CN109553568A - It is conjugated alkynyl anthracene derivant and its method as visible light photosensitizer regulation atom transfer radical polymerization - Google Patents
It is conjugated alkynyl anthracene derivant and its method as visible light photosensitizer regulation atom transfer radical polymerization Download PDFInfo
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- CN109553568A CN109553568A CN201811386343.0A CN201811386343A CN109553568A CN 109553568 A CN109553568 A CN 109553568A CN 201811386343 A CN201811386343 A CN 201811386343A CN 109553568 A CN109553568 A CN 109553568A
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- alkynyl
- visible light
- conjugation
- free radical
- anthracene derivant
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- -1 alkynyl anthracene Chemical compound 0.000 title claims abstract description 51
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 241001597008 Nomeidae Species 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000033228 biological regulation Effects 0.000 title claims abstract description 18
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 15
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 230000007704 transition Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 230000021615 conjugation Effects 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical group CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- IQZBMUCMEBSKSS-UHFFFAOYSA-N 10-ethylphenothiazine Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3SC2=C1 IQZBMUCMEBSKSS-UHFFFAOYSA-N 0.000 claims description 2
- VRJVOTTZESKWPD-UHFFFAOYSA-N 10-hexylphenothiazine Chemical compound C1=CC=C2N(CCCCCC)C3=CC=CC=C3SC2=C1 VRJVOTTZESKWPD-UHFFFAOYSA-N 0.000 claims description 2
- YCWUVACOIYLEMX-UHFFFAOYSA-N 9-dodecylcarbazole Chemical group C1=CC=C2N(CCCCCCCCCCCC)C3=CC=CC=C3C2=C1 YCWUVACOIYLEMX-UHFFFAOYSA-N 0.000 claims description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical group C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 claims description 2
- SHUQFBKCOHURJQ-UHFFFAOYSA-N 9-hexylcarbazole Chemical group C1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 SHUQFBKCOHURJQ-UHFFFAOYSA-N 0.000 claims description 2
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical group C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical group C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- 239000003863 metallic catalyst Substances 0.000 abstract description 7
- 238000012682 free radical photopolymerization Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003760 hair shine Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 11
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- YXMGPEPVSMCYTR-UHFFFAOYSA-N 10-dodecyl-3-ethynylphenothiazine Chemical compound C(CCCCCCCCCCC)N1C2=CC=CC=C2SC=2C=C(C=CC1=2)C#C YXMGPEPVSMCYTR-UHFFFAOYSA-N 0.000 description 2
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 2
- SKLVKQDGDJQKBK-UHFFFAOYSA-N 9-dodecyl-3-ethynylcarbazole Chemical compound CCCCCCCCCCCCn1c2ccccc2c2cc(ccc12)C#C SKLVKQDGDJQKBK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 230000003828 downregulation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930000755 gossypol Natural products 0.000 description 1
- 229950005277 gossypol Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method for being conjugated alkynyl anthracene derivant as visible light photosensitizer regulation atom transfer radical polymerization, it is related to Polymer Synthesizing field, metallic catalyst is needed to participate in based on atom transferred free radical photopolymerization, the problem of atom transferred free radical photopolymerization can not be regulated and controled under visible light and propose, the present invention will be the following steps are included: alkynyl anthracene derivative will be conjugated, acrylic ester monomer, the polymerization system of initiator and solvent composition, room temperature carries out atom transition free radical polymerization reaction under the conditions of visible light shines, to generate corresponding polymer, the beneficial effects of the present invention are: realize application of the anthracene derivant in the atom transferred free radical photopolymerization of visible optical drive, it is participated in without metallic catalyst, therefore the polymer obtained is without many and diverse purification process.
Description
Technical field
The present invention relates to Polymer Synthesizing fields, and in particular to a kind of conjugation alkynyl anthracene derivant and its as visible light light
The method of quick dose of regulation atom transfer radical polymerization.
Background technique
Atom transfer radical polymerization provides a kind of realize by free radical polymerization mode and controls molecular weight and molecular weight
Distribution method.The disadvantages of this method is the polymerization that polymerization process needs the participation of transition-metal catalyst, therefore obtains
Object has metallic catalyst residual.This not only affects atom transfer radical polymerization answering in terms of biological medicine, microelectronics
With, while being also a kind of waste of resource.A variety of methods are developed to reduce the load capacity of transition-metal catalyst, and there are also some
Method reports the recycling of metallic catalyst.
From 2014, there are two seminar (Macromolecules, 2014,47 (23): 8255-8261, Journal of
The American Chemical Society 2014,136 (45), 16096-16101) it reports with small molecule organic compound
As a result atom transfer radical polymerization of the object as sensitizer proves that this kind of compound can replace traditional metallic catalyst,
It is atom transfer radical polymerization to fundamentally solve the problems, such as metal ion pollution in atom transfer radical polymerization
Industrialization is laid a good foundation.However, reported this kind of compound absorbing wavelength is shorter, it polymerize light source used and remains as ultraviolet light
Source.It is well known that ultraviolet radiation is harmful to the human body, environmental safety is poor.Therefore develop it is novel, can be in visible light wave
The organic compound of long down regulation atom transfer radical polymerization is increasingly becoming current research hotspot.
Anthracene has good photoelectric property, and Yagci seminar reports the atom transfer using anthracene as sensitizer within 2016
Radical photopolymerization, obtained molecular weight distribution and the controllable polymer of molecular weight (Macromolecules 2016,49 (20),
7785-7792).But the absorbing wavelength of anthracene concentrates on ultraviolet region, can not regulate and control atom transferred free radical under visible light
Photopolymerization.
Summary of the invention
The problem to be solved by the present invention is that atom transferred free radical photopolymerization needs metallic catalyst to participate in, Wu Fa
Visible light down regulation atom transferred free radical photopolymerization.
The present invention adopts the following technical solutions solves above-mentioned technical problem:
It is derivative that the present invention provides a kind of conjugation alkynyl anthracene as visible light photosensitizer regulation atom transfer radical polymerization
The general structure of object, the conjugation alkynyl anthracene derivant is as follows:
Wherein, R be phenyl, triphenylamine, N- dodecyl carbazole, N- hexyl carbazole, N- ethyl carbazole, N- phenyl carbazole,
One of N- dodecyl phenthazine, N- hexyl phenothiazine, N- ethyl-phenothiazine, N- phenyl phenthazine.
The present invention provides a kind of conjugation alkynyl anthracene derivant as visible light photosensitizer and regulates and controls atom transfer radical polymerization
Method, comprising the following steps: the poly- of alkynyl anthracene derivative, acrylic ester monomer, initiator and solvent composition will be conjugated
Zoarium system, room temperature carries out atom transition free radical polymerization reaction under visible light illumination condition, to generate corresponding polymer.
Preferably, the initiator is alpha-brominated ethyl phenylacetate.
Preferably, the acrylic ester monomer is methyl methacrylate.
Preferably, the light source range of the visible light is 400-800nm.
Preferably, the acrylic ester monomer, initiator, be conjugated alkynyl anthracene derivative molar ratio be (50-
1000):(10-100):(1-10)。
Preferably, the solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, toluene, tetrahydrofuran, dichloro
One of methane.
Preferably, the volume ratio of the acrylic ester monomer and solvent is (1-5): (1-20).
Preferably, after the conjugation alkynyl anthracene derivative, acrylic ester monomer, initiator and solvent being mixed, in
It thaws after being vacuumized under freezing conditions.
Preferably, the mixture after defrosting is stirred under visible light illumination condition.
The beneficial effects of the present invention are:
(1) ultravioletvisible absorption wave-length coverage and the absorbing ability that alkynyl anthracene derivant is conjugated in the present invention are equal compared with anthracene
It significantly improves, realizes application of the anthracene derivant in the atom transferred free radical photopolymerization of visible optical drive；
(2) atom transfer radical polymerization of conjugation alkynyl anthracene derivative regulation is joined without metallic catalyst in the present invention
With, therefore obtained polymer is not necessarily to many and diverse purification process, simplifies preparation step.
Detailed description of the invention
Fig. 1 is to be conjugated alkynyl derivatives AND1's in the embodiment of the present invention 11H NMR figure；
Fig. 2 is the structural formula that alkynyl derivatives AND1 is conjugated in the embodiment of the present invention 1；
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure for being conjugated alkynyl derivatives AND1 and AND2；
Fig. 4 is to be conjugated alkynyl derivatives AND2's in the embodiment of the present invention 21H NMR figure；
Fig. 5 is the structural formula that alkynyl derivatives AND2 is conjugated in the embodiment of the present invention 2；
Fig. 6 is the GPC elution curve for being conjugated the polymethyl methacrylate that alkynyl derivatives AND1 and AND2 regulation obtain.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and embodiment.
Test material and reagent as used in the following examples etc., unless otherwise specified, commercially obtain.
In the present invention, disclosed polymer molecular weight and molecular weight distribution are obtained by gel permeation chromatograph measurement
's.
Embodiment 1
It is conjugated the synthesis of alkynyl anthracene derivant AND1, comprising the following steps:
Its reaction equation is as follows:
(1) it weighs 9,10- dibromoanthracene (1.01g, 3mmol), cuprous iodide (28.5mg, 0.15mmol), triphenylphosphine
(39.3mg, 0.15mmol), two (triphenylphosphine) palladium chlorides (21.1mg, 0.01mmol), is added to equipped with magneton and temperature
In the 100mL three-necked flask of meter, 20ml n,N-Dimethylformamide (DMF) is added and 15mL triethylamine (TEA) is allowed to dissolve；
(2) N- dodecyl -3- acetenyl carbazole (1.43g, 7.5mmol) is weighed, is transferred to after being dissolved with 10mL DMF
In constant pressure funnel.Vacuum nitrogen gas is to slowly warm up to 80 DEG C afterwards three times under electromagnetic agitation, after persistently stirring half an hour
Start the DMF solution for the N- dodecyl -3- acetenyl carbazole being added dropwise, TCL stops heating, reaction after monitoring raw material fully reacting
Liquid, which is down to room temperature, solid precipitation, filtering drying, and crude product obtains reddish-orange crystals (1.04g, the conversion of product with Gossypol recrystallized from chloroform
Rate is 62%), to be as conjugated alkynyl anthracene derivant, be named as AND1；
It is conjugated alkynyl anthracene derivant AND1's1H NMR schemes as shown in Figure 1, its hydrogen modal data are as follows:1H NMR(400MHz,
CDCl3) δ 8.90-8.79 (m, 4H), 8.55 (d, J=1.1Hz, 2H), 8.22 (d, J=7.7Hz, 2H), 7.91 (dd, J=
8.4,1.5Hz, 2H), 7.76-7.65 (m, 4H), 7.52 (ddd, J=26.2,12.1,4.4Hz, 6H), 7.33 (t, J=
7.3Hz, 2H), 4.36 (t, J=7.2Hz, 4H), 1.99-1.87 (m, 4H), 1.44-1.25 (m, 36H), 0.90 (t, J=
6.8Hz,6H)；
Product be conjugated alkynyl derivatives AND1 structural formula as shown in Fig. 2, its ultraviolet-visible absorption spectroscopy as shown in figure 3,
It can be seen that the ultravioletvisible absorption wave-length coverage and absorbing ability of conjugation alkynyl anthracene derivant AND1 significantly mention compared with anthracene
It is high.
Embodiment 2
It is conjugated the synthesis of alkynyl anthracene derivant AND2, comprising the following steps:
Its reaction equation is as follows:
(1) it weighs 9,10- dibromoanthracene (1.01g, 3mmol), cuprous iodide (28.5mg, 0.15mmol), triphenylphosphine
(39.3mg, 0.15mmol), two (triphenylphosphine) palladium chlorides (21.1mg, 0.01mmol), is added to equipped with magneton and temperature
In the 100mL three-necked flask of meter, 20mL n,N-Dimethylformamide (DMF) is added and 15mL triethylamine (TEA) is allowed to dissolve；
(2) N- dodecyl -3- acetenyl phenothiazine (2.94g, 7.5mmol) is weighed, is shifted after being dissolved with 10mL DMF
Into constant pressure funnel.Vacuum nitrogen gas is to slowly warm up to 80 DEG C afterwards three times under electromagnetic agitation, persistently stirs half an hour
Start the DMF solution that N- dodecyl -3- acetenyl phenothiazine is added dropwise afterwards；TCL stops heating after monitoring raw material fully reacting, instead
Answering liquid to be down to room temperature has solid precipitation, filtering drying.Crude product with TCM:EA (1:3) recrystallize orange red powder (1.45g,
The conversion ratio of product is 68%), to be as conjugated alkynyl anthracene derivant, be named as AND2；
It is conjugated alkynyl anthracene derivant AND2's1H NMR schemes as shown in figure 4, its hydrogen modal data are as follows:1H NMR(400MHz,
CDCl3) δ 8.61 (dd, J=6.6,3.3Hz, 4H), 7.59 (dd, J=6.7,3.2Hz, 4H), 7.49 (dd, J=8.9,
5.0Hz, 4H), 7.17-7.10 (m, 4H), 6.92 (t, J=7.4Hz, 2H), 6.85 (dd, J=8.2,2.8Hz, 4H), 3.84
(t, J=5.7Hz, 4H), 1.86-1.74 (m, 4H), 1.43 (dd, J=14.2,7.2Hz, 4H), 1.30-1.19 (m, 32H),
0.85 (t, J=6.8Hz, 6H), product are conjugated the structural formula of alkynyl derivatives AND2 as shown in figure 5, its ultravioletvisible absorption light
Spectrum is as shown in Figure 3, it can be seen that the ultravioletvisible absorption wave-length coverage and absorbing ability and anthracene of conjugation alkynyl anthracene derivant AND2
Compared to being significantly increased.
Embodiment 3
The atom transferred free radical that alkynyl anthracene derivant AND1 regulation methacrylate is conjugated in Application Example 1 is poly-
It closes, comprising the following steps:
(1) 20mg AND1, the alpha-brominated ethyl phenylacetate of 100 μ L, 5mL are added in Shrek bottle of the 50mL equipped with magneton
Methyl methacrylate, 5mL tetrahydrofuran (THF), vacuum nitrogen gas after liquid nitrogen frozen, in triplicate；
(2) it is placed on 7W domestic energy-saving lamp wait thaw (Ou Pu illumination/12-LE-47166/7W, light source range is in 400-
Between 800nm) under stir, reaction system is slowly added in 200mL methanol by lasting stirring afterwards for 24 hours, and poly- methyl-prop is obtained by filtration
E pioic acid methyl ester；
Test: gained polymethyl methacrylate is redissolved in tetrahydrofuran, is added in 200mL methanol and is precipitated analysis
Out；It repeats the above steps three times, filters to obtain polymethyl methacrylate, be dried under vacuum to after constant weight to gel permeation chromatography
(GPC) it tests.
Test result: using gravimetric method to survey its conversion ratio as gained polymethyl methacrylate molecular weight is 57.2%, is used
It is M that gel permeation chromatography, which analyzes its molecular weight,n=12955g/mol, dispersion polymerization PDI=1.22, gained polymethyl
Sour methyl esters GPC elution curve is as shown in Figure 6.
Embodiment 4
The atom transferred free radical that alkynyl anthracene derivant AND2 regulation methacrylate is conjugated in Application Example 2 is poly-
It closes, comprising the following steps:
(1) 20mg AND2, the alpha-brominated ethyl phenylacetate of 100 μ L, 5mL are added in Shrek bottle of the 50mL equipped with magneton
Methyl methacrylate, 5mL THF.Vacuum nitrogen gas after liquid nitrogen frozen, repeats the above steps three times；
(2) it is stirred wait thaw to be placed under 7W domestic energy-saving lamp, reaction system is slowly added to by lasting stirring afterwards for 24 hours
In 200mL methanol, polymethyl methacrylate is obtained by filtration.
Test: gained polymethyl methacrylate is redissolved in tetrahydrofuran, is added in 200mL methanol and is precipitated analysis
Out；It repeats the above steps three times, filters to obtain polymethyl methacrylate, be dried under vacuum to after constant weight to gel permeation chromatography
(GPC) it tests.
Test result: using gravimetric method to survey its conversion ratio as gained polymethyl methacrylate molecular weight is 40.3%, is used
It is M that gel permeation chromatography, which analyzes its molecular weight,n=12109g/mol, dispersion polymerization PDI=1.27, gained polymethyl
Sour methyl esters GPC elution curve is as shown in Figure 6.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
It is within the scope of the invention with present inventive concept without the various process programs of substantial differences.
Claims (10)
1. a kind of conjugation alkynyl anthracene derivant as visible light photosensitizer regulation atom transfer radical polymerization, feature exist
In: the general structure of the conjugation alkynyl anthracene derivant is as follows:
Wherein, R is phenyl, triphenylamine, N- dodecyl carbazole, N- hexyl carbazole, N- ethyl carbazole, N- phenyl carbazole, N- ten
One of dialkyl group phenthazine, N- hexyl phenothiazine, N- ethyl-phenothiazine, N- phenyl phenthazine.
2. poly- as visible light photosensitizer regulation atom transferred free radical using conjugation alkynyl anthracene derivant described in claim 1
The method of conjunction, it is characterised in that: the following steps are included: will conjugation alkynyl anthracene derivative, acrylic ester monomer, initiator and
The polymerization system of solvent composition, room temperature carries out atom transition free radical polymerization reaction under visible light illumination condition, to generate
Corresponding polymer.
3. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: the initiator is alpha-brominated ethyl phenylacetate.
4. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: the acrylic ester monomer is methyl methacrylate.
5. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: the light source range of the visible light is 400-800nm.
6. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: the acrylic ester monomer, initiator, be conjugated alkynyl anthracene derivative molar ratio be
(50-1000):(10-100):(1-10)。
7. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: the solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, toluene, tetrahydro furan
It mutters, one of methylene chloride.
8. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: the volume ratio of the acrylic ester monomer and solvent is (1-5): (1-20).
9. conjugation alkynyl anthracene derivant according to claim 2 is poly- as visible light photosensitizer regulation atom transferred free radical
The method of conjunction, it is characterised in that: mix the conjugation alkynyl anthracene derivative, acrylic ester monomer, initiator and solvent
Afterwards, it thaws after being vacuumized under freezing conditions.
10. conjugation alkynyl anthracene derivant according to claim 9 regulates and controls atom transferred free radical as visible light photosensitizer
The method of polymerization, it is characterised in that: be stirred the mixture after defrosting under the conditions of visible light photograph.
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