CN101823000A - Method for preparing poly(p-styrene) sulphonate grafted modified carbon nano tube - Google Patents
Method for preparing poly(p-styrene) sulphonate grafted modified carbon nano tube Download PDFInfo
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- CN101823000A CN101823000A CN 201010137567 CN201010137567A CN101823000A CN 101823000 A CN101823000 A CN 101823000A CN 201010137567 CN201010137567 CN 201010137567 CN 201010137567 A CN201010137567 A CN 201010137567A CN 101823000 A CN101823000 A CN 101823000A
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Abstract
The invention belongs to the technical field of inorganic materials, and particularly relates to a method for preparing a solid acid catalyst-poly (p-styrene) sulphonate grafted modified carbon nano tube. The method comprises the following steps: grafting modified sodium poly (p-styrene) sulphonate on the surface of the carbon nano tube through polymerization reaction of p-styrene sodium sulphonate, and then refluxing acid to obtain the poly (p-styrene) sulphonate grafted modified carbon nano tube. The method is simple, adopts easily obtained raw materials, and can control the grafting amount of poly (p-styrene) sulphonate on the surface of the carbon nano tube. The prepared poly(p-styrene) sulphonate grafted modified carbon nano tube has good dispersion in a polar solvent, can be used as a solid acid catalyst, has high acid catalysis selectivity and activity, is easy to reclaim, and has excellent recycling performance.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to the preparation method of a kind of solid acid catalyst-poly-p styrene sulfonic acid grafted modified carbon nano tube.
Background technology
CNT has high specific area, the good mechanical performance, and ultralight and good chemical thermodynamics stability, these character are widely used in the researchs such as pharmaceutical carrier, catalyst, biology sensor CNT.At present, a series of metal nanoparticle comprises that platinum, gold, silver and ruthenium have all successfully loaded on the CNT and since the specific area of CNT superelevation and superior electrical property make CNT that load has a metal nanoparticle very the conventional metals catalyst compare and have better catalytic activity and selectivity.
The application of CNT in catalyst still is confined to the composite of CNT and metal nanoparticle, but do not see the application report of carbon nano tube compound material as solid acid catalyst.Traditional solid acid catalyst has zeolite, heteropoly acid and perfluorinated sulfonic resin etc., the bad mechanical property of these solid acid catalysts, and poor heat stability, the catalytic activity site is few, makes their application very limited.The research of novel solid acid catalyst still faces many challenges.
Utilizing home position polymerization reaction and acid backflow successfully will gather p styrene sulfonic acid among the present invention has been grafted on the CNT, the poly-p styrene sulfonic acid modified carbon nanotube that obtains has good dispersiveness, in the esterification (typical reaction of preparation bio-fuel) of laurate and methyl alcohol, show excellent acid catalysis activity, just can simple separated product by the method for filtering, and reuse poly-p styrene sulfonic acid modified carbon nanotube and still have very high catalytic activity.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of solid acid catalyst-poly-p styrene sulfonic acid grafted modified carbon nano tube.
The inventive method at first by the polymerisation of sodium p styrene sulfonate, at carbon nano tube surface graft modification poly (sodium 4-styrenesulfonate), refluxes through peracid then and obtains the CNT of poly-p styrene sulfonic acid graft modification.Concrete steps are as follows:
Be dispersed in the sodium p styrene sulfonate aqueous solution CNT is ultrasonic, logical nitrogen deoxygenation added initator after 20～40 minutes, 60～80 ℃ of reactions 3～4 hours; After reaction finishes, separate with filtering with microporous membrane, obtain the CNT of poly (sodium 4-styrenesulfonate) graft modification, product was refluxed under sour environment 12～24 hours, after being cooled to room temperature, with filtering with microporous membrane and spend deionised water, obtain the CNT of poly-p styrene sulfonic acid graft modification to neutral.
Among the present invention, used CNT is SWCN or multi-walled carbon nano-tubes or double-walled carbon nano-tube; Used polymerization single polymerization monomer is α-olefin sulfonic acid sodio-derivatives such as sodium p styrene sulfonate or derivatives thereof, or ALS; Used initator is water soluble starter potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid or azo diisopropyl imidazoline etc., the acid counterflow condition is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetic acid, or nitration mixture etc.
The inventive method is simple, and raw material is easy to get, and preparation amount is big, prepared poly-p styrene sulfonic acid modified carbon nano-tube good dispersion, and acid catalysis is active high, easily reclaims, and reuses still to have high activity.
Domestic and international at present solid acid catalyst such as zeolite, heteropoly acid and the perfluorinated sulfonic resin bad mechanical property of researching and developing, poor heat stability, the catalytic activity site is few, use very limited method, comparatively speaking, the solid acid catalyst of the present invention's preparation-poly-p styrene sulfonic acid modified carbon nano-tube, good dispersion, acid catalysis is active high, easily reclaims, and reuses still to have high activity.
The specific embodiment
The ultrasonic 100mL of being dispersed in of embodiment 1:50mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the potassium peroxydisulfate, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 2:50mg SWCN powder contains in the aqueous solution of 4.0g sodium p styrene sulfonate, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the potassium peroxydisulfate, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the dilute sulfuric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 3:100mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the ammonium persulfate, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the phosphoric acid,diluted condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 4:50mg SWCN powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the potassium peroxydisulfate, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 5:50mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 3.0g ALS, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the ammonium persulfate, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate polyene propyl sulfonic acid sodium modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain polyene propyl sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 6:100mg SWCN powder contains in the aqueous solution of 2.0g ALS, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the potassium peroxydisulfate, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate polyene propyl sulfonic acid sodium modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain polyene propyl sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 7:50mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment be that catalyst is heated to 70 ℃ of reaction 3h with the azo-bis-isobutyrate hydrochloride, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 8:50mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment with azo diisopropyl imidazoline be catalyst be heated to 70 ℃ the reaction 3h, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 9:50mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment with azo dicyano valeric acid be catalyst be heated to 70 ℃ the reaction 3h, 85 ℃ of reaction 2h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the sulfuric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
The ultrasonic 100mL of being dispersed in of embodiment 10:50mg multi-wall carbon nano-tube pipe powder contains in the aqueous solution of 2.0g sodium p styrene sulfonate, under oxygen-free environment with azo two isobutyl imidazoline salt hydrochlorates be catalyst be heated to 70 ℃ the reaction 3h, 85 ℃ of reaction 1h, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane separate the poly (sodium 4-styrenesulfonate) modified carbon nanotube, product is flow through night next time in the hydrochloric acid condition, be cooled to room temperature with 0.45 μ m composite fibre filtering with microporous membrane and spend deionised water, obtain poly-p styrene sulfonic acid modified carbon nanotube to neutral.
Claims (2)
1. the preparation method of a solid acid catalyst-poly-p styrene sulfonic acid grafted modified carbon nano tube is characterized in that concrete steps are as follows:
Be dispersed in the sodium p styrene sulfonate aqueous solution CNT is ultrasonic, logical nitrogen deoxygenation added initator after 20～40 minutes, 60～80 ℃ of reactions 3～4 hours; After reaction finishes, separate with filtering with microporous membrane, obtain the CNT of poly (sodium 4-styrenesulfonate) graft modification, product was refluxed under sour environment 12～24 hours, after being cooled to room temperature, with filtering with microporous membrane and spend deionised water, obtain the CNT of poly-p styrene sulfonic acid graft modification to neutral.
2. a kind of solid acid catalyst according to claim 1---the preparation method of poly-p styrene sulfonic acid grafted modified carbon nano tube is characterized in that used CNT is SWCN or multi-walled carbon nano-tubes or double-walled carbon nano-tube; Used polymerization single polymerization monomer is the sodium p styrene sulfonate or derivatives thereof, or ALS; Used initator is water soluble starter potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid or azo diisopropyl imidazoline, the acid counterflow condition is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetic acid, or nitration mixture.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437632A (en) * | 2014-11-03 | 2015-03-25 | 江苏大学 | Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof |
| CN104736516A (en) * | 2012-10-15 | 2015-06-24 | 东曹有机化学株式会社 | High purity sodium p-styrene sulfonate with excellent hue, method for producing same, sodium polystyrenesulfonate with excellent hue using same, and dispersant obtained by using the sodium polystyrene sulfate, and synthetic paste for cloth finishing |
| CN106423274A (en) * | 2016-04-07 | 2017-02-22 | 华东理工大学 | Sulfonic acid functionalized polymer grafted carbon nanotube composite material, and preparation method and application thereof |
| CN110975935A (en) * | 2019-12-25 | 2020-04-10 | 武汉工程大学 | Preparation method and application of solid acid catalyst |
| CN111763372A (en) * | 2020-06-10 | 2020-10-13 | 杭州联通管业有限公司 | Reinforced modified polypropylene power tube and preparation method thereof |
-
2010
- 2010-04-01 CN CN 201010137567 patent/CN101823000A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《2009年全国高分子学术论文报告会》 20090822 张晓鸿等 磺酸基改性碳纳米管的制备及其在酸催化方面的应用 423 1-2 , 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104736516A (en) * | 2012-10-15 | 2015-06-24 | 东曹有机化学株式会社 | High purity sodium p-styrene sulfonate with excellent hue, method for producing same, sodium polystyrenesulfonate with excellent hue using same, and dispersant obtained by using the sodium polystyrene sulfate, and synthetic paste for cloth finishing |
| CN104437632A (en) * | 2014-11-03 | 2015-03-25 | 江苏大学 | Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof |
| CN106423274A (en) * | 2016-04-07 | 2017-02-22 | 华东理工大学 | Sulfonic acid functionalized polymer grafted carbon nanotube composite material, and preparation method and application thereof |
| CN106423274B (en) * | 2016-04-07 | 2019-04-23 | 华东理工大学 | A kind of composite material and preparation method and application of the macromolecule grafting carbon nanotube of sulfonic acid functional |
| CN110975935A (en) * | 2019-12-25 | 2020-04-10 | 武汉工程大学 | Preparation method and application of solid acid catalyst |
| CN110975935B (en) * | 2019-12-25 | 2023-05-26 | 武汉工程大学 | Preparation method and application of solid acid catalyst |
| CN111763372A (en) * | 2020-06-10 | 2020-10-13 | 杭州联通管业有限公司 | Reinforced modified polypropylene power tube and preparation method thereof |
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Open date: 20100908 |