CN106829948A - Hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification and preparation method thereof - Google Patents
Hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification and preparation method thereof Download PDFInfo
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- CN106829948A CN106829948A CN201710080841.1A CN201710080841A CN106829948A CN 106829948 A CN106829948 A CN 106829948A CN 201710080841 A CN201710080841 A CN 201710080841A CN 106829948 A CN106829948 A CN 106829948A
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- monoisocyanates
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 73
- 230000004048 modification Effects 0.000 title claims abstract description 38
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000002715 modification method Methods 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000012986 modification Methods 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 9
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 heptyl ester Chemical class 0.000 claims description 9
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 8
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NLAGNNORBYGNAV-UHFFFAOYSA-N 2-methylnonacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(C)C NLAGNNORBYGNAV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- XFEWMFDVBLLXFE-UHFFFAOYSA-N 1-isocyanatodecane Chemical class CCCCCCCCCCN=C=O XFEWMFDVBLLXFE-UHFFFAOYSA-N 0.000 claims description 3
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims description 3
- DYQFCTCUULUMTQ-UHFFFAOYSA-N 1-isocyanatooctane Chemical compound CCCCCCCCN=C=O DYQFCTCUULUMTQ-UHFFFAOYSA-N 0.000 claims description 3
- XOHBENIMDRFUIH-UHFFFAOYSA-N 2-isocyanato-2,4,4-trimethylpentane Chemical class CC(C)(C)CC(C)(C)N=C=O XOHBENIMDRFUIH-UHFFFAOYSA-N 0.000 claims description 3
- PIVVYCUAIZAGPB-UHFFFAOYSA-N 2-isocyanatoheptane Chemical class CCCCCC(C)N=C=O PIVVYCUAIZAGPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical class CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 claims description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- VRVUKQWNRPNACD-UHFFFAOYSA-N 1-isocyanatopentane Chemical compound CCCCCN=C=O VRVUKQWNRPNACD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000002780 morpholines Chemical class 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- LIQZZAPDGRFJIP-UHFFFAOYSA-L [dodecanoyloxy-bis(2-methylpropyl)stannyl] dodecanoate Chemical compound CC(C)C[Sn+2]CC(C)C.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O LIQZZAPDGRFJIP-UHFFFAOYSA-L 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 230000008859 change Effects 0.000 description 19
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UCQVWRUWFNVEHI-UHFFFAOYSA-L C(C(C)C)[Sn+2]CC(C)C.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] Chemical compound C(C(C)C)[Sn+2]CC(C)C.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] UCQVWRUWFNVEHI-UHFFFAOYSA-L 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- GFLXBRUGMACJLQ-UHFFFAOYSA-N 1-isocyanatohexadecane Chemical compound CCCCCCCCCCCCCCCCN=C=O GFLXBRUGMACJLQ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JNWLFMYCGXLVJQ-UHFFFAOYSA-N 2-isocyanatohexane Chemical class CCCCC(C)N=C=O JNWLFMYCGXLVJQ-UHFFFAOYSA-N 0.000 description 1
- BHXMYHDVDLZHAG-UHFFFAOYSA-N 2-isocyanatononane Chemical class CCCCCCCC(C)N=C=O BHXMYHDVDLZHAG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Hydrophobic graphene oxide the invention discloses a kind of modification of chain-like alkyl monoisocyanates and preparation method thereof, the hydrophobic graphene oxide is mainly and is formed by chain-like alkyl monoisocyanates and graphene oxide, and chain-like alkyl is connected in graphene oxide layer structure in the way of chemical graft.Relative to prior art, the hydrophobic graphene oxide of the chain-like alkyl monoisocyanates modification that the present invention is provided, due to being grafted hydrophobic long chain alkane structure, with N, N dimethylformamides (DMF) are that the various polarity non-protonic solvent of representative being capable of fine dispersion and stabilization.Preparation method process that the long chain alkane that the present invention is provided modifies hydrophobic graphene oxide is simple and reliable, be easily achieved, for Graphene grafting backbone provides new thinking, while the application prospect of Graphene can be expanded significantly.
Description
Technical field
Hydrophobic graphene oxide the present invention relates to a kind of modification of chain-like alkyl monoisocyanates and preparation method thereof, belongs to
Technical field of nano material field.
Background technology
Graphene (Graphene) is a kind of novel nano-material with two-dimension plane structure being found for 2004, it
Special monoatomic layer structure makes it have the physicochemical properties of many uniquenesses.The Graphene of structural integrity is by without any
The two dimensional crystal that the benzene hexatomic ring of labile bond is combined, the inert state in its surface, interaction with other media compared with
It is weak, and have stronger Van der Waals force between graphene sheet layer, aggregation is easily produced, make its solubility property poor, this gives Graphene
Further research and application cause great difficulty.
Existing research shows that the graphene oxide (Graphene Oxide, GO) that Graphene is obtained after being oxidized is tied
Containing abundant hydroxyl, carboxyl etc. in structure, thus also there is obvious hydrophily, this changes the original hydrophobic property of Graphene
Matter, will retrieve hydrophobic graphene-structured, it is necessary to further be modified graphene oxide and be modified, and be grafted various
The carbon-chain structure of hydrophobic property is one type method.
Someone is reported using the reaction active groups in the carboxyl on GO, hydroxyl or epoxy radicals and polymer segment (such as
Amino etc.) reaction obtain macromolecular grafted graphene oxide.(Niyogi S, Bekyarova E, the Itkis M such as Niyogi
E,et al.Solution properties of graphite and graphene.[J].Journal of the
American Chemical Society,2006,128(24):7720-1.) under reflux conditions, using on octadecylamine (ODA)
Amino and graphene oxide in carboxyl reaction, the modified Graphene of long chain alkylating, the stone of the functionalization is successfully obtained
Black alkene can be in the conventional organic solvent such as tetrahydrofuran (THF) and carbon tetrachloride compared with good dissolving.(Tang the X Z, Li such as Tang
W,Yu Z Z,et al.Enhanced thermal stability in graphene oxide covalently
functionalized with2-amino-4,6-didodecylamino-1,3,5-triazine[J].Carbon,2011,
49(4):1258-1265.) use the double lauryl amine -1,3,5- triazines of the compound in triazine class 2- amino -4,6- with long chain alkane
(ADDT) graphite oxide is modified, the polarity of surface of graphene oxide is changed, due to the effect of long chain alkane, modified outcome is non-
There is good dispersiveness in the chloroform solvent of polarity.Chakraborty etc. (Chakraborty S, Guo W, Hauge R H,
et al.Reductive Alkylation of Fluorinated Graphite[J].Chemistry of Materials,
2008,20(9):3134-3136.) with fluoro graphite as raw material, the graphite that dodecyl is modified is obtained by radical reaction
Alkene, makes it have good dissolubility in the organic solvents such as chloroform.Chinese invention patent application publication No. CN101863465A's
Patent document discloses a kind of polar functional group by functionalization dendritic and Graphene and reacts, and realizes tree-shaped height
The method of molecule grafting, so as to improve dispersive property of the Graphene in polar solvent.Chinese invention patent application publication No.
The patent document of CN103881036A discloses a kind of preparation method of the polymolecularity Graphene of polymer grafting, by function
Change the hydroxyl reaction on initiator and Graphene, the initiator in graphenic surface self assembly, then free radical is triggered by original position
Polymer in situ is grown in graphenic surface by polymerisation.Although the above method can access macromolecular grafted modified oxygen
Graphite alkene, improves the dispersive property of graphene oxide, but reaction efficiency is relatively low on the whole, complex operation, narrow application range,
It is unfavorable for the defects such as mass production.
The content of the invention
Goal of the invention：Hydrophobically modified think of is carried out it is an object of the invention to provide a kind of graft grapheme simple and easy to apply
Road and preparation method.The inventive method process is simple, mild condition, functionalization degree are high, the method functionalization it is hydrophobic
Graphene oxide can be dispersed in the various polarity non-protonic solvents such as N,N-dimethylformamide (DMF) and can be grown
Time keep stabilization, for Graphene be processed further with application provide new thinking.
Technical scheme：To achieve these goals, dredging the invention discloses a kind of modification of chain-like alkyl monoisocyanates
Water graphene oxide, it is mainly and is formed by chain-like alkyl monoisocyanates and graphene oxide, and chain-like alkyl is connect with chemistry
The mode of branch is connected in graphene oxide layer structure.
The a series of chain-like alkyl monoisocyanates being directed to, its structure has following signal：
Wherein, different n correspond to different alkyl monoisocyanates, preferably n=1-50, both including straight chained alkyl structure
Monoisocyanates, and the monoisocyanates including branched chain alkyl moiety, including but not limited to n-butyl isocyanate, isocyanic acid penta
Ester, n-hexyl isocyanates, 2- hexyls isocyanates, the positive heptyl ester of isocyanic acid, 2- heptyl isocyanates, n-Octyl isocyanate,
2- octyl groups isocyanates, t-octyl isocyanates, 2- nonyls isocyanates, decyl isocyanates, the ester of isocyanic acid 11, dodecane
Based isocyanate, tetradecyl isocyanante, hexadecyl isocyanate, octadecylisocyanate, isotriacontane based isocyanate
Deng.
The graphene oxide being directed to, does not have special requirement to described graphene oxide, can use Hummers
Method (ummers W S, Offeman R E.Preparation of Graphitic Oxide, Journal of the
American Chemical Society,1958,80(6):1339) it is prepared.
A kind of hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification of the present invention, is chain-like alkyl Dan Yi
A kind of structure that cyanate is connected generation chemical bond with the hydroxyl on graphene oxide, carboxyl and is formed by NCO,
Its chemical constitution has the feature anticipated as shown in Figure 5：Wherein, hydroxyl, carboxylic are brokenly dispersed with graphene oxide layer
The chemical constitution such as base and epoxy radicals, and on structural moiety after some of them hydroxyl and carboxyl after chemical reaction, it is connected to number
The chain-like alkyl structure that amount is not waited, these chain-like alkyls are connected in graphene oxide layer in the way of chemical graft.
The invention also discloses the preparation method of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification, bag
Include following steps：In not water-containing organic solvent, using trimethylamine class catalyst or organic tin catalyst, by chain-like alkyl
Monoisocyanates and graphene oxide mix, and react under certain condition, obtain final product.
The trimethylamine class catalyst or organic tin catalyst being directed to, including triethylene diamine, morpholine derivative,
Tin dilaurate diisobutyl tin, stannous iso caprylate etc., but be not limited thereto.
The not water-containing organic solvent being directed to, including DMF (DMF), DMA
(DMAc), tetrahydrofuran (THF), alkane such as n-hexane, normal butane, hexamethylene etc., aromatic solvent such as benzene,toluene,xylene
Deng, but be not limited thereto.
In preparation method of the present invention, the chemical reaction process of chain-like alkyl monoisocyanates modification graphene oxide only has one
Individual step.
Wherein the ratio of chain-like alkyl monoisocyanates consumption and graphene oxide consumption is in 5mmol:1g to 50mmol:1g
Between, more excellent ratio is in 25mmol:1g to 50mmol:Between 1g.
In the reaction condition of the preparation method, reaction temperature is not required particularly, between room temperature (25 DEG C) to 80
Between DEG C, more excellent reaction temperature is between 30 DEG C -50 DEG C.
In the reaction condition of the preparation method, the reaction time is not required particularly, between 1-48 hours, more
The excellent reaction time is between 12-24 hours.
Technique effect：Relative to prior art, the hydrophobic oxidation of the chain-like alkyl monoisocyanates modification that the present invention is provided
Graphene, due to being grafted hydrophobic long chain alkane structure, in the various poles with DMF (DMF) as representative
Property non-protonic solvent being capable of fine dispersion and stabilization.The long chain alkane that the present invention is provided modifies the system of hydrophobic graphene oxide
Preparation Method process is simple and reliable, be easily achieved, for Graphene grafting backbone provides new thinking, while can expand significantly
The application prospect of Graphene.
Brief description of the drawings
Fig. 1 is that the Fourier of the hydrophobic graphene oxide of graphite, graphite oxide and chain-like alkyl monoisocyanates modification becomes
Change infrared spectrum (FTIR) figure；
Fig. 2 is x-ray photoelectron power spectrum (XPS) spectrum of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification
Figure；
Fig. 3 is the X-ray diffraction of the hydrophobic graphene oxide of graphite, graphite oxide and chain-like alkyl monoisocyanates modification
(XRD) spectrogram；
Fig. 4 is the dispersive property of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification；
Fig. 5 is the chemical constitution schematic diagram of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates modification.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but the scope of protection of present invention is not limited to
Scope described by embodiment.
Following graphene oxide is using Hummers methods (Hummers W S, Offeman R E.Preparation
Of Graphitic Oxide, Journal of the American Chemical Society, 1958,80 (6):1339)
Prepared graphene oxide.
Embodiment 1：
Weigh 1g graphene oxides to be placed in single-necked flask, add the anhydrous DMFs of 100mL (DMF) molten
Agent, it is continuous ultrasonic 30 minutes with ultrasonic cleaner power (50W) at room temperature so that graphene oxide is dispersed, adds
5g dodecyl isocyanates and 0.05g tin dilaurate diisobutyl tin, magnetic agitation is reacted 24 hours at 50 DEG C.Reaction mixing
Thing dichloromethane cyclic washing, centrifugation obtain ten to remove unreacted dodecyl isocyanate after vacuum drying
The hydrophobic graphene oxide (C12-GO) of dialkyl isocyanate modification.
The hydrophobic graphene oxide (C12-GO) modified the graphene oxide (GO) in graphite, this example and chain-like alkyl
Characterize and determined.
In the infrared spectrogram of accompanying drawing 1, the infrared spectrum of graphite is almost straight line, and contrast GO's and C12-GO is infrared
Spectrogram, in the spectrogram of C12-GO, 2918cm-1、2848cm-1There is the absworption peak of methyl, methylene at wave number.Modification
It is successful that the change of infrared spectrum demonstrate chain-like alkyl monoisocyanates to modify hydrophobic graphene oxide from an angle afterwards.
Accompanying drawing 2 is x-ray photoelectron energy-spectrum scanning (XPS) spectrogram of C12-GO, shows that C, O, N element are deposited in full spectrum
To the N1s absworption peaks of N element in the smart scanning discovery C12-GO of 401eV positions, it was confirmed that the presence of N element, and N element
It is non-existent in original graphene oxide, so as to confirm chain-like alkyl monoisocyanates to oxidation stone from another angle
The modification of black alkene is successful.
In X-ray diffraction (XRD) spectrogram of accompanying drawing 3, graphite has a sharp absworption peak near 2 θ=26 °；Work as quilt
After being oxidized to graphene oxide, this peak position is displaced to 2 θ=10.2 °, and this is mainly due to surface of graphene oxide oxygen-containing group
The effect of group, increases interlamellar spacing；After dodecyl isocyanate is grafted to surface of graphene oxide, this peak is further
Offset to low-angle, at 2 θ=7.3 °, this shows the hydrophobic graphene oxide of chain-like alkyl monoisocyanates grafting
Layer structure is further peeled.
Accompanying drawing 4 is graphene oxide after the grafting of chain-like alkyl monoisocyanates in water and N,N-dimethylformamide
(DMF) deployment conditions in.Hydrophobic graphene oxide after being modified through chain-like alkyl monoisocyanates stands 24 hours in water
Afterwards, bottom is all deposited in, and after standing 24 hours in DMF (DMF), is appointed and is shown good dispersion
Property, this shows that chain-like alkyl monoisocyanates is successful to the hydrophobically modified of graphene oxide.
Embodiment 2：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into n-butyl isocyanate, chain
Alkyl monoisocyanate is 5mmol with the usage ratio of graphene oxide:1g, has obtained the modification of chain-like alkyl monoisocyanates
Graphene oxide.
Embodiment 3：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into amyl isocyanate, chain alkane
Base monoisocyanates is 50mmol with the usage ratio of graphene oxide:1g, has obtained the modification of chain-like alkyl monoisocyanates
Graphene oxide.
Embodiment 4：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into n-hexyl isocyanates, chain
Shape alkyl monoisocyanate is 25mmol with the usage ratio of graphene oxide:1g, has obtained chain-like alkyl monoisocyanates and has repaiied
The graphene oxide of decorations.
Embodiment 5：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into 2- hexyl isocyanates, instead
It is 25 DEG C to answer temperature, and the reaction time is 48 hours, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 6：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into isocyanic acid positive heptyl ester, react
Temperature is 80 DEG C, and the reaction time is 1 hour, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 7：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into 2- heptyl isocyanates, instead
It is 30 DEG C to answer temperature, and the reaction time is 24 hours, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 8：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into n-Octyl isocyanate, instead
It is 50 DEG C to answer temperature, and the reaction time is 12 hours, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 9：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into 2- octyl group isocyanates, N,
Dinethylformamide (DMF) replaces with DMA (DMAc), has obtained the modification of chain-like alkyl monoisocyanates
Graphene oxide.
Embodiment 10：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into t-octyl isocyanates, N,
Dinethylformamide (DMF) replaces with tetrahydrofuran (THF), has obtained the graphite oxide of chain-like alkyl monoisocyanates modification
Alkene.
Embodiment 11：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into 2- nonyl isocyanates, N,
Dinethylformamide (DMF) replaces with n-hexane, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 12：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into decyl isocyanates, N, N-
Dimethylformamide (DMF) replaces with toluene, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 13：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into the ester of isocyanic acid 11, N, N-
Dimethylformamide (DMF) replaces with dimethylbenzene, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 14：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into tetradecyl isocyanante,
Dimethylformamide (DMF) replaces with normal butane, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 15：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into hexadecyl isocyanate,
Catalyst choice triethylene diamine, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 16：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into octadecylisocyanate, it is catalyzed
Agent selects tin dilaurate diisobutyl tin, has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 17：
It is same as Example 1, simply change the dodecyl isocyanate in embodiment 1 into isotriacontane base isocyanic acid
Ester, catalyst choice stannous iso caprylate has obtained the graphene oxide of chain-like alkyl monoisocyanates modification.
Embodiment 2-17 gained graphene oxides, are detected, testing result and the knot of embodiment 1 according to the method for embodiment 1
It is really essentially identical, hydrophobically modified success of the chain-like alkyl monoisocyanates to graphene oxide.
Claims (10)
1. the hydrophobic graphene oxide that a kind of chain-like alkyl monoisocyanates is modified, it is characterised in that it is mainly by chain alkane
Base monoisocyanates and graphene oxide are formed, and chain-like alkyl is connected to graphene oxide layer knot in the way of chemical graft
On structure.
2. the hydrophobic graphene oxide that chain-like alkyl monoisocyanates according to claim 1 is modified, it is characterised in that institute
The structural formula for stating chain-like alkyl monoisocyanates is as follows：
Wherein, different n correspond to different alkyl monoisocyanates, both including the monoisocyanates of straight chained alkyl structure, and
Monoisocyanates including branched chain alkyl moiety.
3. the hydrophobic graphene oxide that chain-like alkyl monoisocyanates according to claim 2 is modified, it is characterised in that institute
State n=1-50.
4. the hydrophobic graphene oxide that chain-like alkyl monoisocyanates according to claim 1 is modified, it is characterised in that institute
State chain-like alkyl monoisocyanates for n-butyl isocyanate, amyl isocyanate, n-hexyl isocyanates, 2- hexyls isocyanates,
The positive heptyl ester of isocyanic acid, 2- heptyl isocyanates, n-Octyl isocyanate, 2- octyl groups isocyanates, t-octyl isocyanates, 2- nonyls
Based isocyanate, decyl isocyanates, the ester of isocyanic acid 11, dodecyl isocyanate, tetradecyl isocyanante, hexadecane
Based isocyanate, octadecylisocyanate or isotriacontane based isocyanate.
5. the hydrophobic graphene oxide that chain-like alkyl monoisocyanates according to claim 1 is modified, it is characterised in that institute
Stating chemical graft is：Chain-like alkyl monoisocyanates is connected life by NCO with the hydroxyl on graphene oxide, carboxyl
Into chemical bond.
6. described in any one of claim 1-5 chain-like alkyl monoisocyanates modification hydrophobic graphene oxide preparation method,
It is characterised in that it includes following steps：In not water-containing organic solvent, it is catalyzed using trimethylamine class catalyst or organic tin
Agent, chain-like alkyl monoisocyanates and graphene oxide are mixed, and are reacted under certain condition, are obtained final product.
7. the preparation method of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates according to claim 6 modification, its
It is characterised by, the not water-containing organic solvent is DMF (DMF), DMA (DMAc), four
Hydrogen furans (THF), n-hexane, normal butane, hexamethylene, benzene, toluene or dimethylbenzene.
8. the preparation method of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates according to claim 6 modification, its
It is characterised by, the trimethylamine class catalyst is triethylene diamine or morpholine derivative；The organic tin catalyst is two
Laurate diisobutyl tin or stannous iso caprylate.
9. the preparation method of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates according to claim 6 modification, its
It is characterised by, the chain-like alkyl monoisocyanates is (5-50mmol) with the usage ratio of graphene oxide:1g, more preferably
(20-50)mmol:1g。
10. the preparation method of the hydrophobic graphene oxide of chain-like alkyl monoisocyanates according to claim 6 modification, its
It is characterised by, the condition during reaction is：Reaction temperature is 25-80 DEG C, more preferably 30 DEG C -50 DEG C；Reaction time is 1-48
Hour, more preferably 12-24 hours.
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| CN108559092A (en) * | 2018-03-14 | 2018-09-21 | 上海交通大学 | The water-borne dispersions of carbon material dispersant and preparation method thereof and the carbon material of stabilization containing the dispersant |
| CN111592655A (en) * | 2020-05-22 | 2020-08-28 | 陕西科技大学 | Self-healing flexible composite material and preparation method thereof |
| CN113694898A (en) * | 2021-10-13 | 2021-11-26 | 黑龙江省科学院高技术研究院 | Preparation method of linear alkyl modified expanded graphite |
| CN114181716A (en) * | 2021-10-19 | 2022-03-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction |
| CN117903699A (en) * | 2024-01-16 | 2024-04-19 | 弘瑞力丰复合材料(沭阳)有限公司 | Low-temperature-resistant marine plywood and preparation method thereof |
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| CN108559092A (en) * | 2018-03-14 | 2018-09-21 | 上海交通大学 | The water-borne dispersions of carbon material dispersant and preparation method thereof and the carbon material of stabilization containing the dispersant |
| CN108559092B (en) * | 2018-03-14 | 2021-02-26 | 上海交通大学 | Carbon material dispersant, method for producing the same, and stable aqueous dispersion of carbon material containing the dispersant |
| CN111592655A (en) * | 2020-05-22 | 2020-08-28 | 陕西科技大学 | Self-healing flexible composite material and preparation method thereof |
| CN113694898A (en) * | 2021-10-13 | 2021-11-26 | 黑龙江省科学院高技术研究院 | Preparation method of linear alkyl modified expanded graphite |
| CN113694898B (en) * | 2021-10-13 | 2023-08-22 | 黑龙江省科学院高技术研究院 | Preparation method of linear alkyl modified expanded graphite |
| CN114181716A (en) * | 2021-10-19 | 2022-03-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application in Suzuki reaction |
| CN114181716B (en) * | 2021-10-19 | 2023-08-15 | 太原理工大学 | Gas response type Pickering emulsifier, preparation method and application thereof in Suzuki reaction |
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