chloro phenol 15ml; Constant CO pressure 2MPa reacted 2 hours termination reaction behind the relief pressure down in 70 ℃; Solution is isolated catalystsystem earlier with the centrifugal 10min of whizzer 5000r/min, and filtrating is with absolute ethyl alcohol deposition, filtration; Washed product is in 40 ℃ of vacuum-dryings.The palladium-carbon catalyst that drying is good adds in the still again, add 2,2 successively '-dipyridyl, para benzoquinone, tosic acid, vinylbenzene, methyl alcohol and ortho chloro phenol, reuse, can ignore up to the amount that produces polyketone (STCO).Weigh the gross weight of products therefrom, calculate total catalytic activity (application examples 1).
Application examples 2～6
Step that should use-case is with application examples 1, and different is to adopt catalyzer (b), (c), (d), (e), (f) to replace the catalyzer (a) in the application examples 1 respectively.
The parameter of above-mentioned six catalyzer that application examples is used and the quality of prepared polyketone, shown in table one:
Table one
Claims (1)
1. the preparation method of the activated carbon-supported nitrile group ionic liquid phase-palladium catalyst of a polyketone synthesis; Described catalyzer; Acid chloride and N-penta cyanic acid-N '-ion liquid homogeneous membrane of Methylimidazole hexafluorophosphate in load on gac, and wherein, the charge capacity of acid chloride is pressed Pd
2+Meter is 1%～10% of quality of activated carbon, and N-penta cyanic acid-N '-ion liquid charge capacity of Methylimidazole hexafluorophosphate is 5%～20% of a quality of activated carbon, it is characterized in that may further comprise the steps:
1) with the gac of 50～60 order numbers with the hydrochloric acid soln of mass concentration 10%～30% in 40 ℃～60 ℃ immersion treatment 2～4h of temperature; The ammonia soln that the gained gac adds mass concentration 2%～10% again behind the suction filtration is heated to 90 ℃～100 ℃ and keeps 10min～20min; And then the gac behind the suction filtration used the deionized water heated scrub, remove Cl
-, NH
4 +Add deionized water, per 10 gram gacs again with the ydrogen peroxide 50 15mL～25mL of mass concentration 10%～30% and with mass concentration 5%～15% chlorine bleach liquor 5mL～10mL; Soaking at room temperature 4h～6h; Through filtering, washing,, obtain pretreated gac in 40 ℃～50 ℃ following vacuum-drying 12h～14h of temperature;
2) by pretreated gac and Pd
2+Mass ratio and with N-penta cyanic acid-N '-ion liquid mass ratio of Methylimidazole hexafluorophosphate be 1: (0.01～0.10): (0.05～0.20); Acid chloride and N-penta cyanic acid-N '-Methylimidazole hexafluorophosphate ionic liquid are dissolved in the solvent acetone; Under 25 ℃～35 ℃ of temperature, stir 2h～4h, in solution, add pretreated gac again; Continue to stir 12h～14h; Acetone solvent is removed in distillation, in 40 ℃～50 ℃ following vacuum-drying 12h～14h of temperature, obtains the activated carbon-supported nitrile group ionic liquid phase-palladium catalyst of polyketone synthesis.
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| DE102011114132A1 (en) * | 2011-08-14 | 2013-02-14 | BLüCHER GMBH | Filter material useful e.g. in or as filter for gas treatment and in filters for removing pollutants, comprises activated carbon, which is present in form of discrete activated carbon particles, preferably in spherical or granular shape |
| DE102011114133A1 (en) * | 2011-08-14 | 2013-02-14 | BLüCHER GMBH | Activated carbon, preferably activated carbon equipped and/or fitted with metal component comprising a metal-containing, preferably metal compound-containing ionic liquid, useful as protective material for civil or military purpose |
| CN105126831A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of nano-palladium catalyst |
| CN113769736B (en) * | 2021-09-06 | 2024-02-27 | 陕西瑞科新材料股份有限公司 | Preparation method of palladium hydroxide carbon supported catalyst |
| CN117327301B (en) * | 2023-11-27 | 2024-02-13 | 江苏新视界先进功能纤维创新中心有限公司 | Ionic liquid and preparation method and application thereof |
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| CN1939953A (en) * | 2006-09-26 | 2007-04-04 | 天津大学 | Microwave synthesis for producing polyketone ionic liquid |
| CN1962727A (en) * | 2006-11-22 | 2007-05-16 | 天津大学 | Method for repeatedly using catalyst for preparing polyketone in imidazole type ion liquid |
| JP2008063306A (en) * | 2006-09-11 | 2008-03-21 | Japan Enviro Chemicals Ltd | Method for producing imidazole compound |
| JP2009214094A (en) * | 2008-02-15 | 2009-09-24 | Tokyo Institute Of Technology | Oxidation catalyst, oxidizing method, oxidation apparatus, and antimicrobial agent |
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Patent Citations (6)
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|---|---|---|---|---|
| CN1061418A (en) * | 1990-11-13 | 1992-05-27 | 国际壳牌研究有限公司 | Carbon monoxide and cinnamic polymkeric substance |
| CN1477139A (en) * | 2003-07-11 | 2004-02-25 | 天津大学 | Methd for preparing polyketone by means of carbon oxide and olepine copolymerization |
| JP2008063306A (en) * | 2006-09-11 | 2008-03-21 | Japan Enviro Chemicals Ltd | Method for producing imidazole compound |
| CN1939953A (en) * | 2006-09-26 | 2007-04-04 | 天津大学 | Microwave synthesis for producing polyketone ionic liquid |
| CN1962727A (en) * | 2006-11-22 | 2007-05-16 | 天津大学 | Method for repeatedly using catalyst for preparing polyketone in imidazole type ion liquid |
| JP2009214094A (en) * | 2008-02-15 | 2009-09-24 | Tokyo Institute Of Technology | Oxidation catalyst, oxidizing method, oxidation apparatus, and antimicrobial agent |
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