CN105111335A - Preparation method of carbon nano tube supported efficient isoprene catalyst - Google Patents
Preparation method of carbon nano tube supported efficient isoprene catalyst Download PDFInfo
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- CN105111335A CN105111335A CN201510579660.4A CN201510579660A CN105111335A CN 105111335 A CN105111335 A CN 105111335A CN 201510579660 A CN201510579660 A CN 201510579660A CN 105111335 A CN105111335 A CN 105111335A
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Abstract
The invention discloses a carbon nano tube supported efficient isoprene catalyst, and belongs to the technical field of material science. First, purification and modification are performed on carbon nano tube carriers, late transition metal catalysts containing multiple pi electron groups or polar groups of -OH, -NH2 and others are supported on the surfaces of the carbon nano tube carriers through pi-pi interaction or in a chemical-bond-forming mode, and through adjusting the purification and modification mode and the supporting technology of carbon nano tubes, the supporting rate and effective distribution of late transition metal on the surfaces of the carbon nano tube carriers are controlled. The supported catalyst prepared through the method has high catalytic activity for the isoprene monomers, regulates and controls the single configuration of the polyisoprene, and prolongs the service life of active centers. Related experimental operations and conditions are simple and not strict, and the carbon nano tube supported efficient isoprene catalyst is suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanotube loaded efficient isoprene catalyzer, comprise catalyst component, the preparation method of loaded catalyst and application, belong to materials science field.
Technical background
Alkene catalyst is the key in olefinic polymerization, the successful research and development of new olefin catalyzer at reduction production cost, simplify production technique and there is obvious pushing effect, for alkene industry brings change in enhancing product performance.In recent years, for making up the wretched insufficiency of natural rubber productive rate, the preparation of isoprene catalyzer is a polyolefinic important developing direction.Current isoprene polymerization catalyzer has Al-Ti catalyzer, rare earth metal complex catalyzer and late transition metal complex catalyst etc.These catalyzer have his own strong points in catalytic activity, the three-dimensional tacticity of controlled polyisoprene etc., especially late transition metal complex catalyst due to building-up process simple, the feature such as raw materials cost is low, catalytic activity is high, stability is high and polymer architecture controllability is good is the Main way of present stage isoprene polymerization catalyst research.But, the polymerization technique of modern industrialization has embodied the deficiency of homogeneous catalyst in actual production, and determine the urgent demand to supported heterogeneous catalyst, to reach form and the performance that can also control polymkeric substance while keeping catalytic activity, realize real continuous seepage.
For supported catalyst, silicon oxide and magnesium chloride are more common carriers.Such as, in isoprene polymerization industrial production, the main supported catalyst used is Ziegler-Natta catalyst.This catalyzer is carrier with magnesium chloride, has that catalytic activity is high, polymer process is easy to the features such as control, but the structure of this catalyzer and catalytic mechanism are also fuzzyyer.Carbon nanotube loaded polyolefine late transition metal catalyst is the extensive concern just causing everybody recent years, because carbon nanotube has strong delocalizedπelectron, conjugative effect is remarkable and have good heat conductivility and mechanical property etc., not only in raising catalytic activity in catalytic process, the aspects such as polymer architecture is controlled play favourable effect, simultaneously, in the course of the polymerization process, polymer overmold is on the surface of carbon nanotube, carbon nanotube particulate is dispersed in the middle of polymkeric substance uniformly as a kind of additive, improve mechanical property and the thermal property of isoprene copolymer to a certain extent, indirectly provide a kind of method of synthesized high-performance matrix material.Such as, Chinese patent CN104387507A discloses the isoprene polymerization catalyzer of a kind of carbon nanotube/Magnesium Chloride Anhydrous as carrier, synthesize polyisoprene/carbon nano tube compound material, but this catalyzer is mainly catalytic center with titanium series metal, be that the one of Ziegler-Natta catalyst is improved.
It take late transition metal complex catalyst as preparation method and the application of the catalyzer of the carbon nanometer tube loaded type isoprene polymerization of catalytic center that the present invention mainly provides a kind of, is mainly used in improving isoprene monomer polymerization activity, polymer tacticity and synthesizing a kind of polyisoprene/carbon nano tube compound material.
Summary of the invention
Object of the present invention: the preparation method that a kind of carbon nanotube loaded efficient isoprene catalyzer is provided.The present invention carries out purifying, modification to carbon nanotube carrier, will containing many π-electrons group or-OH ,-NH
2the late transition metal catalyst of isopolarity group, is interacted by π-π or forms the surface that the mode of chemical bond loads to carbon nanotube carrier.By regulating the purifying of carbon nanotube and the condition such as ratio, loading process solvent, temperature of reaction of modification mode, carbon nanotube and late transition metal catalyst, thus control the load factor of rear transition metal on carbon nanotube carrier surface and effectively distribution.
Technical scheme of the present invention: the preparation method that the invention provides a kind of carbon nanotube loaded efficient isoprene catalyzer, by carbon nanotube dispersed with stirring in organic solvent, be warming up to 25-60 DEG C, the organic solution being dissolved with late transition metal complex catalyst is added in carbon nano-tube solution, wherein late transition metal complex catalyst accounts for the massfraction of carbon nanotube carrier is 1%-70%, reaction 0.5-24 hour, centrifuging, and clean black solid with organic solvent, place 48 hours in 60 DEG C of vacuum drying ovens, obtain carbon nanotube loaded catalyzer.
Described carbon nanotube carrier is purified or the single wall of functionalization or many walls rod carbon nanotube.
Described late transition metal complex is the title complexs such as pyridine imine class N^N bidentate iron, cobalt, nickel, palladium, the various fragrant group based on imine structure phenyl ring, naphthalene nucleus, anthracene nucleus and pyrene ring or at least one contained in-OH ,-NH2 isopolarity group;
One or several in described organic solvent preferred alcohol, acetone, methylene dichloride, trichloromethane, tetrahydrofuran (THF), DMF equal solvent.
Beneficial effect of the present invention: be carrier with carbon nanotube, has prepared carbon nanotube loaded late transition metal complex isoprene polymerization catalyzer.This loaded catalyst has very high catalytic activity to isoprene monomer, and achieves the regulation and control to the single configuration of polyisoprene.Meanwhile, due to catalytic active center Stable distritation on the carbon nanotubes, improve the life-span in active centre.The experimental implementation that this invention relates to and condition simply, not harsh, be practically applicable to large-scale industrial production.
Accompanying drawing explanation
Accompanying drawing 1 is the TEM electromicroscopic photograph of the carbon nanotube loaded catalyzer 1 of example 1.
Embodiment
Below by examples of implementation, set forth outstanding advantages of the present invention and distinguishing feature further, but the present invention is in no way limited to examples of implementation.
Example 1
1g carbon nanotube is joined in 250mLShlenck bottle, vacuumizes 30min, add in 50mL methylene dichloride after nitrogen replacement 3 times.Then when nitrogen protection, the 20mL dichloromethane solution containing 0.01g2-pyridine imine iron complex is joined reaction flask, at room temperature react 0.5 hour.Centrifuging, and use methylene dichloride and ethanol purge black solid respectively, until scavenging solution is colourless.Drying 48 hours in 60 DEG C of vacuum drying ovens, obtain carbon nanotube loaded catalyzer 1, the mass percentage of ferro element is 0.8wt%.
Example 2
1g carbon nanotube is joined in 250mLShlenck bottle, vacuumizes 30min, add in 50mL ethanol after nitrogen replacement 3 times, and be warming up to 40 DEG C.Then when nitrogen protection, the 20mL ethanolic soln containing 0.5g2-pyridine imine cobalt complex is joined reaction flask, react 24 hours.Centrifuging, and use ethanol purge black solid respectively, until scavenging solution is colourless.Drying 48 hours in 60 DEG C of vacuum drying ovens, obtain carbon nanotube loaded catalyzer 2, the mass percentage of cobalt element is 1.3wt%.
Example 3
1g carbon nanotube is joined in 250mLShlenck bottle, vacuumizes 30min, add in 50mL tetrahydrofuran (THF) after nitrogen replacement 3 times.In time being warming up to 60 DEG C, the 20mL tetrahydrofuran solution containing 0.7g2-pyridine imine nickel complex is joined reaction flask, react 10 hours.Centrifuging, and use tetrahydrofuran (THF) and ethanol purge black solid respectively, until scavenging solution is colourless.Drying 48 hours in 60 DEG C of vacuum drying ovens, obtain carbon nanotube loaded catalyzer 3, the mass percentage of nickel element is 1.5wt%.
Example 4
1g carbon nanotube is joined in 250mLShlenck bottle, vacuumizes 30min, add in 50mL tetrahydrofuran (THF) after nitrogen replacement 3 times.Then when nitrogen protection, the 20mL tetrahydrofuran solution containing 0.3g2-pyridine imine palladium complex is joined reaction flask, at room temperature react 6 hours.Centrifuging, and use tetrahydrofuran (THF) and ethanol purge black solid respectively, until scavenging solution is colourless.Drying 48 hours in 60 DEG C of vacuum drying ovens, obtain carbon nanotube loaded catalyzer 4, the mass percentage of palladium element is 1.2wt%.
Claims (4)
1. the preparation method of a carbon nanotube loaded efficient isoprene catalyzer, by carbon nanotube dispersed with stirring in organic solvent, be warming up to 25-60 DEG C, the organic solution being dissolved with late transition metal complex catalyst is added in carbon nano-tube solution, wherein late transition metal complex catalyst accounts for the massfraction of carbon nanotube carrier is 1%-70%, reaction 0.5-10 hour, centrifuging, and clean black solid with organic solvent, place 48 hours in 60 DEG C of vacuum drying ovens, obtain carbon nanotube loaded catalyzer.
2. the preparation method of efficient isoprene catalyzer as carbon nanotube loaded in claim 1 one kind, described carbon nanotube carrier is purified or the single wall of functionalization or many walls rod carbon nanotube.
3. the preparation method of efficient isoprene catalyzer as carbon nanotube loaded in claim 1 one kind, described late transition metal complex is the title complexs such as pyridine imine class N^N bidentate iron, cobalt, nickel, palladium, the various fragrant group based on imine structure phenyl ring, naphthalene nucleus, anthracene nucleus and pyrene ring or at least one contained in-OH ,-NH2 isopolarity group.
4. the preparation method of efficient isoprene catalyzer as carbon nanotube loaded in claim 1 one kind, one or several in described organic solvent preferred alcohol, acetone, methylene dichloride, trichloromethane, tetrahydrofuran (THF), DMF equal solvent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586641A (en) * | 2018-04-28 | 2018-09-28 | 中国科学院青岛生物能源与过程研究所 | A kind of high-efficient iron-series catalyst and the preparation method and application thereof of catalysis isoprene polymerization |
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| CN1922347A (en) * | 2003-12-15 | 2007-02-28 | 丹尼尔·E·里萨斯科 | Rhenium catalysts and methods for production of single-walled carbon nanotubes |
| CN102516422A (en) * | 2011-11-23 | 2012-06-27 | 华东理工大学 | Preparation method for homopolymer or copolymer of cyclohexyl ethylene and catalyst |
| CN104387507A (en) * | 2014-11-17 | 2015-03-04 | 青岛科技大学 | Diolefin polymerization catalyst with carbon nano-tube/anhydrous magnesium chloride as carrier as well as preparation method and application of diolefin polymerization catalyst |
| CN104829488A (en) * | 2015-04-30 | 2015-08-12 | 天津工业大学 | Supported alpha-diimine metal complex, and its application in olefin polymerization |
-
2015
- 2015-09-11 CN CN201510579660.4A patent/CN105111335A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1922347A (en) * | 2003-12-15 | 2007-02-28 | 丹尼尔·E·里萨斯科 | Rhenium catalysts and methods for production of single-walled carbon nanotubes |
| CN102516422A (en) * | 2011-11-23 | 2012-06-27 | 华东理工大学 | Preparation method for homopolymer or copolymer of cyclohexyl ethylene and catalyst |
| CN104387507A (en) * | 2014-11-17 | 2015-03-04 | 青岛科技大学 | Diolefin polymerization catalyst with carbon nano-tube/anhydrous magnesium chloride as carrier as well as preparation method and application of diolefin polymerization catalyst |
| CN104829488A (en) * | 2015-04-30 | 2015-08-12 | 天津工业大学 | Supported alpha-diimine metal complex, and its application in olefin polymerization |
Non-Patent Citations (1)
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| 王基铭 等: "《石油化工技术进展》", 30 April 2002 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586641A (en) * | 2018-04-28 | 2018-09-28 | 中国科学院青岛生物能源与过程研究所 | A kind of high-efficient iron-series catalyst and the preparation method and application thereof of catalysis isoprene polymerization |
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Application publication date: 20151202 |