CN102585425A - Preparation method of temperature-sensitive controllable graphene-polymer composite material - Google Patents
Preparation method of temperature-sensitive controllable graphene-polymer composite material Download PDFInfo
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- CN102585425A CN102585425A CN2011104421701A CN201110442170A CN102585425A CN 102585425 A CN102585425 A CN 102585425A CN 2011104421701 A CN2011104421701 A CN 2011104421701A CN 201110442170 A CN201110442170 A CN 201110442170A CN 102585425 A CN102585425 A CN 102585425A
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Abstract
The invention relates to a temperature-sensitive controllable graphene-polymer composite material and a preparation method thereof. The method comprises the steps that a temperature-sensitive copolymer with a pyrene end group is synthesized by utilizing a reversible addition-fragmentation chain transfer (RAFT) polymerization method, and the copolymer is connected to graphene through a Pi-Pi additive effect of the pyrene end group and the graphene. The modified graphene has numerous characteristics of the copolymer and can be applied to various fields.
Description
Technical field
This method relates to a kind of Graphene-polymer composite and preparation method thereof, and matrix material of especially a kind of thermally sensitive controlled copolymerized macromolecule and Graphene and preparation method thereof belongs to the preparation and the Application Areas of novel material.
Background technology
Graphene has unique two-dimension plane structure, excellent mechanics, electricity and thermal property, thereby in the near future, Graphene will be widely used in fields such as supercomputer, novel material, microtronics and transmitter.
Preparation method of graphene has a variety of, and for example mechanically peel method, oxidation reduction process, epitaxial growth method, vapour deposition process etc. are to prepare the most frequently used method of Graphene with the chemical method redox graphene wherein.Yet; Prepare in the process of Graphene disappearance with this method along with hydrophilic radicals such as carboxyl, hydroxyls; The hydrophobicity of graphene oxide is more and more stronger, and after hydrophilic radical was reduced, the new Graphene that forms can irreversible aggrengation take place because of Van der Waals force in the aqueous solution.
In numerous research focuses of Graphene, Graphene is carried out the emphasis that modification is undoubtedly people's research.Polymer can be connected on the Graphene to reach the purpose of modified graphene through covalent linkage effect amino, ester group.Ye and its colleague have successfully made amphiphatic Graphene through the method for original position radical polymerization.Yet, thisly can destroy the conjugated structure of Graphene simultaneously, and then influence the electroconductibility of Graphene greatly with the method for covalent linkage effect modified graphene.In such cases, the grapheme modified aspect that is introduced in of π-π additive effect has shown remarkable advantages, especially aspect the protection of graphene conductive performance.On this basis, people are connected to Graphene on through π-π additive effect many molecules (like the pyrene butyric acid) that have big pi-conjugated structure and are applied to multiple field.
The temperature sensitive type material is one type of intelligent polymer material responsive to temperature variation, also more and more receives publicity in recent years.Modal temperature sensing material is the PNIPAM class; No. 200910045398 patents have proposed a kind of preparation method of thermosensitive degradable graft copolymer; Multipolymer with N-NSC 11448 and other hydrophilic monomer is a hydrophilic backbone, is the hydrophobicity side chain with the degradable polyester.Thermosensitive degradable graft copolymer of the present invention has biocompatibility, absorbability matter and the temperature-responsive of degradable polymer simultaneously.Liu etc. have also successfully synthesized and have had temperature-sensitive and have pyrenyl end group SEPIGEL 305, and utilize the synergetic method of π-π successfully to transform Graphene to have obtained thermally sensitized Graphene SEPIGEL 305 matrix material.No. 201010134317 patented inventions a kind of thermosensitive graphene/polymer composite material and preparation method thereof, in fields such as transmitter, environment, medicine sustained release application promise in clinical practice is arranged.Liu etc. successfully utilize OEG and DEG to synthesize a kind of controlled temperature sensitive multipolymer, and are used for modified graphene.
Summary of the invention:
The objective of the invention is to propose a kind of temperature sensitive controlled Graphene-polymer composite and preparation method thereof, reach the purpose of modified graphene in the hope of utilizing special high molecular temperature sensitivity.This method is synthesized thermally sensitive pyrenyl end group multipolymer through RAFT (RAFT) polymerization, and through π-π additive effect the pyrenyl end group is connected on the Graphene.The great advantage of handling like this is to be issued in the prerequisite of not destroying the Graphene conjugated structure purpose of modified graphene.
Invention is to realize like this.Mainly comprise the following steps:
(1) pyrenyl end group temperature sensitive polymer is synthetic: the CH that a certain proportion of oligomerisation of ethylene alcohol propenoate (OEG-A) and two polyvinyl alcohol vinyl ether propenoate (DEG-A) (common 6.45mmol) is dissolved in 5～10ml
3In the CN solution, add pyrenyl end group RAFT reagent (3.24 * 10
-5Mol, structure is seen Figure of description) (AIBN, 1.38mg 8.1 * 10 to add the initiator Diisopropyl azodicarboxylate
-6Mol), in system, feed nitrogen, continue 30min, place 70 ℃ water bath with thermostatic control to react 7h system then to drive away oxygen wherein.With normal hexane and methylene dichloride purifying resulting polymers, and use
1H NMR and GPC confirm the molecular weight of pyrenyl end group group and polymkeric substance, confirm the lower critical solution temperature (LCST) of the multipolymer under the different ratios through uv-absorbing.Before polymerization, material proportion that can be through control OEG and DEG is controlled at 31 to 82 ℃ with the lower critical solution temperature (LCST) of multipolymer.Resulting pyrenyl end group multipolymer further prepares polymer/graphene composite material (accompanying drawing 1) with the Graphene effect, and the lower critical solution temperature of gained matrix material can be controlled at 22 to 72 ℃ (accompanying drawings 2).
(2) preparation of Graphene-polymer composite: gained pyrenyl end group temperature sensitive polymer in (1) is dissolved in the graphene aqueous solution of 0.025mg/ml, with mixed solution supersound process 30min, stirring reaction 5h then.Excessive centrifugal repeatedly (the 14000rpm 30min)-dispersion-centrifugal process of pyrenyl end group polymer warp separates to be removed, and obtains purified Graphene-polymer composite.
Description of drawings:
1 π-π additive effect prepares Graphene-polymer composite synoptic diagram
The compound front and back LCST of 2 multipolymers and Graphene is with the variation of feed composition
Embodiment
Embodiment 2. changes amount of substance ratio in 1 into OEG: DEG=2: 8, and other are like embodiment 1.
Embodiment 5. changes amount of substance ratio in 1 into OEG: DEG=5: 5, and other are like embodiment 1.
Embodiment 6. changes amount of substance ratio in 1 into OEG: DEG=6: 4, and other are like embodiment 1.
Embodiment 7. changes amount of substance ratio in 1 into OEG: DEG=7: 3, and other are like embodiment 1.
Claims (5)
1. temperature sensitive controlled Graphene-polymer composite and preparation method thereof is characterized in that comprising the following steps:
(1) pyrenyl end group temperature sensitive polymer is synthetic: the CH that a certain proportion of oligomerisation of ethylene alcohol propenoate (OEG-A) and two polyvinyl alcohol vinyl ether propenoate (DEG-A) (common 6.45mmol) is dissolved in 5～10ml
3In the CN solution, add pyrenyl end group RAFT reagent (3.24 * 10
-5Mol, structure is seen Figure of description) (AIBN, 1.38mg 8.1 * 10 to add the initiator Diisopropyl azodicarboxylate
-6Mol), in system, feed nitrogen, continue 30min, place 70 ℃ water bath with thermostatic control to react 7h system then to drive away oxygen wherein.With normal hexane and methylene dichloride purifying resulting polymers, and use
1H NMR confirms the molecular weight of pyrenyl end group group and polymkeric substance, confirms the lower critical solution temperature (LCST) of the multipolymer under the different ratios through uv-absorbing.Before polymerization, material proportion that can be through control OEG and DEG is controlled at 31 to 82 ℃ with the lower critical solution temperature (LCST) of multipolymer.Resulting pyrenyl end group multipolymer further prepares polymer/graphene composite material (accompanying drawing 1) with the Graphene effect, and the lower critical solution temperature of gained matrix material is reduced to 22 to 72 ℃ (accompanying drawings 2).
(2) preparation of Graphene-polymer composite: gained pyrenyl end group temperature sensitive polymer in (1) is dissolved in the graphene aqueous solution of 0.025mg/ml, with mixed solution supersound process 30min, stirring reaction 5h then.Excessive centrifugal repeatedly (the 14000rpm 30min)-dispersion-centrifugal process of pyrenyl end group polymer warp separates to be removed, and obtains comparatively purified Graphene-polymer composite.
2. according to the described preparation method of claim 1, it is characterized in that: the total amount of two kinds of comonomers and revocable in the step (1) can change the monomer consumption in proportion according to the needs of molecular weight of copolymer.
3. according to the described preparation method of claim 1, it is characterized in that: temperature of reaction can be regulated in the step (1), all can in 65～80 ℃ of scopes.
4. according to the described preparation method of claim 1, it is characterized in that: solvent for use is not limited in CH in the step (1)
3CN can also use other polar solvents, like THF, and DMF, DMSO, 1,4-dioxane etc.
5. according to the described preparation method of claim 1, it is characterized in that: ratio and the on-fixed of RAFT reagent and AIBN in the step (1), RAFT/AIBN=2-8.
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| CN104181258A (en) * | 2013-05-24 | 2014-12-03 | 北京蛋白质组研究中心 | Glycoprotein N-carbohydrate chain one-step enrichment-derivation processing method based on graphene and MALDI-TOF-MS analysis method |
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| CN103316352B (en) * | 2013-06-25 | 2018-09-07 | 中国科学院深圳先进技术研究院 | Stannic oxide/graphene nano pharmaceutical carrier, antitumor drug and preparation method thereof |
| CN103316352A (en) * | 2013-06-25 | 2013-09-25 | 中国科学院深圳先进技术研究院 | Graphene oxide nano-drug carrier and anti-tumor drug as well as preparation method of anti-tumor drug |
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| CN106430159B (en) * | 2016-08-31 | 2018-05-25 | 北京航空航天大学 | Pi bond is conjugated the tough highly conductive bionic laminar graphene composite material preparation method of integration |
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Application publication date: 20120718 |