CN109553568B - Conjugated alkynyl anthracene derivative and method for regulating atom transfer radical polymerization by using same as visible light photosensitizer - Google Patents
Conjugated alkynyl anthracene derivative and method for regulating atom transfer radical polymerization by using same as visible light photosensitizer Download PDFInfo
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- -1 alkynyl anthracene derivative Chemical class 0.000 title claims abstract description 41
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 22
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical group CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010257 thawing Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 150000001454 anthracenes Chemical class 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 10
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000000304 alkynyl group Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 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
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 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
- 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
- 238000005481 NMR spectroscopy Methods 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
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 238000001595 flow curve Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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 1
- LLLJAYXRHGSUEZ-UHFFFAOYSA-N 10-dodecylphenothiazine Chemical compound C1=CC=C2N(CCCCCCCCCCCC)C3=CC=CC=C3SC2=C1 LLLJAYXRHGSUEZ-UHFFFAOYSA-N 0.000 description 1
- IQZBMUCMEBSKSS-UHFFFAOYSA-N 10-ethylphenothiazine Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3SC2=C1 IQZBMUCMEBSKSS-UHFFFAOYSA-N 0.000 description 1
- VRJVOTTZESKWPD-UHFFFAOYSA-N 10-hexylphenothiazine Chemical compound C1=CC=C2N(CCCCCC)C3=CC=CC=C3SC2=C1 VRJVOTTZESKWPD-UHFFFAOYSA-N 0.000 description 1
- WSEFYHOJDVVORU-UHFFFAOYSA-N 10-phenylphenothiazine Chemical compound C12=CC=CC=C2SC2=CC=CC=C2N1C1=CC=CC=C1 WSEFYHOJDVVORU-UHFFFAOYSA-N 0.000 description 1
- SKLVKQDGDJQKBK-UHFFFAOYSA-N 9-dodecyl-3-ethynylcarbazole Chemical compound CCCCCCCCCCCCn1c2ccccc2c2cc(ccc12)C#C SKLVKQDGDJQKBK-UHFFFAOYSA-N 0.000 description 1
- YCWUVACOIYLEMX-UHFFFAOYSA-N 9-dodecylcarbazole Chemical compound C1=CC=C2N(CCCCCCCCCCCC)C3=CC=CC=C3C2=C1 YCWUVACOIYLEMX-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- SHUQFBKCOHURJQ-UHFFFAOYSA-N 9-hexylcarbazole Chemical compound C1=CC=C2N(CCCCCC)C3=CC=CC=C3C2=C1 SHUQFBKCOHURJQ-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- 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 invention discloses a method for regulating atom transfer radical polymerization by using a conjugated alkynyl anthracene derivative as a visible light photosensitizer, which relates to the field of polymer synthesis and is provided based on the problem that atom transfer radical photopolymerization needs a metal catalyst to participate and cannot be regulated under visible light, and the method comprises the following steps: the method comprises the following steps of carrying out atom transfer radical polymerization reaction on a polymerization system consisting of a conjugated alkynyl anthracene derivative, an acrylate monomer, an initiator and a solvent at room temperature under the condition of visible light illumination to generate a corresponding polymer, wherein the polymerization system has the beneficial effects that: the application of the anthracene derivative in visible light driven atom transfer radical photopolymerization is realized, and a metal catalyst is not needed, so that the obtained polymer does not need complicated purification treatment.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to a conjugated alkynyl anthracene derivative and a method for regulating atom transfer radical polymerization by using the same as a visible light photosensitizer.
Background
Atom transfer radical polymerization provides a means to control molecular weight and molecular weight distribution via radical polymerization. The method has a disadvantage in that the polymerization process requires the participation of a transition metal catalyst, and thus the resulting polymer has a metal catalyst residue. This not only affects the application of atom transfer radical polymerization in biomedicine and microelectronics, but also is a waste of resources. Various methods have been developed to reduce the loading of the transition metal catalyst, and there are also some methods reporting the recycling of the metal catalyst.
In 2014, there are two subject groups (Macromolecules,2014,47(23):8255-8261, Journal of the American Chemical Society 2014,136(45),16096-16101) reporting atom transfer radical polymerization with small molecule organic compounds as sensitizer, and the results prove that the compounds can replace the traditional metal catalyst, thereby fundamentally solving the problem of metal ion pollution in atom transfer radical polymerization and laying the foundation for the industrialization of atom transfer radical polymerization. However, the compounds have been reported to have a short absorption wavelength, and the light source used for polymerization is still an ultraviolet light source. As is well known, ultraviolet radiation is harmful to human bodies and has poor environmental protection safety. Therefore, the development of novel organic compounds capable of controlled atom transfer radical polymerization at visible wavelengths is becoming a current research focus.
Anthracene has good photoelectric properties, and atom transfer radical photopolymerization with anthracene as a sensitizer is reported by Yagci task group in 2016, and a polymer with controllable molecular weight distribution and molecular weight is obtained (Macromolecules 2016,49(20), 7785-7792). But the absorption wavelength of anthracene is concentrated in the ultraviolet region, and atom transfer radical photopolymerization cannot be regulated and controlled under visible light.
Disclosure of Invention
The problem to be solved by the invention is that atom transfer radical photopolymerization needs a metal catalyst to participate, and cannot be regulated under visible light.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a conjugated alkynyl anthracene derivative used as a visible light photosensitizer for regulating atom transfer radical polymerization, which has the following structural general formula:
wherein R is one of phenyl, triphenylamine, N-dodecyl carbazole, N-hexyl carbazole, N-ethyl carbazole, N-phenyl carbazole, N-dodecyl phenothiazine, N-hexyl phenothiazine, N-ethyl phenothiazine and N-phenyl phenothiazine.
The invention provides a method for regulating atom transfer radical polymerization by using a conjugated alkynyl anthracene derivative as a visible light photosensitizer, which comprises the following steps: a polymerization system consisting of the conjugated alkynyl anthracene derivative, the acrylate monomer, the initiator and the solvent is subjected to atom transfer radical polymerization reaction at room temperature under the condition of visible light illumination, so that a corresponding polymer is generated.
Preferably, the initiator is ethyl alpha-bromophenylacetate.
Preferably, the acrylate monomer is methyl methacrylate.
Preferably, the light source range of the visible light is 400-800 nm.
Preferably, the molar ratio of the acrylate monomer, the initiator and the conjugated alkynyl anthracene derivative is (50-1000): 10-100): 1-10.
Preferably, the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran and dichloromethane.
Preferably, the volume ratio of the acrylate monomer to the solvent is (1-5) to (1-20).
Preferably, the conjugated alkynyl anthracene derivative, the acrylate monomer, the initiator and the solvent are mixed, and then the mixture is vacuumized under the freezing condition and then is unfrozen.
Preferably, the thawed mixture is stirred under visible light.
The invention has the beneficial effects that:
(1) the ultraviolet-visible absorption wavelength range and the light absorption capacity of the conjugated alkynyl anthracene derivative are remarkably improved compared with those of anthracene, and the application of the anthracene derivative in visible light-driven atom transfer radical photopolymerization is realized;
(2) according to the invention, atom transfer radical polymerization regulated by the conjugated alkynyl anthracene derivative does not need a metal catalyst, so that the obtained polymer does not need complicated purification treatment, and the preparation steps are simplified.
Drawings
FIG. 1 shows the preparation of the conjugated alkynyl derivative AND1 in example 1 of the present invention1H NMR chart;
FIG. 2 is a structural formula of a conjugated alkynyl derivative AND1 in example 1 of the present invention;
FIG. 3 is a diagram showing the UV-VIS absorption spectra of the conjugated alkynyl derivatives AND1 AND AND 2;
FIG. 4 shows the preparation of conjugated alkynyl derivative AND2 in example 2 of the present invention1H NMR chart;
FIG. 5 is a structural formula of conjugated alkynyl derivative AND2 in example 2 of the present invention;
FIG. 6 is a GPC outflow curve of polymethyl methacrylate obtained by controlling the conjugated alkynyl derivatives AND1 AND AND 2.
Detailed Description
The invention will be described in further detail below with reference to the drawings and examples of the specification.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the present invention, the molecular weight and molecular weight distribution of the disclosed polymer are measured by gel permeation chromatography.
Example 1
The synthesis of the conjugated alkynyl anthracene derivative AND1 comprises the following steps:
the reaction equation is as follows:
(1) 9, 10-dibromoanthracene (1.01g, 3mmol), cuprous iodide (28.5mg, 0.15mmol), triphenylphosphine (39.3mg, 0.15mmol), bis (triphenylphosphine) palladium dichloride (21.1mg, 0.01mmol) were weighed out and charged into a 100mL three-necked flask equipped with a magneton and a thermometer, and 20mL of N, N-Dimethylformamide (DMF) and 15mL of Triethylamine (TEA) were added to dissolve them;
(2) n-dodecyl-3-ethynylcarbazole (1.43g, 7.5mmol) was weighed, dissolved in 10mL of DMF and transferred to a constant pressure dropping funnel. Vacuumizing AND filling nitrogen for three times under electromagnetic stirring, slowly heating to 80 ℃, continuously stirring for half an hour, then starting dropwise adding a DMF (dimethyl formamide) solution of N-dodecyl-3-ethynylcarbazole, monitoring that the raw materials completely react by TCL (thermal chemical vapor deposition), stopping heating after the reaction liquid is cooled to room temperature, separating out solids, filtering AND drying, recrystallizing the crude product by using chloroform to obtain an orange-red crystal (1.04g, the conversion rate of the product is 62%), namely the conjugated alkynyl anthracene derivative, which is named as AND 1;
of conjugated alkynylanthracene derivatives AND11The H NMR chart is shown in FIG. 1, and the hydrogen spectrum data is as follows:1H NMR(400MHz,CDCl3)δ8.90–8.79(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)；
the structural formula of the product conjugated alkynyl derivative AND1 is shown in FIG. 2, AND the ultraviolet-visible absorption spectrum is shown in FIG. 3, so that the ultraviolet-visible absorption wavelength range AND the light absorption capacity of the conjugated alkynyl anthracene derivative AND1 are both remarkably improved compared with anthracene.
Example 2
The synthesis of the conjugated alkynyl anthracene derivative AND2 comprises the following steps:
the reaction equation is as follows:
(1) 9, 10-dibromoanthracene (1.01g, 3mmol), cuprous iodide (28.5mg, 0.15mmol), triphenylphosphine (39.3mg, 0.15mmol), bis (triphenylphosphine) palladium dichloride (21.1mg, 0.01mmol) were weighed out and charged into a 100mL three-necked flask equipped with a magneton and a thermometer, and 20mL of N, N-Dimethylformamide (DMF) and 15mL of Triethylamine (TEA) were added to dissolve them;
(2) n-dodecyl-3-ethynylphenothiazine (2.94g, 7.5mmol) was weighed, dissolved in 10mL of DMF and transferred to a constant pressure dropping funnel. Vacuumizing and filling nitrogen for three times under electromagnetic stirring, slowly heating to 80 ℃, continuously stirring for half an hour, and then dropwise adding a DMF (dimethyl formamide) solution of N-dodecyl-3-ethynylphenothiazine; and (3) monitoring by TCL that the raw materials stop heating after completely reacting, cooling the reaction solution to room temperature, separating out solids, filtering and drying. The crude product was purified in TCM: recrystallizing EA (1: 3) to obtain orange red powder (1.45g, the conversion rate of the product is 68%), namely the conjugated alkynyl anthracene derivative which is named as AND 2;
of conjugated alkynylanthracene derivatives AND21The H NMR chart is shown in FIG. 4, and the hydrogen spectrum data is 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 ═ 5.7, 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 ═ 6.8, 6H), the product alkynyl derivative 2, its conjugated absorption spectrum is shown in fig. 5, AND its conjugated uv absorption spectrum is significantly higher than that of anthracene derivative, as shown in fig. 3.
Example 3
The application of the conjugated alkynyl anthracene derivative AND1 in example 1 to regulate AND control atom transfer radical polymerization of methacrylate comprises the following steps:
(1) adding 20mg of AND1, 100 mu L of alpha-bromophenylacetic acid ethyl ester, 5mL of methyl methacrylate AND 5mL of Tetrahydrofuran (THF) into a 50mL Schlenk bottle filled with magnetons, freezing by using liquid nitrogen, vacuumizing, filling nitrogen, AND repeating for three times;
(2) after thawing, stirring the mixture under a 7W household energy-saving lamp (European general illumination/12-LE-47166/7W, light source range between 400 and 800 nm), continuously stirring the mixture for 24 hours, slowly adding the reaction system into 200mL of methanol, and filtering the mixture to obtain polymethyl methacrylate;
and (3) testing: the obtained polymethyl methacrylate is re-dissolved in tetrahydrofuran, and is added into 200mL of methanol for precipitation and separation; repeating the steps for three times, filtering to obtain polymethyl methacrylate, drying in vacuum to constant weight, and testing by Gel Permeation Chromatography (GPC).
And (3) testing results: the conversion rate was determined by gravimetric method to be 57.2% molecular weight of the resulting polymethylmethacrylate, which was analyzed by gel permeation chromatography to have a molecular weight Mn12955g/mol and a polydispersity PDI of 1.22, the GPC flow curve of the resulting polymethyl methacrylate is shown in FIG. 6.
Example 4
Application example 2 the conjugated alkynyl anthracene derivative AND2 regulated atom transfer radical polymerization of methacrylate, comprising the following steps:
(1) in a 50mL Schlenk flask containing magnetons, 20mg of AND2, 100. mu.L of ethyl α -bromophenylacetate, 5mL of methyl methacrylate, 5mL of THF were added. After freezing by liquid nitrogen, vacuumizing and filling nitrogen, and repeating the steps for three times;
(2) after thawing, stirring the mixture under a 7W household energy-saving lamp, continuously stirring the mixture for 24 hours, slowly adding the reaction system into 200mL of methanol, and filtering the mixture to obtain the polymethyl methacrylate.
And (3) testing: the obtained polymethyl methacrylate is re-dissolved in tetrahydrofuran, and is added into 200mL of methanol for precipitation and separation; repeating the steps for three times, filtering to obtain polymethyl methacrylate, drying in vacuum to constant weight, and testing by Gel Permeation Chromatography (GPC).
And (3) testing results: the conversion rate was determined by gravimetric method to be 40.3% molecular weight of the resulting polymethylmethacrylate, which was analyzed by gel permeation chromatography to determine its molecular weight MnThe polydispersity PDI of 12109g/mol was 1.27, and the GPC flow curve of the resulting polymethyl methacrylate is shown in fig. 6.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.
Claims (9)
1. A conjugated alkynyl anthracene derivative used as a visible light photosensitizer for regulating atom transfer radical polymerization is characterized in that: the structural formula of the conjugated alkynyl anthracene derivative is shown as follows:
2. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative of claim 1 as a visible light photosensitizer, wherein the method comprises the following steps: the method comprises the following steps: adding the conjugated alkynyl anthracene derivative, the acrylate monomer, the initiator and the solvent into a Schlenk bottle filled with magnetons, freezing by using liquid nitrogen, vacuumizing and filling nitrogen, and repeating for three times; after thawing, the mixture is placed under the condition of visible light illumination for atom transfer radical polymerization reaction at room temperature, so that a corresponding polymer is generated.
3. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 2, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: the initiator is alpha-bromophenylacetic acid ethyl ester.
4. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 2, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: the acrylate monomer is methyl methacrylate.
5. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 2, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: the light source range of the visible light is 400-800 nm.
6. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 2, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: the molar ratio of the acrylate monomer, the initiator and the conjugated alkynyl anthracene derivative is (50-1000): 10-100): 1-10.
7. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 2, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, toluene, tetrahydrofuran and dichloromethane.
8. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 2, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: the volume ratio of the acrylate monomer to the solvent is (1-5) to (1-20).
9. The method for regulating atom transfer radical polymerization by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer according to claim 1, wherein the atom transfer radical polymerization is carried out by using the conjugated alkynyl anthracene derivative as a visible light photosensitizer: and stirring the unfrozen mixture under the condition of visible light.
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