CN103923234A - Pyrenyl-containing radical initiator, and synthesis method and use thereof - Google Patents
Pyrenyl-containing radical initiator, and synthesis method and use thereof Download PDFInfo
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- 239000003999 initiator Substances 0.000 title claims abstract description 75
- 125000001725 pyrenyl group Chemical group 0.000 title claims abstract description 74
- 238000001308 synthesis method Methods 0.000 title abstract 2
- -1 azo compound Chemical class 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 229960001701 chloroform Drugs 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 8
- RPENMORRBUTCPR-UHFFFAOYSA-M sodium;1-hydroxy-2,5-dioxopyrrolidine-3-sulfonate Chemical compound [Na+].ON1C(=O)CC(S([O-])(=O)=O)C1=O RPENMORRBUTCPR-UHFFFAOYSA-M 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 6
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- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 2
- 238000001149 thermolysis Methods 0.000 claims description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims 1
- 125000005581 pyrene group Chemical group 0.000 abstract description 14
- 238000007112 amidation reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
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- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
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- 150000003334 secondary amides Chemical class 0.000 description 4
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JEGQDOJIGCZMHV-UHFFFAOYSA-N butan-1-ol;pyrene Chemical class CCCCO.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 JEGQDOJIGCZMHV-UHFFFAOYSA-N 0.000 description 3
- OIVGABMEJONVKJ-UHFFFAOYSA-N formic acid pyrene Chemical compound C(=O)O.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34 OIVGABMEJONVKJ-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
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- 230000009467 reduction Effects 0.000 description 3
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- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
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- NVSXNYFKHSNOQL-UHFFFAOYSA-N methanamine;pyrene Chemical compound NC.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 NVSXNYFKHSNOQL-UHFFFAOYSA-N 0.000 description 2
- 230000004001 molecular interaction Effects 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
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- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- 0 C*C(CC1)=C2C=CC3=C*CC4C=C=*1C2C3*4 Chemical compound C*C(CC1)=C2C=CC3=C*CC4C=C=*1C2C3*4 0.000 description 1
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- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 1
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a pyrenyl-containing radical initiator, and a synthesis method and use thereof. The initiator is a pyrenyl-containing azo compound with a symmetric structure, and can generate two primary radicals containing pyrenyl with the same molecular structures after thermal decomposition. A common commodity azo initiator and a pyrenyl-containing small molecule compound are taken as raw materials, and synthesis is carried out by adopting esterification reaction or amidation reaction. The pyrenyl-containing radical initiator disclosed by the invention can be used as a thermal initiator for alkene compound polymerization reaction to synthesize the pyrenyl-containing high-molecular compound, the pyrene group is located at the tail end of a macromolecular chain, and a single macromolecular chain contains 0.9-1.2 pyrene groups averagely; the synthesized pyrenyl-containing high-molecular compound can serve as a dispersing aid to be applied to a dispersing aid-assisted liquid-phase stripping method, so as to prepare graphene from natural graphite.
Description
Technical field
The present invention relates to functionalized photoinitiators field, more particularly relate to a kind of innovation containing pyrenyl azo radical initiator and preparation method and use thereof.
Background technology
Graphene, because of its unique structure, the performance of excellence and wide application prospect, caused worldwide research boom, and low cost preparation in macroscopic quantity high-quality Graphene is the basis of supporting all research and application since 2004 come out.Preparing Graphene taking natural graphite as raw material is the effective way of obtaining at present grapheme material, and its main preparation methods has micromechanics stripping method, graphite oxide reduction method and liquid phase stripping method.Wherein, micromechanics stripping method can be produced high-quality Graphene, but productive rate is low, is only applicable to fundamental research.Though graphite oxide reduction method can realize the low cost preparation in macroscopic quantity of Graphene, gained Graphene is because existing more defect to cause partial properties (as electric property) loss, and range of application is restricted.Be similar to micromechanics stripping method, liquid phase stripping method also can be produced high-quality Graphene, and the indexs such as cost control and Graphene productive rate are close to graphite oxide reduction method.This just implements possibility for the Application Areas of a large amount of high-quality Graphenes of needs such as such as multifunctional polymer matrix material provides.Liquid phase stripping method thereby day by day become the study hotspot of graphene preparation method.
Adopt liquid phase stripping method, people have prepared concentration up to 1.5mg.mL
-1graphene dispersing solution, this with the current loose liquid concentration 1～7mg.mL of the best result of the graphene oxide of application the most widely
-1quite.Blemish in an otherwise perfect thing, this high concentration dispersion can only just can obtain by long-time (>200h) supersound process in surface can be close to a small amount of high boiling solvent of Graphene (being difficult to remove completely in subsequent applications).Even make it comprise low boiling point organic solvent water, shorten the supersound process time, solve the problems such as dispersion stability is poor for widening solvent scope; people have been developed again the improvement liquid phase stripping method (i.e. " dispersing auxiliary is assisted liquid phase stripping method ") that uses dispersing auxiliary in dispersion system; and obtain remarkable effect (J.N.Coleman Accounts of Chemical Research; 2013; 46,14-22; J.A.Mann, W.R.Dichtel The Journal of Physical Chemistry Letters, 2013,4,2649-2657; D.Parviz, S.Das, H.S.Tanvir Ahmed, F.Irin, S.Bhattacharia, M.J.Green ACS Nano, 2012,6,8857-8867; E.-Y.Choi, T.H.Han, J.Hong, J.E.Kim, S.H.Lee, H.W.Kim, S.O.Kim Journal of Material Chemistry, 2010,20,1907-1912).In numerous dispersing auxiliaries of having applied, a compounds that contains pyrenyl group is particularly noticeable.
Why causing people's interest containing pyrenyl compound, is to interact because pyrenyl group can form π-π with Graphene surface.Even this interaction is suitable with hydrogen bond chemical bond in intensity, be to select the most important condition of dispersing auxiliary and produce strong molecular interaction between energy and Graphene.This strong molecular interaction is mainly because of extremely close between the two chemical structure (pyrene can be regarded as a part for Graphene in chemical structure).Contain in pyrenyl compound various, can provide more solvation point containing pyrenyl macromolecular compound with respect to containing pyrenyl micromolecular compound, i.e. so-called " polymer effect (polymer effect) ", therefore in the situation that consumption is suitable, have the stronger ability that separates Graphene from graphite containing pyrenyl macromolecular compound, the graphene dispersing solution of gained also has higher concentration and the stability of Geng Jia.For containing pyrenyl macromolecular compound, the molecular designing that has and only have 1 pyrenyl group to be positioned at the polymer end of the chain (being single pyrenyl end-blocking polymer) can guarantee that the macromolecular chain number that is adsorbed in Graphene surface maximizes, thereby is more conducive to promote dispersing auxiliary peeling off and disperseing usefulness graphite.
Single pyrenyl end-blocking polymer based on vinyl compound is main ionic polymerization (Chinese invention patent ZL200910231370.5) and the active free radical polymerization (J.Zhang of adopting at present; Y.Li; S.P.Armes; S.Liu The Journal of Physical Chemistry B; 2007; 111,12111-12118; Tang Tingji, Ye Yu, plum minister, Du Fusheng, Zhang Xin, the continuous chemical journal of Li Fu, 2002,60,931-938) synthesize.Wherein, ionic polymerization not only has high selectivity to vinyl compound, and very harsh to polymerization system and reaction conditions requirement, and applicable limitation is very large.Active free radical polymerization has changed the predicament that ionic polymerization faces to a great extent, and its applicable vinyl compound kind is relatively many, and reaction conditions is also gentleer.But compared with traditional radical polymerization, the applicable vinyl compound kind of active free radical polymerization is still aobvious less, still aobvious higher to the requirement of polymerization system and reaction conditions, still have that initiator is expensive, some auxiliary agent easily causes the shortcomings such as polymer is aging without commercially available reagent and preparation process complexity, remaining reagent.Comparatively speaking, traditional radical polymerization has that polymerization technique is simple, implementation method is various, good economy performance, is applicable to the advantages such as nearly all vinyl compound polymerization.Although not yet there is at present the directly high molecular research report of synthetic pyrenyl group end-blocking of this polyreaction of employing, but initiator residue is positioned at the polymerization mechanism indication of the polymer end of the chain: if pyrenyl group can be introduced to radical initiator, just completely likely synthesize the polymer of pyrenyl group end-blocking; For example, if (taken appropriate measures again, use chain-transfer agent, rising polymerization temperature etc.) in polymerization process, eliminate/suppress coupling termination, just completely likely further synthesize every macromolecular chain by approximately 1 pyrenyl group end-blocking containing pyrenyl macromolecular compound.Therefore, in development when single pyrenyl end-blocking polymer, if the indexs such as the molecular weight to target product, molecular weight distribution, taxis without strict demand, radical polymerization also should become one of selection scheme.
In sum, the auxiliary liquid phase stripping method of dispersing auxiliary be taking natural graphite as raw material, the effective ways of low cost preparation in macroscopic quantity high-quality Graphene.The key of this preparation method's successful implementation is to select suitable dispersing auxiliary, and single pyrenyl end-blocking polymer is a kind of dispersing auxiliary of wherein having outstanding performance.For obtaining single pyrenyl end-blocking polymer, main ionic polymerization and the active free radical polymerization of adopting synthesizes at present, but this two type of polymerization more or less exists the shortcomings such as applicable vinyl compound kind is few, reaction conditions is harsh, economy is poor.Radical polymerization, as most widely used polyreaction in high polymer synthesis industry, has clear superiority in these areas.The most important thing is, radical polymerization also can synthesize in theory every macromolecular chain by approximately 1 pyrenyl group end-blocking containing pyrenyl polymer, the key of its successful implementation is to develop a kind of novel containing pyrenyl radical initiator.
Summary of the invention
The present invention In view of the foregoing, provides a kind of containing pyrenyl radical initiator and preparation method and use thereof.This initiator is to utilize initiator residue to be positioned at the radical polymerization mechanism of the polymer end of the chain and special molecular designing, synthetic one are novel containing pyrenyl azo compound.It is taking existing goods initiator and contain pyrenyl micromolecular compound as raw material, adopts the skillful simple organic chemical reactions of mechanism to synthesize.Synthetic work once completes in same reactor, and without intermediate product is carried out to extra separation, purification, process window is wide in range, simple to operate, and controllability is strong, and productive rate is high.It has solved conventional commercial initiators and has not been suitable for the synthetic high molecular problem of special groups end-blocking, thereby provide a kind of new selection scheme for obtaining containing pyrenyl polymer (every macromolecular chain is by approximately 1 pyrenyl group end-blocking), and then prepared Graphene for the auxiliary liquid phase stripping method of dispersing auxiliary and lay a good foundation.
In order to achieve the above object, of the present inventionly represented by following general formula (A) containing pyrenyl radical initiator
R in general formula
1for
one of, wherein a=0～4, b=0～1, c=0～3, d=0～3; In its chemical structure, be a kind of symmetric form containing pyrenyl azo compound, after thermolysis, can produce two molecular structures identical containing the elementary free radical of pyrenyl.
The pyrenyl radical initiator that contains of the present invention adopts esterification or amidate action to synthesize.Under reaction promoter exists, be dissolved in organic solvent and react by conventional commercial initiators with containing pyrenyl micromolecular compound, temperature of reaction is 10～60 DEG C, and the reaction times is 6～72 hours, and reaction atmosphere is air, nitrogen or argon gas; Synthetic work once completes in same reactor, without intermediate product is carried out to extra separation, purification.
The compound of conventional commercial initiators for adopting general formula (B) to represent
R
2-N=N-R
2 （B）
R in general formula
2for
(being called for short B1),
(being called for short B2)
one of (being called for short B3).
Compound containing pyrenyl micromolecular compound for adopting general formula (C) to represent
R in general formula
3for-OH(is called for short C1, wherein x=0～4) ,-NH
2(be called for short C2, wherein x=0～1) or
one of (being called for short C3, wherein x=0～3); Consumption is the conventional commercial initiators of the every 1mol of 2.2～2.5mol.
The conventional commercial initiators of esterification is B1, B2 or B3, is C1 or C3 containing pyrenyl micromolecular compound.
The reaction promoter of esterification is " 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDC.HCl)+DMAP (DMAP) " or " EDC.HCl+DMAP+1-hydroxybenzotriazole (HOBT) ", and consumption is the conventional commercial initiators of the every 1mol of 2.3～2.6mol EDC.HCl, 0.3～0.5mol DMAP, 2.5～2.9molHOBT.
The conventional commercial initiators of amidate action is B1, is C2 containing pyrenyl micromolecular compound.
The reaction promoter of amidate action is " EDC.HCl+N-N-Hydroxysuccinimide (NHS) " or " EDC.HCl+N-hydroxy thiosuccinimide (Sulfo-NHS) ", and consumption is the conventional commercial initiators of the every 1mol of 2.3～2.6mol EDC.HCl, 2.5～2.9mol NHS, 2.5～2.9mol Sulfo-NHS.
Organic solvent is the mixture of one or two or more solvent in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dimethyl formamide, and consumption is the conventional commercial initiators of the every 1mg of 0.3～1.5ml.
The esterification condition of optimizing is: reaction promoter adopts " EDC.HCl+DMAP+HOBT ", and organic solvent adopts methylene dichloride or trichloromethane, and temperature of reaction is 25～35 DEG C, and the reaction times is 18～28 hours, and reaction atmosphere is nitrogen.Adopt after the reaction conditions of this optimization, effect is best.
The amidation reaction condition of optimizing is: reaction promoter adopts " EDC.HCl+Sulfo-NHS ", and organic solvent adopts methylene dichloride or trichloromethane, and temperature of reaction is 25～35 DEG C, and the reaction times is 18～28 hours, and reaction atmosphere is nitrogen.Adopt after the reaction conditions of this optimization, effect is best.
The thermal initiator that can be used as vinyl compound polyreaction containing pyrenyl radical initiator of the present invention.Applicable vinyl compound is to adopt conventional commodity azo-initiator to carry out the unsaturated compound of polymerization.This ethylenically unsaturated compounds can be monomer, oligopolymer or their mixture.
Applicable ethylenically unsaturated monomers is selected from vinylbenzene, (methyl) acrylate, vinyl imidazole, vinyl pyrrolidone, vinyl acetate, (methyl) vinylformic acid, (methyl) acrylamide, vinyl cyanide, propenal, maleic anhydride, fumaric acid anhydride, vinyl halide, vinylidene halide, ethene and conjugated dienes.Preferably vinylbenzene, (methyl) acrylate, vinyl imidazole, vinyl pyrrolidone, vinyl acetate, (methyl) acrylamide and maleic anhydride.Particularly preferably be vinylbenzene, methyl methacrylate and vinyl imidazole.
Applicable alkene class unsaturated oligomer is selected from polyethers (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester, polyurethane(s) (methyl) acrylate, epoxy resin (methyl) acrylate, siloxanes (methyl) acrylate and the acrylic copolymer containing (methyl) acryl.Preferably polyethers (methyl) acrylate.Particularly preferably be polyoxyethylene glycol methacrylic acid monoester, its number-average molecular weight is 200～5000, preferably 350～750.
Of the present inventionly can be used for the polyreaction of vinyl compound containing pyrenyl radical initiator, its implementation method is identical during with employing routine commodity azo-initiator with processing condition.Implementation method can be mass polymerization, solution polymerization, suspension polymerization and letex polymerization, preferred solution polymerization; Consumption containing pyrenyl radical initiator is 0.1～1% of vinyl compound amount; Polymerization temperature is 50～120 DEG C, preferably 70～100 DEG C; Polymerization time is 5～72 hours, preferably 18～28 hours.
Of the present invention containing pyrenyl radical initiator can be used for synthetic based on vinyl compound containing pyrenyl polymer, wherein pyrenyl group is positioned at macromolecular chain end, average each macromolecular chain is containing 0.9～1.2 pyrenyl group.Synthetic method is, in above-mentioned solution polymerization process, even suppress to eliminate coupling termination with chain-transfer agent and/or rising polymerization temperature.
, mainly take to eliminate/suppress coupling termination with the measure of chain-transfer agent to the insensitive polyreaction of polymerization temperature for chain termination mode.Taking styrene monomer as example, its polyreaction is carried out under the condition of fixing polymerization temperature and use chain-transfer agent.Polymerization temperature can be any temperature within the scope of 70～100 DEG C; Chain-transfer agent can be the mixture of 1-lauryl mercaptan, 1-undecyl mercaptan, 1-tetradecyl mercaptan, 1-Stearyl mercaptan, 1-pentan-thiol, 1-hexylmercaptan, 1-heptanthiol, 1-spicy thioalcohol, 1-mercaptan in the ninth of the ten Heavenly Stems or above-mentioned two or more mercaptan, preferably 1-lauryl mercaptan, its consumption is 0.08～0.15% of styrene monomer amount; The average pyrene end group number of synthetic polystyrene is 0.94～1.15.In control sample, while not using chain-transfer agent, polymerization temperature to be 85 DEG C, the average pyrene end group number of synthetic polystyrene is 1.78.
Polyreaction for chain termination mode to polymerization temperature sensitivity, mainly takes the measure that improves polymerization temperature to eliminate/suppress coupling termination.Taking methyl methacrylate monomer as example, polymerization temperature is within the scope of 85～100 DEG C time, and the average pyrene end group number of synthetic polymethylmethacrylate is 1.05～1.20.In control sample, when polymerization temperature is 70 DEG C, the average pyrene end group number of synthetic polymethylmethacrylate is 1.62.
Can be used as dispersing auxiliary containing pyrenyl macromolecular compound (pyrenyl group is positioned at macromolecular chain end, and single macromolecular chain is on average containing 0.9～1.2 pyrenyl group) and prepare Graphene for the auxiliary liquid phase stripping method of dispersing auxiliary in the present invention.These can be dissolved in the conventional low boiling point organic solvents such as chloroform, tetrahydrofuran (THF), acetone, ethanol or water containing pyrenyl macromolecular compound, form uniform solution.It is suitable with the usefulness of (namely common liquid phase stripping method) in surface can be close to the high boiling point neat solvent of Graphene that the usefulness of Graphene peeled off, is dispersed into by natural graphite in gained solution, but significantly shortened the supersound process time, the stability of gained graphene dispersing solution is also better.To contain pyrenyl polystyrene (PyPS) as example, first appropriate PyPS is dissolved in 50ml chloroform, then by 150mg natural graphite (300 orders, purity >99%) after 1 hour, be scattered in wherein (concrete dispersion step is referring to embodiment 13) through supersound process, depending on the concentration difference (0.5～10mg.ml of PyPS solution
-1), finally record the content of Graphene in uniform dispersion between 82.4～630mg.L
-1between; Room temperature left standstill after 7 days, the 86-95% that the Graphene content in the stillness of night of upper strata is initial content.In the pure chloroform of control sample and pure N-Methyl pyrrolidone (a kind of high boiling solvent that is usually used in liquid phase stripping method), the dispersed amount of Graphene is respectively 5.2 and 89.6mg.L
-1; Extend the supersound process time to 100 hour, the dispersion amount of Graphene in pure N-Methyl pyrrolidone is 712mg.L
-1, room temperature left standstill after 7 days, and the Graphene content in the stillness of night of upper strata is initial content 88%.The remarkable lifting of preparing usefulness for explanation Graphene not only derives from polystyrene backbone structure or the pyrenyl group structure of PyPS, in two other control sample, be dissolved in respectively in 50ml chloroform and be mixed with 2mg.ml by polystyrene with containing pyrenyl micromolecular compound (as shown in general formula C1, wherein x=4)
-1solution, then each 150mg natural graphite is scattered in wherein according to identical operation, measured graphene uniform dispersion amount is respectively 10.2mg.L
-1and 56.4mg.L
-1.
Brief description of the drawings
Fig. 1 is the FTIR spectrogram containing pyrenyl radical initiator of synthesized in embodiment 3.
Fig. 2 be in embodiment 3 synthesized containing pyrenyl radical initiator
1h-NMR spectrogram.
Fig. 3 is the FTIR spectrogram containing pyrenyl polystyrene of synthesized in embodiment 10.
Fig. 4 be in embodiment 10 synthesized containing pyrenyl polystyrene
1h-NMR spectrogram.
Fig. 5 is atomic force microscope test (AFM) result of Graphene prepared in embodiment 13: left is AFM photo, and the right side is the height map of Graphene sample.
Fig. 6 is the transmission electron microscope photo of Graphene prepared in embodiment 13.
Embodiment
Listed embodiment is for being described more specifically the present invention below, but the present invention is also not only confined to this place row
Embodiment.
Embodiment 1
Get 1 150ml there-necked flask, by 40ml methylene dichloride, 50.1mg(0.18mmol) 4,4'-azo (4-cyanopentanoic acid) (as shown in Formula B 1), 92.9mg(0.40mmol) pyrene methyl alcohol is (as shown in general formula C1, wherein x=1), 8.6mg(0.07mmol) DMAP, 64.9mg(0.48mmol) HOBT successively adds wherein, under magnetic agitation, is mixed with uniform solution.Then,, under ice-water bath, nitrogen protection condition, slowly drip EDC.HCl/ dichloromethane solution (86.3mg(0.45mmol) EDC.HCl and be dissolved in 10ml methylene dichloride).Be added dropwise to complete after 30 minutes, remove ice-water bath, reaction system is warming up to 30 DEG C, reacts 24 hours.By reacting liquid filtering, filtrate is diluted to 100ml with methylene dichloride.This solution is through 3 1M HCl(3 × 50ml), 3 saturated NaHCO
3after solution (3 × 50ml), 3 distilled water (3 × 50ml) washing, organic phase MgSO
4dry 1 hour, filter, under room temperature, remove solvent under reduced pressure, obtain crude product.For further separation and purification, crude product is dissolved in 4ml dimethyl formamide, then add 20ml methyl alcohol to carry out recrystallization.In 20 DEG C of refrigerators of mixture Zhi Yu –, after 12 hours, solid collected by filtration thing.After another twice recrystallization operation, solid collection thing is dried to 24 hours in 40 DEG C of vacuum drying ovens again.Obtain light yellow solid compound, productive rate is greater than 90%,
Molecular structural formula is:
Embodiment 2
By substituting with pyrene butanols (as shown in general formula C1, wherein x=4) containing pyrenyl micromolecular compound pyrene methyl alcohol in embodiment 1, consumption is 104.3mg(0.38mmol); Methylene dichloride consumption is adjusted into 45ml, and DMAP consumption is adjusted into 19.5mg(0.16mmol), do not use HOBT, EDC.HCl consumption is adjusted into 80.5mg(0.42mmol), temperature of reaction is adjusted into 25 DEG C, and the reaction times is extended for 26 hours; Other operational condition is identical with embodiment 1.Obtain light yellow solid compound, productive rate is greater than 86%, and molecular structural formula is:
Embodiment 3
Get 1 150ml there-necked flask, by 70ml methylene dichloride, 50.3mg(0.18mmol) 4,4'-azo (4-cyanopentanoic acid), 97.1mg(0.42mmol) pyrene methylamine is (as shown in general formula C2, wherein x=1), 106.4mg(0.49mmol) Sulfo-NHS successively adds wherein, under magnetic agitation, is mixed with uniform solution.Then,, under ice-water bath, nitrogen protection condition, slowly drip EDC.HCl/ dichloromethane solution (89.7mg(0.47mmol) EDC.HCl and be dissolved in 10ml methylene dichloride).Be added dropwise to complete after 1 hour, remove ice-water bath, reaction system is warming up to 35 DEG C, reacts 18 hours.By reacting liquid filtering, filtrate is diluted to 100ml with methylene dichloride.This solution is through 3 1M HCl(3 × 50ml), 3 saturated NaHCO
3after solution (3 × 50ml), 3 distilled water (3 × 50ml) washing, organic phase MgSO
4dry 1 hour, filter, under room temperature, remove solvent under reduced pressure, obtain crude product.For further separation and purification, crude product is dissolved in 2ml, the dimethyl formamide of 40 DEG C, then add 10ml methyl alcohol to carry out recrystallization.In 20 DEG C of refrigerators of mixture Zhi Yu –, after 12 hours, solid collected by filtration thing.After another twice recrystallization operation, solid collection thing is dried to 24 hours in 40 DEG C of vacuum drying ovens again.Obtain light yellow solid compound, productive rate is greater than 84%, and molecular structural formula is:
Fig. 1 is the FTIR spectrogram containing pyrenyl radical initiator of synthesized in embodiment 3.3270 and 3063cm
-1, the N-H stretching vibration of secondary amide; 1650cm
-1, the C=O stretching vibration of secondary amide; 1560cm
-1, the C-N-H flexural vibration of secondary amide; 2240cm
-1, C ≡ N stretching vibration; 842cm
-1, the C-H flexural vibration on pyrene ring.
Fig. 2 be in embodiment 3 synthesized containing pyrenyl radical initiator
1h-NMR spectrogram.
Embodiment 4
By substituting with pyrene amine (as shown in general formula C2, wherein x=0) containing pyrenyl micromolecular compound pyrene methylamine in embodiment 3, consumption is 93.4mg(0.43mmol); Sulfo-NHS substitutes with NHS, and consumption is 57.5mg(0.50mmol); Methylene dichloride substitutes with trichloromethane, and consumption is adjusted into 60ml; EDC.HCl consumption is adjusted into 92.0mg(0.48mmol), temperature of reaction is adjusted into 25 DEG C, and the reaction times is extended for 28 hours; Other operational condition is identical with embodiment 3.Obtain light yellow solid compound, productive rate is greater than 87%, and molecular structural formula is:
Embodiment 5
By the conventional commercial initiators 4 in embodiment 1,2,2'-azo for 4'-azo (4-cyanopentanoic acid) (2-methyl-N-(2-hydroxyethyl) propionic acid amide) (as shown in Formula B 2) substitutes, and consumption is 49.8mg(0.17mmol); Substitute with pyrene formic acid (as shown in general formula C3, wherein x=0) containing pyrenyl micromolecular compound pyrene methyl alcohol, consumption is 101.0mg(0.41mmol); Methylene dichloride consumption is adjusted into 70ml, DMAP consumption is adjusted into 6.2mg(0.05mmol), HOBT consumption is adjusted into 58.1mg(0.43mmol), EDC.HCl consumption is adjusted into 74.8mg(0.39mmol), temperature of reaction is adjusted into 25 DEG C, and the reaction times extends to 28 hours; Other operational condition is identical with embodiment 1.Obtain light yellow solid compound, productive rate is greater than 85%, and molecular structural formula is:
Embodiment 6
By substituting with pyrene butyric acid (as shown in general formula C3, wherein x=3) containing pyrenyl micromolecular compound pyrene formic acid in embodiment 5, consumption is 106.7mg(0.37mmol); Methylene dichloride substitutes with trichloromethane, and consumption is 75ml; DMAP consumption is adjusted into 25.7mg(0.21mmol), do not use HOBT, EDC.HCl consumption is adjusted into 76.7mg(0.40mmol), temperature of reaction is adjusted into 30 DEG C, and the reaction times is 24 hours; Other operational condition is identical with embodiment 5.Obtain light yellow solid compound, productive rate is greater than 88%, and molecular structural formula is:
Embodiment 7
By the conventional commercial initiators 4 in embodiment 1,4'-azo (4-cyanopentanoic acid) substitutes with 4,4'-azo two (4-cyano group amylalcohol) (as shown in Formula B 3), and consumption is 50.4mg(0.20mmol); Substitute with pyrene butyric acid (as shown in general formula C3, wherein x=3) containing pyrenyl micromolecular compound pyrene methyl alcohol, consumption is 144.2mg(0.5mmol); Methylene dichloride consumption is adjusted into 90ml, and DMAP consumption is adjusted into 12.4mg(0.1mmol), HOBT consumption is adjusted into 78.3mg(0.58mmol), EDC.HCl consumption is adjusted into 99.7mg(0.52mmol); Other operational condition is identical with embodiment 1.Obtain light yellow solid compound, productive rate is greater than 93%, and molecular structural formula is:
Embodiment 8
By substituting with pyrene formic acid (as shown in general formula C3, wherein x=0) containing pyrenyl micromolecular compound pyrene butyric acid in embodiment 7, consumption is 110.8mg(0.45mmol); Methylene dichloride consumption is adjusted into 75ml, and DMAP consumption is adjusted into 30.6mg(0.25mmol), do not use HOBT, EDC.HCl consumption is adjusted into 95.9mg(0.50mmol); Other operational condition is identical with embodiment 7.Obtain light yellow solid compound, productive rate is greater than 89%, and molecular structural formula is:
Embodiment 9
Thermal initiator containing pyrenyl radical initiator as vinyl compound polyreaction.This vinyl compound is methyl methacrylate monomer.Synthetic method is as follows:
Get 1 50ml single port flask, by 150mg(0.21mmol) successively adding wherein containing pyrenyl radical initiator, 10ml dimethyl formamide of being synthesized by embodiment 1, under magnetic agitation, be mixed with uniform solution.Then,, under room temperature and condition of nitrogen gas, add 10ml(94.3mmol) methyl methacrylate monomer.Reaction system is warming up to 95 DEG C, polyreaction 18 hours.After polymerization finishes, deposit polymerisate with 100ml methyl alcohol.After filtration, solids is put into 80 DEG C of vacuum drying ovens and is dried to constant weight, finally must contain pyrenyl polymethylmethacrylate.Number-average molecular weight is 15,600, and molecular weight distributing index is 2.16, and the average pyrene end group number of macromolecular chain is 1.08.
Embodiment 10
Thermal initiator containing pyrenyl radical initiator as vinyl compound polyreaction.This vinyl compound is styrene monomer.Synthetic method is as follows:
Get 1 50ml single port flask, by 210mg(0.30mmol) successively adding wherein containing pyrenyl radical initiator, 15ml dimethyl formamide of being synthesized by embodiment 3, under magnetic agitation, be mixed with uniform solution.Then,, under room temperature and condition of nitrogen gas, add 10ml(87.3mmol) styrene monomer and 18.2mg(0.09mmol) 1-lauryl mercaptan.Reaction system is warming up to 85 DEG C, polyreaction 24 hours.After polymerization finishes, deposit polymerisate with 120ml methyl alcohol.After filtration, solids is put into 60 DEG C of vacuum drying ovens and is dried to constant weight, finally must contain pyrenyl polystyrene.Number-average molecular weight is 18,300, and molecular weight distributing index is 3.20, and the average pyrene end group number of macromolecular chain is 1.04.
Fig. 3 is the FTIR spectrogram containing pyrenyl polystyrene of synthesized in embodiment 10.3064 and 3025cm
-1, the C-H stretching vibration on phenyl ring; 1675cm
-1, the C=O stretching vibration of secondary amide; 1602,1540,1495,1451cm
-1, the stretching vibration of phenyl ring; 839cm
-1, the C-H flexural vibration on pyrene ring.
Fig. 4 be in embodiment 10 synthesized containing pyrenyl polystyrene
1h-NMR spectrogram.
Embodiment 11
Thermal initiator containing pyrenyl radical initiator as vinyl compound polyreaction.This vinyl compound is N-vinyl imidazole monomer.Synthetic method is as follows:
Get 1 50ml single port flask, by 410mg(0.55mmol) successively adding wherein containing pyrenyl radical initiator, 20ml dimethyl formamide of being synthesized by embodiment 5, under magnetic agitation, be mixed with uniform solution.Then,, under room temperature and condition of nitrogen gas, add 10ml(110.3mmol) N-vinyl imidazole monomer and 22.3mg(0.11mmol) 1-lauryl mercaptan.Reaction system is warming up to 75 DEG C, polyreaction 20 hours.After polymerization finishes, deposit polymerisate by 150ml ethyl acetate.After filtration, solids is put into 80 DEG C of vacuum drying ovens and is dried to constant weight, finally must contain pyrenyl polyvinyl imidazol.Number-average molecular weight is 8,800, and molecular weight distributing index is 2.25, and the average pyrene end group number of macromolecular chain is 1.18.
Embodiment 12
Thermal initiator containing pyrenyl radical initiator as vinyl compound polyreaction.This vinyl compound is alkene class unsaturated oligomer-polyoxyethylene glycol methacrylic acid monoester, and number-average molecular weight is 500.Synthetic method is as follows:
Get 1 50ml single port flask, by 72.1mg(0.09mmol) synthesized by embodiment 7 containing pyrenyl radical initiator, the about 10mmol of 5g() polyoxyethylene glycol methacrylic acid monoester, 2.1mg(0.01mmol) 1-lauryl mercaptan, 20ml dimethyl formamide successively add wherein, under magnetic agitation, is mixed with uniform solution.Then, under room temperature and condition of nitrogen gas, reaction system is warming up to 80 DEG C, polyreaction 28 hours.After polymerization finishes, deposit polymerisate with 150ml ether.After filtration, solids is put into 60 DEG C of vacuum drying ovens and is dried to constant weight, finally must contain pyrenyl macromolecular compound.Number-average molecular weight is 40,210, and molecular weight distributing index is 2.62, and the average pyrene end group number of macromolecular chain is 1.21.
Embodiment 13
Get the test tube of 5 100ml, add respectively 50ml chloroform, then add successively in embodiment 10 synthetic containing pyrenyl polystyrene 25,50,100,250,500mg.After dissolving completely containing pyrenyl polystyrene, add respectively 150mg natural graphite (300 orders, purity >99%), test tube mouth is placed in 0～30 DEG C of water-bath to supersound process 1 hour with polyethylene film sealing, ultrasonic power is 80W, and ultrasonic frequency is 60KHz.Gained dispersion liquid leaves standstill 1 hour, and 3/4ths supernatant liquids are taken out with dropper, after 1.5 hours, carefully collects the upper strata stillness of night via centrifugation (500 revs/min), obtains the light grey graphene uniform dispersion to black.The spectroscopic techniques (Nature Nanotechnology, 2008,3,563-568) that utilizes the people such as Coleman to set up, records in dispersion liquid that the content of Graphene is respectively 82.4,173.2,498.5,601.0,630.0mg.L
-1.Room temperature left standstill after 7 days, in supernatant liquid the content of Graphene be respectively 72.5,149.1,473.5,560.7,567.8mg.L
-1, be about 88%, 86%, 95%, 93%, 90% of Graphene initial content.
Atomic force microscopy and the transmission electron microscope photo of the prepared Graphene of the present embodiment are shown in respectively Fig. 5 and Fig. 6.
Reference examples 1
Except polymeric reaction temperature being reduced to 70 DEG C, other operational condition is identical with embodiment 9.Gained is 16,780 containing the number-average molecular weight of pyrenyl polymethylmethacrylate, and molecular weight distributing index is 3.77, and the average pyrene end group number of macromolecular chain is 1.62.
Reference examples 2
Except not using chain-transfer agent 1-lauryl mercaptan, other operational condition is identical with embodiment 10.Gained is 23,100 containing the number-average molecular weight of pyrenyl polystyrene, and molecular weight distributing index is 2.24, and the average pyrene end group number of macromolecular chain is 1.78.
Reference examples 3
Get the test tube of 3 100ml, be labeled as A – C, add successively 50ml chloroform, 50ml N-Methyl pyrrolidone, 50ml N-Methyl pyrrolidone, then add respectively 150mg natural graphite (300 orders, purity >99%).For the sample in A, B test tube, adopt the dispersion step identical with embodiment 13, in gained dispersion liquid the content of Graphene be respectively 5.2,89.6mg.L
-1.For the sample in C test tube, except extending supersound process time to 100 hour, other dispersion step is identical with embodiment 13, and in gained dispersion liquid, the content of Graphene is 712mg.L-1; Room temperature left standstill after 7 days, and in supernatant liquid, the content of Graphene is 627mg.L
-1, be about 88% of Graphene initial content.
Reference examples 4
Get the test tube of 2 100ml, add respectively 50ml chloroform, then (number-average molecular weight is 20 to add successively polystyrene, 130, molecular weight distributing index is 2.67, taking Diisopropyl azodicarboxylate as initiator, polymeric reaction condition is identical with reference examples 2) and the each 100mg of pyrene butanols (as shown in general formula C1, wherein x=4).After polystyrene and pyrene butanols dissolve completely, in 2 test tubes, add respectively 150mg natural graphite (300 orders, purity >99%), dispersion step is identical with embodiment 13.Record in uniform dispersion the content of Graphene and be respectively 10.2 and 56.4mg.L
-1.
Claims (8)
1. containing a pyrenyl radical initiator, it is characterized in that it is represented by following general formula (A)
R in general formula
1for
one of, wherein a=0～4, b=0～1, c=0～3, d=0～3; In its chemical structure, be a kind of symmetric form containing pyrenyl azo compound, after thermolysis, can produce two molecular structures identical containing the elementary free radical of pyrenyl.
2. the synthetic method containing pyrenyl radical initiator claimed in claim 1, it is characterized in that adopting esterification to synthesize, under reaction promoter exists, conventional commercial initiators with in organic solvent, carry out chemical reaction containing pyrenyl micromolecular compound, temperature of reaction is 10～60 DEG C, reaction times is 6～72 hours, and reaction atmosphere is air, nitrogen or argon gas; Synthesize in same reactor and once complete, without intermediate product is carried out to extra separation, purification; The compound of above-mentioned conventional commercial initiators for adopting general formula (B) to represent
R
2-N=N-R
2 （B）
Wherein R
2for
compound containing pyrenyl micromolecular compound for adopting general formula (C) to represent
Wherein R
3for-corresponding x=0～4 of OH() or
(corresponding x=0～3), consumption is the conventional commercial initiators of the every 1mol of 2.2～2.5mol; Reaction promoter is " EDC.HCl+DMAP; consumption mol ratio: EDC.HCl:DMAP: conventional commercial initiators=2.3～2.6:0.3～0.5:1 " or " EDC.HCl+DMAP+HOBT, consumption mol ratio: EDC.HCl:DMAP:HOBT: conventional commercial initiators=2.3～2.6:0.3～0.5:2.5～2.9:1 "; The organic solvent of reaction is the mixture of one or two or more solvent in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dimethyl formamide, and consumption is the conventional commercial initiators of the every 1mg of 0.3～1.5ml.
3. the synthetic method containing pyrenyl radical initiator claimed in claim 1, it is characterized in that adopting amidate action to synthesize, under reaction promoter exists, conventional commercial initiators with in organic solvent, carry out chemical reaction containing pyrenyl micromolecular compound, temperature of reaction is 10～60 DEG C, reaction times is 6～72 hours, and reaction atmosphere is air, nitrogen or argon gas; Synthesize in same reactor and once complete, without intermediate product is carried out to extra separation, purification; The compound of above-mentioned conventional commercial initiators for adopting general formula (B) to represent
R
2-N=N-R
2 （B）
Wherein R
2for
compound containing pyrenyl micromolecular compound for adopting general formula (C) to represent
Wherein R
3for-NH
2(corresponding x=0～1), consumption is the conventional commercial initiators of the every 1mol of 2.2～2.5mol; The reaction promoter of amidate action is " EDC.HCl+NHS; consumption mol ratio is EDC.HCl:NHS: conventional commercial initiators=2.3～2.6:2.5～2.9:2.5～2.9:1 " or " EDC.HCl+Sulfo-NHS ", and consumption mol ratio is EDC.HCl:Sulfo-NHS: conventional commercial initiators=2.3～2.6:2.5～2.9:1 "; The organic solvent of reaction is the mixture of one or two or more solvent in methylene dichloride, trichloromethane, tetrahydrofuran (THF), dimethyl formamide, and consumption is the conventional commercial initiators of the every 1mg of 0.3～1.5ml.
4. according to the synthetic method containing pyrenyl radical initiator described in claim 2 or 3, it is characterized in that organic solvent adopts methylene dichloride or trichloromethane, temperature of reaction is 25～35 DEG C, and the reaction times is 18～28 hours, and reaction atmosphere is nitrogen.
5. the purposes containing pyrenyl radical initiator according to claim 1, is characterized in that the thermal initiator as vinyl compound polyreaction, to synthesize containing pyrenyl macromolecular compound; Vinyl compound is to adopt conventional commodity azo-initiator to carry out the unsaturated compound of polymerization, and this ethylenically unsaturated compounds can be monomer, oligopolymer or their mixture; Polyreaction implementation method is mass polymerization, solution polymerization, suspension polymerization or letex polymerization; Consumption containing pyrenyl radical initiator is 0.1～1% of vinyl compound amount; Polymerization temperature is 50～120 DEG C, and polymerization time is 5～72 hours.
6. the purposes containing pyrenyl radical initiator according to claim 5, it is characterized in that said vinyl compound is one of vinylbenzene, methyl methacrylate, N-vinyl imidazole or polyoxyethylene glycol methacrylic acid monoester, the polyreaction of vinyl compound adopts solution polymerization process, solvent is dimethyl formamide, pimelinketone or N,N-DIMETHYLACETAMIDE, polymerization temperature is 70～100 DEG C, and polymerization time is 18～28 hours.
7. the purposes containing pyrenyl radical initiator according to claim 5, is characterized in that saidly having pyrenyl group containing pyrenyl macromolecular compound and being positioned at macromolecular chain end, single macromolecular chain on average containing 0.9～1.2 pyrenyl group.
8. the purposes containing pyrenyl macromolecular compound synthetic according to claim 5, can be used as dispersing auxiliary containing pyrenyl macromolecular compound and prepare Graphene for the auxiliary liquid phase stripping method of dispersing auxiliary, the raw material of Graphene is natural graphite, and solvent is low boiling point organic solvent or the water such as chloroform, tetrahydrofuran (THF), acetone, ethanol.
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Cited By (6)
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| CN104292376A (en) * | 2014-10-11 | 2015-01-21 | 浙江工业大学 | Pyrenyl hyperbranched polyethylene and application thereof in preparing graphene |
| CN106009466A (en) * | 2016-08-01 | 2016-10-12 | 湖南大学 | Modified nano carbon material, carbon material/polymer composite material and preparation method thereof |
| CN107987195A (en) * | 2017-12-07 | 2018-05-04 | 中国科学院长春应用化学研究所 | Single metallocene-titanium metal compound, olefin polymerization catalysis |
| CN108946715A (en) * | 2018-09-28 | 2018-12-07 | 嘉兴烯成新材料有限公司 | Water soluble starter prepares graphene oxide method |
| CN111647113A (en) * | 2019-10-15 | 2020-09-11 | 浙江工业大学 | Pyrenyl terpolymer and intermediate, preparation and application thereof |
| CN112500727A (en) * | 2020-11-20 | 2021-03-16 | 厦门大学 | Weather-resistant paint containing graphene-based composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104292376A (en) * | 2014-10-11 | 2015-01-21 | 浙江工业大学 | Pyrenyl hyperbranched polyethylene and application thereof in preparing graphene |
| CN106009466A (en) * | 2016-08-01 | 2016-10-12 | 湖南大学 | Modified nano carbon material, carbon material/polymer composite material and preparation method thereof |
| CN107987195A (en) * | 2017-12-07 | 2018-05-04 | 中国科学院长春应用化学研究所 | Single metallocene-titanium metal compound, olefin polymerization catalysis |
| CN107987195B (en) * | 2017-12-07 | 2020-05-19 | 中国科学院长春应用化学研究所 | Half-metallocene titanium metal compound and olefin polymerization catalyst |
| CN108946715A (en) * | 2018-09-28 | 2018-12-07 | 嘉兴烯成新材料有限公司 | Water soluble starter prepares graphene oxide method |
| CN111647113A (en) * | 2019-10-15 | 2020-09-11 | 浙江工业大学 | Pyrenyl terpolymer and intermediate, preparation and application thereof |
| CN111647113B (en) * | 2019-10-15 | 2022-09-13 | 浙江工业大学 | Pyrenyl terpolymer and intermediate, preparation and application thereof |
| CN112500727A (en) * | 2020-11-20 | 2021-03-16 | 厦门大学 | Weather-resistant paint containing graphene-based composite material and preparation method thereof |
| CN112500727B (en) * | 2020-11-20 | 2021-09-17 | 厦门大学 | Weather-resistant paint containing graphene-based composite material and preparation method thereof |
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