CN105111344A - Carbon nano tube/polyisoprene composite material and preparation method thereof - Google Patents
Carbon nano tube/polyisoprene composite material and preparation method thereof Download PDFInfo
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- CN105111344A CN105111344A CN201510579784.2A CN201510579784A CN105111344A CN 105111344 A CN105111344 A CN 105111344A CN 201510579784 A CN201510579784 A CN 201510579784A CN 105111344 A CN105111344 A CN 105111344A
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Abstract
The invention discloses a carbon nano tube/polyisoprene composite material and a preparation method thereof, and belongs to the technical field of material science. Mainly through a coordination solution polymerization method, with carbon nano tube supported N>N bidentate iron, cobalt, nickel, palladium and other late transition metal compounds being catalysts, organic aluminum being a catalyst promoter, and an organic reagent being solvent, dealkylation reagents are added to form isoprene monomers in a catalytic polymerization mode, and then the carbon nano tube/polyisoprene composite material is prepared. Compared with other methods, the coordination solution polymerization method is adopted, and therefore the advantages of catalytic activity and polymer structure controllability are achieved. Meanwhile, the carbon nano tube supported catalysts are adopted, catalytic activity centers are anchored on the surfaces of carbon nano tubes, in the polymerization process, polymers easily grow from the surfaces of the carbon nano tubes, and the interaction between the carbon nano tubes and the polymers is improved. The experimental operations and conditions are simple and not strict, the carbon nano tubes are easily and evenly dispersed in polyisoprene, and the carbon nano tube/polyisoprene composite material is convenient to apply to large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of carbon nano-tube/poly isoprene composite and preparation method thereof, belong to material science.
Background technology
Polymer nanocomposites, because of the size of high dispersing nano material in the polymer, quantum and electron tunneling effect etc., makes matrix material have to be different from the mechanics of polymkeric substance and micron order matrix material, calorifics and other is functional.Wherein, polyisoprene matrix material is with performances such as high friction resistance, high strength, snappiness and erosion resistances, be widely used in the vehicles, medicine equipment, material of construction and industrial equipments etc. multi-field, therefore, polyisoprene matrix material preparation method and how to improve its application performance be more popular research direction always.
At present, prepare the nanometer composite technology involved by polyisoprene matrix material, mainly contain melt powder blending method, in-situ intercalative polymerization and sol-gel method etc.Wherein, blended nanometer composite technology is the simplest method, mainly nano material is evenly mixed in elastomeric material by the mode that conventional mechanical is blended, but due to the viscosity of rubber high, there is the nano material content that is mixed into low and can not homodisperse problem; Meanwhile, nano particle dry powder is easily in atmosphere floating, also there is the problem of very large processing pollution.Give the improvement to aforesaid method, patent CN104053710 discloses a kind of preparation method of rubber wet masterbatch, patent CN1238353A discloses a kind of preparation method of clay-rubber nm-class composite material, patent CN104212000 discloses the preparation method that a kind of preparation method of high elasticity abrasion-proof elastomeric material and patent CN1415653A disclose carbon black filled powder rubber, its something in common is a different types of nano material prepared composition prose style free from parallelism and is distributed in rubber latex by mechanical stirring, prepares various rubber composite finally by aftertreatment.The method, while solution processing pollution problem, also improves the content of nano material in mixture to a certain extent.US Patent No. 4889885 discloses and adopts in-situ inserted polymerization to disclose the preparation method of butadiene-isoprene-styrol copolymer/clay composite material for the research method of clay/rubber matrix nanocomposites and Chinese patent CN1690117, its something in common is to be joined by the nano particle that reflection is good in the solvent containing polymerization body, adds initiator initiated polymerization and prepares polymer composites.
Carbon nanotube has strong delocalizedπelectron, high specific surface area, good heat conductivility and mechanical property etc., is enhancing packing material ideal in field of compound material.Such as Chinese patent CN102675802 discloses the preparation method that a kind of modified carbon nano-tube strengthens Polydicyclopentadiencomposite composite material, modified carbon nano-tube dispersion is joined in dicyclopentadiene monomer solution, add tungsten catalyst and aluminum alkyls initiation dicyclopentadiene ring-opening polymerization, the carbon nanotube Polydicyclopentadiencomposite composite material of preparation high tenacity.The present invention mainly causes isoprene monomer polymerization with carbon nanotube loaded late transition metal complex catalyst for catalyzer, prepares a kind of carbon nano-tube/poly isoprene composite.
Summary of the invention
Object of the present invention: the method being prepared carbon nano-tube/poly isoprene composite by carbon nanotube loaded late transition metal catalyst solution polymerization process is provided.The present invention is mainly through coordination solution polymerization process, with the late transition metal complexs such as carbon nanotube loaded N^N bidentate iron, cobalt, nickel, palladium be catalyzer, organoaluminum is promotor, organic reagent is for solvent, add dealkylating reagent and realize isoprene monomer polymerization, prepare carbon nano-tube/poly isoprene composite.Compared with additive method, the present invention adopt polycomplexation legal catalytic activity and polymer architecture controlled etc. in there is advantage.Meanwhile, adopt carbon nanometer tube loaded type catalyzer, catalytic active center is anchored at the surface of carbon nanotube, and in the process of polymerization, polymkeric substance is easy to the surface growth from carbon nanotube, enhances the interaction between carbon nanotube and polymkeric substance.
Technical scheme of the present invention: the invention provides a kind of carbon nano-tube/poly isoprene composite and preparation method thereof: polymerization bottle, through pump drainage and inert gas replacement several, adds the above-mentioned carbon nanotube loaded catalyzer of metering, solvent, aluminum alkyl catalyst, dealkylating reagent and isoprene monomer etc. successively.Wherein loaded catalyst and isoprene mol ratio are 1-25000, loaded catalyst and promotor mol ratio are 1-5000, the mol ratio of loaded catalyst and dealkylating reagent is 0.5-5, and temperature of reaction is-33-40 DEG C, and polymerization time is 5min-24h.Be polymerized rear Muriatic terminator and stopped polymerization, cleaned three times again with straight alcohol, in resulting polymers 60 DEG C of vacuum drying ovens, be dried to constant mass.
The invention provides a kind of carbon nano-tube/poly isoprene composite and preparation method thereof, comprise carbon nanotube loaded catalyzer, monomeric species, organic solvent, catalyst type, promotor, dealkylating reagent and polymerization terminator etc.
In described polyreaction, carbon nanotube loaded catalyzer is the late transition metal complex catalysts such as carbon nanotube loaded N^N bidentate iron, cobalt, nickel, palladium.
In described polyreaction, solvent is one or more in toluene, dimethylbenzene, tetrahydrofuran (THF), methylene dichloride.
Carry out in rare gas element (argon gas or nitrogen) atmosphere in described polyreaction.
Described polyreaction promotor: aluminum compound (R1 is alkyl, cycloalkyl, alkoxyl group or alkaryl) or the alkyl aluminum chloride compound of the present invention's promotor used is to be at least a kind of chemical formula be AlR.
Described polyreaction dealkylating reagent: have at least a kind of dealkylating reagent to exist in the present invention.
Described polymerization terminator is the methyl alcohol of hcl acidifying, ethanol, Virahol and water.
Beneficial effect of the present invention: carbon nanotube loaded late transition metal complex is the polymerization of catalyst isoprene monomer, has prepared a kind of carbon nano-tube/poly isoprene composite.The present invention adopt polycomplexation legal catalytic activity and polymer architecture controlled etc. in there is advantage, and adopt single stage method to be distributed in polyisoprene by even carbon nanotube, 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 SEM electromicroscopic photograph of example 1 carbon nano-tube/poly isoprene composite 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
Under argon shield, by iron complex content be the carbon nanotube loaded iron catalyst of 0.3umol, 0.3umol triphen carbon four (pentafluorophenyl group) borate, 0.15ml (
ipr)
3al (0.2Mintoluene) and 100ml toluene join successively in the flask of 250mL and stir two minutes, then add 1.0mL isoprene monomer.(25 DEG C) stirring reaction 30min at normal temperatures.After reaction terminates, with the ethanolic soln neutralization reaction liquid of hcl acidifying, obtain polymkeric substance precipitation, wash for several times with ethanol, vacuum drying is to constant weight, and 0.5g polymkeric substance of weighing to obtain, the transformation efficiency of polyreaction is 73.5%.Polymer Tg=-25.8 DEG C (Tg is the melt temperature of polymkeric substance, tests gained by DSC).
The invention provides a kind of preparation method of carbon nano-tube/poly isoprene composite: polymerization bottle, through pump drainage and inert gas replacement several, adds the above-mentioned carbon nanotube loaded catalyzer of metering, solvent, aluminum alkyl catalyst, dealkylating reagent and isoprene monomer etc. successively.Wherein loaded catalyst and isoprene mol ratio are 1-25000, loaded catalyst and promotor mol ratio are 1-5000, the mol ratio of loaded catalyst and dealkylating reagent is 0.5-5, and temperature of reaction is-33-40 DEG C, and polymerization time is 5min-24h.Be polymerized the Muriatic industrial spirit of rear use 0.1% and stopped polymerization, cleaned three times again with straight alcohol, in resulting polymers 60 DEG C of vacuum drying ovens, be dried to constant mass.
Example 2
Under argon shield; the MMAO (0.76Mintoluene) of 0.3umol CNTs-supported Co catalysts, 1.5umol triphen carbon four (pentafluorophenyl group) borate, 5ml and 100ml toluene are joined successively in the flask of 250mL and stir two minutes, then add 7.5mL isoprene monomer.At 35 DEG C of stirring reaction 24h.After reaction terminates, with the methanol solution neutralization reaction liquid of hcl acidifying, obtain polymkeric substance precipitation, with methanol wash column several, vacuum drying is to constant weight, and 3.7g polymkeric substance of weighing to obtain, the transformation efficiency of polyreaction is 72.5%.Polymer Tg=-29.8 DEG C.
Example 3
Under argon shield; the MAO (1Mintoluene) of carbon nanotube loaded for 3umol nickel catalyzator, 0.05g triphen carbon four (pentafluorophenyl group) borate, 15ml and 100ml toluene are joined successively in the flask of 250mL and stir two minutes, then add 7.5mL isoprene monomer.At-33 DEG C of stirring reaction 0.5h.After reaction terminates, with the aqueous isopropanol neutralization reaction liquid of hcl acidifying, obtain polymkeric substance precipitation, with isopropyl alcohol wash several, vacuum drying is to constant weight, and 1.3g polymkeric substance of weighing to obtain, the transformation efficiency of polyreaction is 25.4%.Polymer Tg=-21.5 DEG C.
Example 4
Under argon shield, by the Et of carbon nanotube loaded for 3umol palladium catalyst, 6umol triphen carbon four (pentafluorophenyl group) borate, 3ml
2alCl and 100ml toluene joins successively in the flask of 250mL and stirs two minutes, then adds 7.5mL isoprene monomer.At 10 DEG C of stirring reaction 10h.After reaction terminates, with the ethanolic soln neutralization reaction liquid of 5% hcl acidifying, obtain polymkeric substance precipitation, wash for several times with ethanol, vacuum drying is to constant weight, and 0.7g polymkeric substance of weighing to obtain, the transformation efficiency of polyreaction is 13.7%.Polymer Tg=-18.1 DEG C.
Claims (7)
1. the invention provides a kind of carbon nano-tube/poly isoprene composite and preparation method thereof: polymerization bottle, through pump drainage and inert gas replacement several, adds the above-mentioned carbon nanotube loaded catalyzer of metering, solvent, aluminum alkyl catalyst, dealkylating reagent and isoprene monomer etc. successively.Wherein loaded catalyst and isoprene mol ratio are 1-25000, loaded catalyst and promotor mol ratio are 1-5000, the mol ratio of loaded catalyst and dealkylating reagent is 0.5-5, and temperature of reaction is-33-40 DEG C, and polymerization time is 5min-24h.Be polymerized rear Muriatic terminator and stopped polymerization, cleaned three times again with straight alcohol, in resulting polymers 60 DEG C of vacuum drying ovens, be dried to constant mass.
2. carbon nanotube loaded catalyzer is the late transition metal complex catalysts such as carbon nanotube loaded N^N bidentate iron, cobalt, nickel, palladium in polyreaction as claimed in claim 1.
3. solvent is one or more in toluene, dimethylbenzene, tetrahydrofuran (THF), methylene dichloride in polyreaction as claimed in claim 1.
4. carry out in rare gas element (argon gas or nitrogen) atmosphere in polyreaction as claimed in claim 1.
5. polyreaction promotor as claimed in claim 1: be aluminum compound (R1 is alkyl, cycloalkyl, alkoxyl group or alkaryl) or the alkyl aluminum chloride compound of to be at least a kind of chemical formula be AlR.
6. polyreaction dealkylating reagent as claimed in claim 1: have at least a kind of dealkylating reagent to exist in the present invention.
7. polymerization terminator is the methyl alcohol of hcl acidifying, ethanol, Virahol and water as claimed in claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111574651A (en) * | 2020-05-09 | 2020-08-25 | 江南大学 | Complex catalyst for catalyzing isoprene polymerization and preparation method thereof |
| CN112778473A (en) * | 2020-12-31 | 2021-05-11 | 宁波伟裕工贸有限公司 | Carbon nano tube modified isoprene rubber composite material with high thermal stability and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111574651A (en) * | 2020-05-09 | 2020-08-25 | 江南大学 | Complex catalyst for catalyzing isoprene polymerization and preparation method thereof |
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| CN112778473A (en) * | 2020-12-31 | 2021-05-11 | 宁波伟裕工贸有限公司 | Carbon nano tube modified isoprene rubber composite material with high thermal stability and preparation method thereof |
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Application publication date: 20151202 |