CN115572372B - Pi-conjugated donor-acceptor-based polymer material with similar structure, and preparation method and application thereof - Google Patents
Pi-conjugated donor-acceptor-based polymer material with similar structure, and preparation method and application thereof Download PDFInfo
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- 239000002861 polymer material Substances 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 19
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 16
- 238000013375 chromatographic separation Methods 0.000 claims description 7
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 5-bromothiophene-2-yl Chemical group 0.000 description 8
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 3
- 241000402754 Erythranthe moschata Species 0.000 description 3
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- 230000032683 aging Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-UHFFFAOYSA-N 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000007822 carvacrol derivatives Chemical class 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- XPQPWPZFBULGKT-UHFFFAOYSA-N methyl undecanoate Chemical compound CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
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- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- FAHUKNBUIVOJJR-UHFFFAOYSA-N 1-(4-fluorophenyl)-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazine Chemical compound C1=CC(F)=CC=C1C1C2=CC=CN2CCN1 FAHUKNBUIVOJJR-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical class CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 1
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 1
- 235000007746 carvacrol Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002194 fatty esters Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a pi-conjugated donor-acceptor (D-A) -based polymer material with a similar structure, and a preparation method and application thereof, and belongs to the technical field of functional materials. The structural polymer material has the structural formula: . The pi-conjugated D-A structure-based material provided by the invention is used as a GC stationary phase, has high selectivity to components with similar properties, and can be used for efficiently separating various component mixtures with different polarities, in particular various isomer mixtures which are difficult to separate. The D-A functional material has stable structure, good thermal stability, good solubility and film forming property in organic solvents, and is easy to prepare chromatographic columns with high column efficiency. The pi-conjugated D-A structural material has the advantages of low raw material cost, simple synthesis method and high product yield.
Description
Technical Field
The invention relates to a pi-conjugated donor-acceptor-based polymer material with a similar structure, and a preparation method and application thereof, and belongs to the technical field of functional materials.
Background
GC has high performance in separation, qualitative and quantitative analysis, and has been widely used in various fields for analysis and measurement of complex sample components. The core and key of chromatographic separation analysis determination are the selectivity and separation performance of chromatographic stationary phases.
At present, a high-efficiency organic solar cell generally adopts a conjugated polymer with a D-A structure, and the polymer has good thermal stability and planarity, so that intermolecular accumulation is promoted, intermolecular charge transmission is effectively promoted, and the polymer can be used as an excellent device and widely applied to the organic solar cell. From the characteristics of the molecules, the PBDB-T polymer has good chemical and thermal stability. At present, conjugated polymers of D-A structure have not been reported in chromatographic separations.
Disclosure of Invention
In view of the above, the invention provides a pi-conjugated donor (D-A) -based polymer material with similar structure, which has high selectivity and separation capability for various components and isomers with similar properties when used as a chromatographic stationary phase for gas chromatographic analysis and measurement, and the chromatographic column prepared by adopting the functional material has good thermal stability, repeatability and reproducibility and good application prospect in gas chromatographic separation. In addition, the raw materials used for preparing the functional material have low cost, simple synthesis method and high product yield.
The invention also provides a preparation method of the polymer material with the similar structure.
Another object of the present invention is to provide the use of a structural like polymeric material as described above.
The invention aims at realizing the following technical scheme:
the invention provides a pi-conjugated donor-based polymer material with a similar structure, which has the structural formula:
；
And n is 1-20.
The invention also provides a preparation method of the polymer material with the similar structure, which comprises the following steps:
(1) Accurately weighing (4, 8-bis (5- (2-ethylhexyl) thiophene-2-yl benzo [1,2-b:4,5-b '] dithiophene-2, 6-diyl) bis (trimethylstannane), 1, 3-bis (5-bromothiophene-2-yl) -5, 7-bis (2-ethylhexyl) -4H and 8H-benzo [1,2-c:4,5-c' ] dithiophene-4, 8-dione and tetra triphenylphosphine palladium respectively, sequentially adding into an eggplant-shaped bottle, dissolving with toluene, carrying out ultrasonic vibration, and then heating the mixed solution for reaction to obtain a reaction solution;
(2) After the reaction is finished, dropping the reaction solution into methanol to precipitate solids, carrying out suction filtration and drying, then placing the crude product into a Soxhlet extractor, carrying out reflux flushing with methanol, then carrying out reflux flushing with normal hexane, finally dissolving with chloroform, concentrating the concentration of the sample by rotary evaporation, then dropping methanol, and slowly precipitating solids to obtain PBDB-T material.
Further, in the step (1), the mass ratio of the (4, 8-bis (5- (2-ethylhexyl) thiophen-2-ylbenzo [1,2-b:4,5-b '] dithiophene-2, 6-diyl) bis (trimethylstannane), 1, 3-bis (5-bromothiophen-2-yl) -5, 7-bis (2-ethylhexyl) -4H and 8H-benzo [1,2-c:4,5-c' ] dithiophene-4, 8-dione to the tetraphenylphosphine palladium is 0.09-0.1:0.05-0.1:0.006.
Further, in step (1), the 8H-benzo [1,2-c: the concentration of 4,5-c' ] dithiophene-4, 8-dione and tetraphenylphosphine palladium in toluene is 0.6-1.2 mg/mL.
Further, in the step (1), the ultrasonic oscillation time is 10-15 min; the reaction is carried out for 10-15 hours at 100-120 ℃.
Further, in the step (2), the methanol reflux flushing time is 5-10 hours; and the time for refluxing and flushing the n-hexane is 6-10 hours.
The invention also provides application of the polymer material with the similar structure as a stationary phase for gas chromatographic separation in gas chromatographic analysis.
The material molecules provided by the invention have good planarity, and the PBDB-T molecules can be effectively piled in the tube in a special piling mode, so that the selective adsorption can be effectively carried out when the mixed gas passes through. In addition, PBDB-T is a pi-type semiconductor material that itself has electron donating properties that should be significantly selective for molecules with strong electron withdrawing groups so that it can be effectively analyzed for the separation of certain analytes.
The beneficial effects of the invention are as follows:
(1) The pi-conjugated D-A structure-based material provided by the invention is used as a GC stationary phase, has high selectivity to components with similar properties, and can be used for efficiently separating various component mixtures with different polarities, in particular various isomer mixtures which are difficult to separate.
(2) The D-A functional material has stable structure, good thermal stability, good solubility and film forming property in organic solvents, and is easy to prepare chromatographic columns with high column efficiency.
(3) The pi-conjugated D-A structural material has the advantages of low raw material cost, simple synthesis method and high product yield.
Drawings
FIG. 1 is a GPC chart of PBDB-T materials prepared.
FIG. 2 is a chromatogram of a sample mixture of PBDB-T stationary phase separated alkanes and esters; wherein, substances corresponding to chromatographic peaks of No. 1-14 are as follows: nonane, methyl caproate, decane, methyl heptanoate, undecane, methyl caprylate, dodecane, methyl pelargonate, tridecane, methyl caprate, tetradecane, methyl undecanoate, pentadecane and methyl laurate.
FIG. 3 is a separation chromatogram of PBDB-T prepared as a mixture of fixed relative phenolic isomers; wherein, the substances corresponding to the chromatographic peaks of No. 1 to No. 9 are as follows: phenol, 2, 6-xylenol, o-cresol, p-cresol, m-cresol, 2, 5-xylenol, 2, 3-xylenol, 3, 5-xylenol, and 3, 4-xylenol.
FIG. 4 is a chromatogram of the preparation PBDB-T as stationary phase separation chloronitrobenzene isomers; wherein, substances corresponding to No. 1-3 chromatographic peaks in the graph are as follows: m-chloronitrobenzene, p-chloronitrobenzene, and o-chloronitrobenzene.
FIG. 5 is a separation chromatogram of a preparation PBDB-T as a mixture of fixed relative aromatic trimethylbenzene and trichlorobenzene isomers; wherein, the substances corresponding to the chromatographic peaks of 1 to 6 are as follows: 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, 1,3, 5-trichlorobenzene, 1,2, 4-trichlorobenzene and 1,2, 3-trichlorobenzene.
FIG. 6 is a chromatogram of a prepared PBDB-T as stationary phase separation of the musk carvacrol isomer of nerol; wherein, substances corresponding to No. 1-4 chromatographic peaks in the graph are as follows: nerol, geraniol, musk phenol and carvacrol.
Detailed Description
The invention will be further described with reference to the drawings and detailed description which follow, wherein the process is conventional, unless otherwise indicated, and wherein the starting materials are commercially available from the public disclosure.
The pi-conjugated D-A material functional material prepared in the embodiment is used as a stationary phase, and the steps for preparing the capillary chromatographic column are as follows:
Taking a quartz capillary column with a certain length (5 m-30 m) and an inner diameter of 0.25 mm, flushing 20 min with dichloromethane, and then aging 3h at 260 ℃ in nitrogen atmosphere; then, continuously introducing saturated solution of sodium chloride and methanol into the capillary column under the pressure of nitrogen until the outflow liquid is turbid, discharging the solution in the capillary column, and keeping the temperature of the solution at 200 ℃ under the nitrogen to be 3 h; dissolving PBDB-T materials prepared in the example in dichloromethane to prepare stationary phase solution with proper concentration (0.10 mg/mL-0.50 mg/mL, w/v), introducing the stationary phase solution into a capillary column after ultrasonic treatment for 5min, sealing one end of the capillary column, connecting the other end of the capillary column with a vacuum pump, evaporating the solvent in a water bath at 40 ℃, depositing the stationary phase on the inner wall of the capillary column, and then aging the capillary column under the following aging conditions: maintaining the temperature at 40 ℃ for 30 min ℃ firstly, then heating to 180 ℃ at the heating rate of 1 ℃ per minute and maintaining the temperature at 6h, and obtaining the aged capillary column which is the chromatographic column for GC analysis and determination.
Example 1
The specific preparation steps of the D-A compound PBDB-T are as follows:
(1) 90.46 mg (4, 8-bis (5- (2-ethylhexyl) thiophen-2-ylbenzo [1,2-b:4,5-b '] dithiophene-2, 6-diyl) bis (trimethylstannane), 0.0766g of 1, 3-bis (5-bromothiophen-2-yl) -5, 7-bis (2-ethylhexyl) -4H and 6 mg of 8H-benzo [1,2-c:4,5-c' ] dithiophene-4, 8-dione and tetrakis triphenylphosphine palladium were weighed accurately, sequentially added to a 10 mL single-neck eggplant-shaped bottle, dissolved with 6 mL toluene, 10 min was sonicated, the gas in the mixture was discharged, and the mixture was heated to 110℃to react 12H.
(2) After the reaction is finished, the solution is dripped into 40 mL methanol to separate out solid, the solid is filtered and dried, then the crude product is put into a Soxhlet extractor, the methanol is firstly used for reflux washing 6 h, then the n-hexane is used for reflux washing 6 h, finally chloroform is used for dissolution, and the concentration of the sample is concentrated by rotary evaporation. Then, 40 mL methanol was added dropwise, and the solid was slowly precipitated (yield: 71%). M.w. =7148, molecular weight distribution pdi=1.16, as determined by GPC, see figure 1. Since the larger molecular weight pi-conjugated material is less soluble in DCM, m.w. =7148 was chosen.
The PBDB-T was dissolved in methylene chloride to prepare a stationary phase solution with a concentration of 1.0. 1.0 mg/mL, and a quartz capillary chromatographic column (5 m) was prepared. Separating the combined samples, wherein the separation results are shown in figures 2-6; the chromatographic parameters of the No. 2-6 graphs are as follows: nitrogen is used as carrier gas, and the carrier gas flow rate is as follows: the flow rate is 1 mL/min, and the flow rate split ratio of the carrier gas flow rate is 50:1; FIG. 2 shows the temperature programming of 60 ℃ (2 min) -10 ℃/min-150 ℃; FIG. 3 is a temperature programming 90 oC (1 min)-5 oC /min-150 o C; FIG. 4 is a temperature programming 40 oC -5 oC /min-150 o C; FIG. 5 is a temperature programming 70 oC（2 min）-10 oC /min-150 o C; FIG. 6 shows a constant temperature 80 o C. As can be seen from FIGS. 2 to 6, PBDB-T is used as a stationary phase for gas chromatographic separation, and the obtained chromatographic peak shape has good symmetry and shows good chromatographic separation performance. Each pair of adjacent alkanes and fatty esters in fig. 2 have very close boiling points, such as nonane (150.8 ℃) and methyl caproate (149.8 ℃) boiling points differing by only 1 ℃, which presents a challenge for the separation performance of the column. PBDB-T columns achieved baseline separation of each pair of adjacent alkyl, ester components; the analytes in fig. 3 are cresol and xylenol isomer mixtures, their separation and detection are of great importance as important raw materials for the medical and dye fields. The phenolic isomers have larger polarity, are easy to adsorb on a chromatographic column, cause tailing or signal reduction, but have symmetrical peak shapes on the stationary phase and have good separation degree; in fig. 4-6, we selected different polarity isomers to further examine the column, which covered medium polarity chloronitrobenzene, nonpolar trimethylbenzene and medium polarity trichlorobenzene mixtures and polar nerol musk carvacrol isomers. From the figure we can see that both the nonpolar and polar isomers are well separated on the column.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. Use of a pi-conjugated donor-based polymeric material as stationary phase for gas chromatographic separation in gas chromatographic analysis, characterized in that the polymeric material has the structural formula:
；
and n is 1-20, and n is not 1.
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| WO2018014163A1 (en) * | 2016-07-18 | 2018-01-25 | South University Of Science And Technology Of China | Donor-acceptor polymer with 4-alkoxyl thiophene as conjugated side chain and composition having the same |
| CN108250222A (en) * | 2018-01-30 | 2018-07-06 | 常州大学 | (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials |
| CN112300107A (en) * | 2020-10-23 | 2021-02-02 | 北京理工大学 | Triptycene functional material, preparation method and application thereof |
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| CN102906151B (en) * | 2010-06-25 | 2014-05-07 | 海洋王照明科技股份有限公司 | Conjugated polymer based on benzodithiophene and thienopyrazine, preparation method and uses thereof |
| US20200313104A1 (en) * | 2019-03-26 | 2020-10-01 | New York University | Organic solar cells and methods of making the same |
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| US5262052A (en) * | 1992-03-09 | 1993-11-16 | Brigham Young University | Polysiloxanes containing pendant cyano substituted biphenyls as stationary phases for chromatographic columns |
| WO2001051163A1 (en) * | 2000-01-12 | 2001-07-19 | The Board Of Governors For Higher Education, State Of Rhode Island And Providence Plantations | Chromatographic and electrophoretic separation of chemicals using electrically conductive polymers |
| WO2018014163A1 (en) * | 2016-07-18 | 2018-01-25 | South University Of Science And Technology Of China | Donor-acceptor polymer with 4-alkoxyl thiophene as conjugated side chain and composition having the same |
| CN108250222A (en) * | 2018-01-30 | 2018-07-06 | 常州大学 | (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials |
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