CN101402053A - Process for producing sea urchin shaped polyaniline microsphere supported catalyst - Google Patents
Process for producing sea urchin shaped polyaniline microsphere supported catalyst Download PDFInfo
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- CN101402053A CN101402053A CNA2008102269498A CN200810226949A CN101402053A CN 101402053 A CN101402053 A CN 101402053A CN A2008102269498 A CNA2008102269498 A CN A2008102269498A CN 200810226949 A CN200810226949 A CN 200810226949A CN 101402053 A CN101402053 A CN 101402053A
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Abstract
The invention provides a method for preparing a sea urchin like polyaniline microspheres supported catalyst, which belongs to the technical field of polymer supported catalytic material preparation, wherein polystyrene microspheres prepared by a soap-free emulsion polymerization method are used as seeds, and sea urchin like polyaniline microspheres are prepared by a seed swelling polymerization method. The method comprises the following steps: firstly, adding aniline monomers into aqueous solution of the polystyrene microspheres, stirring the mixture for a period of time so that the aniline monomers are swelled into the polystyrene microspheres; secondly, adding the mixture into aqueous solution of iron-based oxidants so that the aniline monomers swelled into the polystyrene microspheres can react with the oxidants so as to obtain the sea urchin like polyaniline composite microspheres; and thirdly, using a catalyst MoO2(acac)2 to perform load reaction with the prepared sea urchin like polyaniline composite microspheres to syntheize a polyaniline supported molybdenum-based catalyst. When the prepared polyaniline supported molybdenum-based catalyst is used for catalyzing cyclooctene to perform epoxidation, and tert-butyl hydroperoxide is used as an oxygen source, and good catalytic activity and the recycling performance are represented.
Description
Technical field
The invention belongs to polymer support materials for catalysts preparing technical field, be specifically related to a kind of preparation method and loaded catalyst thereof of sea urchin shaped polyaniline complex microsphere.
Background technology
Epoxide (as expoxy propane, epoxychloropropane, Styryl oxide) is the important intermediate in the organic synthesis, is widely used in petrochemical industry, fine chemistry industry, organic synthesis, pharmacy, spices and electronics industry.The main approach of preparation epoxides is exactly an epoxidation reaction of olefines, so epoxidation reaction is all to occupy an important position in organic synthesis or in chemical industry, is the focus that people study always.Traditional organic oxidizing reaction exists drawbacks such as expensive raw material price, reaction time are long, serious waste of resources, thereby has limited their extensive uses in industry.Therefore, the catalysis epoxidation method of environmental friendliness, economical rationality has been subjected to researcher's great attention and has obtained extensive studies.
Advantages such as molybdenum series catalyst is nontoxic with it, low price and stable in properties have been subjected to paying close attention to widely and having obtained a large amount of achievements in research.In the relevant at home and abroad research of catalysis material, molybdenum is that transition metal becomes active day by day as the catalytic reaction activity center, a series of efficient homogeneous phase molybdenum catalysis materials are seen in report in succession, but homogeneous catalyst is recycled difficulty, therefore are difficult to bring into play its advantage in actual production.Having focused on that people will study again is convenient on separation and the reusable heterogeneous catalysis agent material.One of effective means of everybody the preparation heterogeneous catalysis of generally acknowledging is immobilized at present, and the carrier of solid-carrying type catalyst mainly concentrates on the base materials such as mesopore molecular sieve or polymer.Carrier as catalyst, it is simple that macromolecular compound has preparation, the heat endurance advantages of higher forms the focus of paying close attention to into people, and existing different types of polymer is as catalyst carrier, as ion exchange resin, polystyrene, grafted polystyrene, polyimides etc.For example: people such as Shahram utilize the activated centre of molybdenum as catalytic reaction, to form loaded catalyst after its load, with the TBHP is oxygen source, obtained very high catalytic activity, and this loaded catalyst is after recycling 8 times, still keep very high activity, the basis of research is provided for the practical application of load catalyst in industrial production.
Electrically conductive polyaniline is owing to have an excellent physical chemistry, unique mechanism of doping effect and the class nano-functional material that advantage has become tool DEVELOPMENT PROSPECT such as be easy to synthesize.Exist in the molecular structure of polyaniline and have the N atom that has lone pair electrons, can form coordinate bond with transition metal with unoccupied orbital, form loaded catalyst, polyaniline successfully load multiple metals such as molybdenum, vanadium, rhenium, but the polyaniline carrier that uses mostly is nanofiber, smooth microballoon etc., the former is difficult for evenly disperseing in catalyst system and catalyzing and recycling, and latter's specific area is less.Recently, patent " the polystyrene hollow microsphere is the method that template prepares the sea urchin shaped conductive polymers hollow microsphere " (application number 200710063574.3) has reported that adopting polymer hollow particles is the method that template prepares the sea urchin shaped polyaniline hollow microsphere, utilization elder generation loading aniline monomer in cavity is placed into ball the class interfacial polymerization method in the aqueous oxidizing agent solution then, obtained the compound hollow microsphere of polyaniline nano fiber in microsphere surface growth and arranged radially, this ball specific area is big, it is good catalyst carrier, step of going forward side by side carries out catalyst cupport and uses (preparation method of conductive polyaniline microsphere carrier load epoxidation molybdenum catalyst, application number 200810101418.6).But the problem that this method exists is, behind osmosis loading aniline monomer, need the eccentric cleaning step to remove the outer and surperficial monomer solution of ball, microballoon with cavity load monomer is distributed in the aqueous oxidizing agent solution again, eccentric cleaning has increased treatment step, and bad control, and wash number is too much, overlong time can cause monomer diffusion minimizing in the microballoon, very few ball external series gap and the outer surface monomer of causing again of wash number retains too much, influences the product pattern.
Summary of the invention
The objective of the invention is to: be equipped with the sea urchin shaped polyaniline microsphere of nanofiber arranged radially with the seed swelling legal system, a kind of method that is easy to control and prepare efficiently the sea urchin shaped polyaniline complex microsphere is provided.
Another object of the present invention is to: the bigger serface advantage of utilizing sea urchin shaped polyaniline complex microsphere special appearance to cause is come supported catalyst, and EPOXIDATION OF ALKENES CATALYZED BY provides a kind of catalytic epoxidation catalyst system and catalyzing of efficient reusable edible.
The objective of the invention is to realize by the following technical solutions:
The present invention adopts the emulsifier-free emulsion polymerization legal system to be equipped with polystyrene microsphere as seed, utilize the seed swelling polymerization to prepare the sea urchin shaped polyaniline complex microsphere, at first aniline monomer is joined in the aqueous solution of polystyrene microsphere, through stirring after a while, the aniline monomer swelling enters polystyrene microsphere, adding iron then is the aqueous solution of oxidant, the aniline monomer that swelling enters polystyrene microsphere can react with oxidant, obtains the sea urchin shaped polyaniline complex microsphere that is assembled by the 1-dimention nano fiber.Select commercialization effective catalyst MoO again for use
2(acac)
2Carry out load-reaction, synthesized polyaniline support type molybdenum series catalyst with the sea urchin shaped polyaniline complex microsphere of preparation.With the polyaniline support type molybdenum series catalyst catalysis cyclo-octene epoxidation reaction of preparation, be oxygen source with the TBHP, show good catalytic activity and recycling performance.
Concrete preparation process is:
1) preparation of sea urchin shaped polyaniline complex microsphere:
Adopt the method for emulsifier-free emulsion polymerization, obtain polystyrene microsphere.Take by weighing the polystyrene microsphere of above-mentioned preparation, and it is distributed in the deionized water, being made into concentration is 5～50gL
-1Emulsion, add aniline monomer, magnetic agitation, 10～60 ℃ of following swellings 1～10 hour, the concentration of aniline monomer was 3～300gL
-1Add oxidant subsequently, the mol ratio of oxidant and aniline monomer is 1: 1～1: 10,0～40 ℃ of reaction 6～24 hours, carries out emulsion centrifugal after reaction finishes, and use deionized water and absolute ethanol washing successively, obtain blackish green sea urchin shaped polyaniline complex microsphere powder after the drying.
Described oxidant is selected a kind of in iron chloride, ferric nitrate, the ferric sulfate for use.
2) sea urchin shaped polyaniline load molybdenum series catalyst preparation:
With MoO
2(acac)
2Mass ratio was pressed 1: 0.5～1: 8 with synthetic sea urchin shaped polyaniline complex microsphere powder by catalyst active center, was distributed in the ethanolic solution, and making polyaniline complex microsphere concentration is 10～80gL
-1, under 20～60 ℃ of magnetic agitation, to react 12～60 hours, reaction finishes centrifugal and cleans with ethanol, obtains sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
Advantage of the present invention is: adopt the seed swelling legal system to be equipped with the sea urchin shaped polyaniline complex microsphere, the preparation method is simple, can be mass-produced; The sea urchin shaped polyaniline complex microsphere of the bigger serface that utilization obtains is as carrier, and adopting the commercialization molybdenum is that effective catalyst is the activated centre, has prepared sea urchin shaped polyaniline complex microsphere load molybdenum series catalyst.Loaded catalyst is an oxygen source with the TBHP in chloroform soln, catalysis cyclo-octene epoxidation, and catalyst not only has high catalytic efficiency, also has advantages such as being easy to separate, can repeating recovery.
Description of drawings
Fig. 1 ferric nitrate is the SEM photo of polyaniline complex microsphere of the sea urchin shape of oxidant preparation;
Fig. 2 iron chloride is the SEM photo of polyaniline complex microsphere of the sea urchin shape of oxidant preparation;
Fig. 3 ferric sulfate is the SEM photo of polyaniline complex microsphere of the sea urchin shape of oxidant preparation.
The specific embodiment
Embodiment 1
1. the preparation of sea urchin shaped polyaniline complex microsphere
1) adopt the emulsifier-free emulsion polymerization method to prepare monodispersed polystyrene microsphere;
2) with polystyrene microsphere synthetic in the step 1), be distributed in the deionized water, form 10gL
-1Emulsion is measured aniline monomer and is joined in the above-mentioned emulsion, and the concentration of aniline monomer is 15gL
-1, swelling is 5 hours under 10 ℃ of magnetic agitation;
3) mol ratio by oxidant and monomer is 1: 2, the oxidant ferric nitrate is joined step 2) mixed solution in, 40 ℃ the reaction 12 hours, centrifugal then, and use distilled water and absolute ethanol washing successively, obtain blackish green sea urchin shaped polyaniline complex microsphere after the drying.
The preparation the sea urchin shaped polyaniline complex microsphere as shown in Figure 1, the diameter of fiber is 15-30nm, average length is 60-90nm, microsphere average grain diameter is 650nm.
2. sea urchin shaped polyaniline supported catalyst preparation and application
1) with MoO
2(acac)
2Catalyst active center and synthetic sea urchin shaped polyaniline complex microsphere are dispersed in the ethanolic solution, and polyaniline complex microsphere concentration is 20gL
-1, MoO
2(acac)
2Catalyst concn is 20gL
-1, reaction is 12 hours under 20 ℃ of magnetic agitation, will react the back solution centrifugal and with the ethanol cleaning, obtain sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
2) get the sea urchin shaped polyaniline support type molybdenum series catalyst that 0.10g obtains, join in the 5g chloroform soln, add the 1g cyclo-octene, add 4g TBHP and 2g nitrobenzene then, in round-bottomed flask, mix, the oil bath heating, 60 ℃ were reacted 10 hours.Product selects for use internal standard method to carry out the detection of catalyst activity by Agilent 6890-5973n gas chromatographic detection, and the conversion ratio of cyclo-octene is 97%, does not have accessory substance to generate.After catalyst circulation was used 5 times, the conversion ratio of catalyst was 90%, did not have accessory substance to generate.
Embodiment 2
1. the preparation of sea urchin shaped polyaniline complex microsphere
1) adopt the emulsifier-free emulsion polymerization method to prepare monodispersed polystyrene microsphere;
2) with polystyrene microsphere synthetic in the step 1), be distributed in the deionized water, form 15gL
-1Emulsion is measured aniline monomer and is joined in the above-mentioned emulsion, and the concentration of aniline monomer is 75gL
-1, swelling is 5 hours under 20 ℃ of magnetic agitation;
3) mol ratio by oxidant and monomer is 1: 4, oxidant chlorination iron is joined step 2) mixed solution in, 20 ℃ the reaction 20 hours, centrifugal then, and use distilled water and absolute ethanol washing successively, obtain blackish green sea urchin shaped polyaniline complex microsphere after the drying.
The preparation the sea urchin shaped polyaniline complex microsphere as shown in Figure 2, the diameter of fiber is 20-50nm, average length is 40-80nm, microsphere average grain diameter is 650nm.
2. sea urchin shaped polyaniline supported catalyst preparation and application
1) with MoO
2(acac)
2Catalyst active center and synthetic sea urchin shaped polyaniline complex microsphere are distributed in the ethanolic solution, and polyaniline complex microsphere concentration is 80gL
-1, MoO
2(acac)
2Catalyst concn is 40gL
-1, reaction is 24 hours under 25 ℃ of magnetic agitation, will react the back solution centrifugal and with the ethanol cleaning, obtain sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
2) get 0.10g sea urchin shaped polyaniline support type molybdenum series catalyst, join in the 5g chloroform soln, add the 1g cyclo-octene, add 4g TBHP and 2g nitrobenzene then, in round-bottomed flask, mix, the oil bath heating, 60 ℃ were reacted 10 hours.Product selects for use internal standard method to carry out the detection of catalyst activity by Agilent 6890-5973n gas chromatographic detection, and the conversion ratio of cyclo-octene is 90%, does not have accessory substance to generate.After catalyst circulation was used 5 times, the conversion ratio of catalyst was 87%, did not have accessory substance to generate.
Embodiment 3
1. the preparation of sea urchin shaped polyaniline complex microsphere
1) adopt the emulsifier-free emulsion polymerization method to prepare monodispersed polystyrene microsphere;
2) with polystyrene microsphere synthetic in the step 1), be distributed in the deionized water, form 20gL
-1Emulsion is measured aniline monomer and is joined in the above-mentioned emulsion, and the concentration of aniline monomer is 100gL
-1, swelling is 6 hours under 30 ℃ of magnetic agitation;
3) mol ratio by oxidant and monomer is 1: 4, oxidant ferric sulfate is joined step 2) mixed solution in, 30 ℃ the reaction 30 hours, centrifugal then, and use distilled water and absolute ethanol washing successively, obtain blackish green sea urchin shaped polyaniline complex microsphere after the drying.
The preparation the sea urchin shaped polyaniline complex microsphere as shown in Figure 3, the diameter of fiber is 5-40nm, average length is 70-120nm, microsphere average grain diameter is 700nm.
2. sea urchin shaped polyaniline supported catalyst preparation and application
1) with MoO
2(acac)
2Catalyst active center and synthetic sea urchin shaped polyaniline complex microsphere are distributed in the ethanolic solution, and polyaniline complex microsphere concentration is 60gL
-1, MoO
2(acac)
2Catalyst concn is 15gL
-1, reaction is 30 hours under 30 ℃ of magnetic agitation, will react the back solution centrifugal and with the ethanol cleaning, obtain sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
2) get 0.10g sea urchin shaped polyaniline support type molybdenum series catalyst, join in the 5g chloroform soln, add the 1g cyclo-octene, add 4g TBHP and 2g nitrobenzene then, in round-bottomed flask, mix, the oil bath heating, 60 ℃ were reacted 10 hours.Product selects for use internal standard method to carry out the detection of catalyst activity by Agilent 6890-5973n gas chromatographic detection, and the conversion ratio of cyclo-octene is 92%, does not have accessory substance to generate.After catalyst circulation was used 5 times, the conversion ratio of catalyst was 88%, did not have accessory substance to generate.
Embodiment 4
1. the preparation of sea urchin shaped polyaniline complex microsphere
1) adopt the emulsifier-free emulsion polymerization method to prepare monodispersed polystyrene microsphere;
2) with polystyrene microsphere synthetic in the step 1), be distributed in the deionized water, form 30gL
-1Emulsion is measured aniline monomer and is joined in the above-mentioned emulsion, and the concentration of aniline monomer is 200gL
-1, swelling is 5 hours under 40 ℃ of magnetic agitation;
3) mol ratio by oxidant and monomer is 1: 7, oxidant is added ferric nitrate to step 2) mixed solution in, 10 ℃ of reactions 10 hours, centrifugal then, and use distilled water and absolute ethanol washing successively, obtain blackish green sea urchin shaped polyaniline complex microsphere after the drying.
The sea urchin shaped polyaniline complex microsphere of preparation, the diameter of surface fiber is 15-30nm, and average length is 60-120nm, and microsphere average grain diameter is 780nm.
2. sea urchin shaped polyaniline supported catalyst preparation and application
1) with MoO
2(acac)
2Catalyst active center and synthetic sea urchin shaped polyaniline complex microsphere are distributed in the ethanolic solution, and polyaniline complex microsphere concentration is 60gL
-1, MoO
2(acac)
2Catalyst concn is 12gL
-1, reaction is 40 hours under 40 ℃ of magnetic agitation, will react the back solution centrifugal and with the ethanol cleaning, obtain sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
2) get 0.10g sea urchin shaped polyaniline support type molybdenum series catalyst, join in the 5g chloroform soln, add the 1g cyclo-octene, add 4g TBHP and 2g nitrobenzene then, in round-bottomed flask, mix, the oil bath heating, 60 ℃ were reacted 10 hours.Product selects for use internal standard method to carry out the detection of catalyst activity by Agilent 6890-5973n gas chromatographic detection, and the conversion ratio of cyclo-octene is 94%, does not have accessory substance to generate.After catalyst circulation was used 5 times, the conversion ratio of catalyst was 85%, did not have accessory substance to generate.
1. the preparation of sea urchin shaped polyaniline complex microsphere
1) adopt the emulsifier-free emulsion polymerization method to prepare polystyrene microsphere;
2) with polystyrene microsphere synthetic in the step 1), be distributed in the deionized water, form 40gL
-1Emulsion is measured aniline monomer and is joined in the above-mentioned emulsion, and the concentration of aniline monomer is 250gL
-1, swelling is 9 hours under 50 ℃ of magnetic agitation;
3) mol ratio by oxidant and monomer is 1: 9, the oxidant ferric nitrate is joined step 2) mixed solution in, 25 ℃ the reaction 14 hours, centrifugal then, and use distilled water and absolute ethanol washing successively, obtain blackish green sea urchin shaped polyaniline complex microsphere after the drying.
The sea urchin shaped polyaniline complex microsphere of preparation, the diameter of surface fiber is 18-32nm, and average length is 63-124nm, and microsphere average grain diameter is 750nm.
2. sea urchin shaped polyaniline supported catalyst preparation and application
1) with MoO
2(acac)
2Catalyst active center and synthetic sea urchin shaped polyaniline complex microsphere are distributed in the ethanolic solution, and polyaniline complex microsphere concentration is 80gL
-1, MoO
2(acac)
2Catalyst concn is 10gL
-1, reaction is 50 hours under 20 ℃ of magnetic agitation, will react the back solution centrifugal and with the ethanol cleaning, obtain sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
2) get 0.10g sea urchin shaped polyaniline support type molybdenum series catalyst, join in the 5g chloroform soln, add the 1g cyclo-octene, add 4g TBHP and 2g nitrobenzene then, in round-bottomed flask, mix, the oil bath heating, 60 ℃ were reacted 10 hours.Product selects for use internal standard method to carry out the detection of catalyst activity by Agilent 6890-5973n gas chromatographic detection, and the conversion ratio of cyclo-octene is 93%, does not have accessory substance to generate.After catalyst circulation was used 5 times, the conversion ratio of catalyst was 90%, did not have accessory substance to generate.
Claims (2)
1, the preparation method of sea urchin shaped polyaniline microsphere supported catalyst is characterized in that, concrete preparation process is:
1) preparation of sea urchin shaped polyaniline complex microsphere
Take by weighing the polystyrene microsphere that adopts the emulsifier-free emulsion polymerization method to make, and it is distributed in the deionized water, being made into concentration is 5～50gL
-1Emulsion, add aniline monomer, magnetic agitation, 10～60 ℃ of following swellings 1～10 hour, the concentration of aniline monomer was 3～300gL
-1, adding oxidant subsequently, the mol ratio of oxidant and aniline monomer is 1: 1～1: 10,0～40 ℃ of reaction 6～24 hours, after reaction finishes emulsion is carried out centrifugal, washing, obtains blackish green sea urchin shaped polyaniline complex microsphere powder after the drying;
2) sea urchin shaped polyaniline load molybdenum series catalyst preparation
With MoO
2(acac)
2Mass ratio was pressed 1: 0.5～1: 8 with synthetic sea urchin shaped polyaniline complex microsphere powder by catalyst active center, was distributed in the ethanolic solution, and making polyaniline complex microsphere concentration is 10～80gL
-1, under 20～60 ℃ of magnetic agitation, to react 12～60 hours, reaction finishes centrifugal and cleans with ethanol, obtains sea urchin shaped polyaniline support type molybdenum series catalyst after the drying.
2, preparation method as claimed in claim 1 is characterized in that, described oxidant is selected a kind of in iron chloride, ferric nitrate, the ferric sulfate for use.
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| CN113546685A (en) * | 2021-07-26 | 2021-10-26 | 南京林业大学 | Preparation method and application of polyaniline lignosulfonic acid loaded aluminum nitrate catalyst |
| CN113546685B (en) * | 2021-07-26 | 2023-06-13 | 南京林业大学 | Preparation method and application of polyaniline lignin sulfonic acid supported aluminum nitrate catalyst |
| CN114891404A (en) * | 2022-07-13 | 2022-08-12 | 佛山慧氟高分子材料有限公司 | Anti-static Teflon film and preparation method and application thereof |
| CN116947640A (en) * | 2023-09-21 | 2023-10-27 | 深圳市普利凯新材料股份有限公司 | Purification method of acetoacetyl ethyl methacrylate |
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