CN107382957B - Bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and synthetic method, its polymer and it is used for photocatalysis - Google Patents
Bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and synthetic method, its polymer and it is used for photocatalysis Download PDFInfo
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- CN107382957B CN107382957B CN201710496160.3A CN201710496160A CN107382957B CN 107382957 B CN107382957 B CN 107382957B CN 201710496160 A CN201710496160 A CN 201710496160A CN 107382957 B CN107382957 B CN 107382957B
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 40
- 230000031709 bromination Effects 0.000 title claims abstract description 39
- 238000005893 bromination reaction Methods 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 title claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 14
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- KBWHYRUAHXHHFO-UHFFFAOYSA-N 3-(bromomethyl)thiophene Chemical compound BrCC=1C=CSC=1 KBWHYRUAHXHHFO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005416 organic matter Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- 238000000746 purification Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000011941 photocatalyst Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000975 dye Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 35
- 239000011787 zinc oxide Substances 0.000 description 24
- 230000015556 catabolic process Effects 0.000 description 10
- 229920000547 conjugated polymer Polymers 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 eluant Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
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- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- 238000011010 flushing procedure Methods 0.000 description 2
- WDPIZEKLJKBSOZ-UHFFFAOYSA-M green s Chemical compound [Na+].C1=CC(N(C)C)=CC=C1C(C=1C2=CC=C(C=C2C=C(C=1O)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](C)C)C=C1 WDPIZEKLJKBSOZ-UHFFFAOYSA-M 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010021033 Hypomenorrhoea Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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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Abstract
The invention discloses bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and synthetic method, its polymer and it is used for photocatalytic degradation of organic matter.Bromination 3- thenyl-N, the synthesis of N- dimethyl-N-alkylammonium is as follows: N being added in three-neck flask, N- dimethyl alkylamine, it is dissolved with a small amount of acetonitrile, it is heated with stirring to 55 DEG C, 3- bromomethyl thiophene is added dropwise with constant pressure funnel, by solvent rotary evaporation after 24 h of reaction, crosses column purification.The polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, due to introducing alkyl chain substituent in polythiofuran derivative, the original rigidity of main chain is destroyed, and the interaction force of molecule interchain reduces therewith, improves its dissolubility.The polymer is used for photocatalytic degradation of organic matter, the hybrid material of the polymer Yu inorganic photochemical catalyst is obtained by chemiadsorption, there is excellent photocatalysis performance.The principle of the invention is reliable, easy to operate, and yield is higher, environmentally protective, has a vast market application prospect.
Description
Technical field
The present invention relates to bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and synthetic method, polymer and polymerizations
The preparation of the inorganic photocatalyst compound material of object, and its in the application of photocatalysis degradation organic contaminant, belong to photocatalysis green wood
Material field.
Background technique
Organic dyestuff has color strength, persistently with feature at low cost, is widely used to the row such as printing and dyeing, food at present
Industry.But organic dyestuff at this stage has the shortcomings that high toxicity, difficult to degrade.Arbitrarily it is discharged into natural environment, it can be to water
Environment damages while also endangering the health of the mankind.Now, many human diseases are all related with water pollution.Cause
This, we must take corresponding measure to remove the harmful organic dyestuff in water.In numerous sewage disposal technologies, photocatalysis
Technology is a kind of Non-aqueous processing technology of novel green high-efficient.The technology is sent out under conditions of illumination using semiconductor material
Given birth to electron transition and produced electrons and holes, they can in sewage oxygen and water react generate free radical activity object, from
There is strong oxidant by base, redox reaction can occur with the organic matter in sewage, decompose organic matter and generate and can drop
The small molecule or carbon dioxide of solution.There is the compound and low charges of high photo-generate electron-hole pairs to turn for traditional photochemical catalyst
The disadvantages of shifting ability.Therefore, scientific research personnel develops new photochemical catalyst one after another, and one of which is exactly to prepare polymer complex light to urge
Agent.Conjugated polymer contains big conjugatedπbond.Big conjugatedπbond can not only make the energy gap of system reduce, and improve system
Light absorptive, while electron transmission ability with higher.Therefore, conjugated polymer has preferable optical property and electric conductivity
Matter.Based on these properties, conjugated polymer be can be used in catalysis material.When conjugated polymer is incorporated into photochemical catalyst
In, can be improved the photo absorption performance of photochemical catalyst, improve the quantity of light induced electron and hole, and the low band gap of conjugated polymer and
High electron transmission ability, can be improved the separating capacity of electron hole, and quickly shift electronics, can reduce electron hole
Recombination rate.To improve the content in light induced electron and hole, and then improve containing for free radical activity object in reaction system
Amount, accelerates redox reaction rate, has reached raising photocatalysis performance.
Polythiophene and its derivative due to prepare be easy, ambient stable is good, by being doped with preferable electric conductivity and good
Good optical property is considered as a kind of conjugated polymer for having very much development potentiality.Unsubstituted polythiophene is then because of its strand
Upper no any substituent group, strand have very big rigidity, and dissolubility is bad in most solvents, is difficult processed etc.
Reason, so can not be used widely in practice.The present invention takes full advantage of using environmentally friendly MOLECULE DESIGN as theory
The characteristics of narrow, controllable band gap of conjugated polymer, appearance high carrier mobility, bromination 3- thenyl-N, N- bis- is synthesized
Methyl-N-alkyl ammonium and its polymer, principle is reliable, and yield is higher, environmentally protective, overcomes the defect and not of the prior art
Foot.
Summary of the invention
The purpose of the present invention is to provide bromination 3- thenyl-N, N- dimethyl-N-alkylammoniums, since the compound contains
There is quaternary ammonium salt structure, improves its dissolubility in water.
The object of the invention is also to provide the synthetic method of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium,
This method principle is reliable, easy to operate, has a vast market application prospect.
Another object of the present invention is to provide the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium,
The polymer causes main polymer chain to be distorted, main chain is former due to introducing alkyl chain substituent in polythiofuran derivative
Some rigidity are destroyed, and the interaction force of molecule interchain also reduces therewith, to substantially improve its dissolubility.
Another object of the present invention, which also resides in, provides the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium
For photocatalytic degradation of organic matter, the hybrid material of the polymer Yu inorganic photochemical catalyst is obtained by chemiadsorption, is one
The novel photocatalyst of kind superior performance solves the problems, such as that other photochemical catalyst photo-generate electron-holes are high compound, has excellent
Photocatalysis performance.
To reach the above technical purpose, the present invention provides following technical scheme.
Bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, structural formula are as follows:
The polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, structural formula are as follows:
In the present invention, when n is 10,12,14,16, bromination 3- thenyl-N, N- dimethyl-N-alkylammonium is distinguished
It is named as s-10, s-12, s-14, s-16, corresponding polymer is then Ps-10, Ps-12, Ps-14, Ps-16.
The synthetic method of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, successively the following steps are included:
A certain amount of N, N- dimethyl alkylamine are added in three-neck flask, the carbon atom number of the alkyl is 10,12,14
Or 16, it is dissolved with a small amount of acetonitrile, is heated with stirring to 55 DEG C, three necks are added dropwise with constant pressure funnel in 3- bromomethyl thiophene and are burnt
In bottle, make itself and N, N- dimethyl alkylamine reacts, N, the molar ratio of N- dimethyl alkylamine and 3- bromomethyl thiophene
For 1.0:1-3.0:1, the reaction time is for 24 hours, after reaction by solvent rotary evaporation, to cross column and purify (column length 12cm, 200-
300 mesh silica gel, eluant, eluent is methylene chloride: methanol=30:1), obtain bromination 3- thenyl-N, N- dimethyl-N-alkyl
Ammonium.
The polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, preparation process are as follows: being added in flask
8-20mL dry chloroform adds 0.3-1g anhydrous ferric trichloride under stirring, stir 0.5-1h, obtains dirty-green muddiness
Liquid, then three chloromethanes that 5-15mL contains 0.1-1.0g bromination 3- thenyl-N, N- dimethyl-N-alkylammonium are added dropwise to the solution
Alkane solution, solution rapidly go to rufous, which continues return stirring 10-30h under nitrogen protection, will after reaction
Solvent is evaporated, and the methanol that acidification is added is precipitated, and is then filtered, with deionized water repeated flushing sediment.By product first
After alcohol soxhlet type 2d, the air drying in vacuum tank obtains poly- bromination 3- thenyl-N, N- dimethyl-N-alkylammonium.
The reaction mechanism mechanism of reaction is as follows:
The polymer of bromination 3- thenyl-N, N- the dimethyl-N-alkylammonium is used for photocatalytic degradation of organic matter, tool
Steps are as follows for gymnastics work:
(1) pass through chemiadsorption for the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and inorganic light
Catalyst hydridization obtains the composite photocatalyst material of hydridization；
(2) 100mL is added in 100mL conical flask and contains certain density organic dyestuff aqueous solution, it then will be a certain amount of
The composite photocatalyst material of hydridization is added in solution, last illumination stirring, so that organic dyestuff decomposes.
Compared with prior art, the invention has the following advantages:
The present invention has narrow, controllable band gap, easy chemical tailoring, high carrier migration using conjugated polymer
Rate, excellent stability and low cost can assist the raw electricity for improving photochemical catalyst after it is with inorganic photochemical catalyst hydridization
The catalysis that the recombination rate of the separation of son-hole, the transfer rate of charge and reduction electron hole reaches raising catalyst is living
The characteristics of property, bromination 3- thenyl-N is synthesized, N- dimethyl-N-alkylammonium passes through FeCl3Oxidation catalysis method has synthesized one
The conjugated polymer of Novel series, for the present invention with the theory of Green Chemistry, preparation method is easy to operate, and yield is higher, green
Environmental protection solves the recombination rate of the high photo-generate electron-hole of other inorganic photochemical catalysts, has a vast market application prospect.
Detailed description of the invention
Fig. 1 is the infrared spectrum of s-12.
Fig. 2 is s-121H NMR spectra.
Fig. 3 is s-1213C NMR spectra.
Fig. 4 is the mass spectrogram of s-12.
Fig. 5 is the GPC figure of Ps-12.
Fig. 6 is Ps-12 (4%)-ZnO photocatalyst XRD diagram.
Fig. 7 is Ps-12 (4%)-ZnO photocatalyst fluorogram.
Fig. 8 is Ps-12 (4%)-ZnO photocatalyst infrared spectrum.
Fig. 9 is the light degradation curve of LGB under ultraviolet light.
Figure 10 is the degradation figure that Ps-12-ZnO (4%) recycles 5 degradation LGB.
Specific embodiment
Below by drawings and examples, invention is further explained.
The present embodiment is served only for that the present invention is further described, but should not be understood as to the scope of the present invention
Limitation, those skilled in the art make some nonessential modifications and adaptations according to above content, also belong to protection of the present invention
Range.
One, bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, its polymer and polymer/inorganic photochemical catalyst
The preparation of composite material
Embodiment 1
Bromination 3- thenyl-N, N- Dimethyl-N-dodecyl ammonium (brief note s-12) and its polymer (brief note Ps-12)
Preparation and polymer (Ps-12)/inorganic photochemical catalyst (ZnO) composite material (brief note Ps-12-ZnO) preparation.
The preparation method of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, successively the following steps are included:
A certain amount of N, N- Dimethyl-N-dodecyl amine, with acetonitrile dry on a small quantity are added in 50mL three-neck flask
Dissolution, be heated with stirring to 55 DEG C, 2g 3- bromomethyl thiophene be added dropwise in three-neck flask with constant pressure funnel, make its with
Tertiary amine reacts.The ratio of N, N- dimethyl alkylamine and 3- bromomethyl thiophene is 1.5:1, and the reaction time is reaction knot for 24 hours
By solvent rotary evaporation after beam, cross column purification (column length 12cm, 200-300 mesh silica gel, eluant, eluent is methylene chloride: methanol=
30:1), the sample obtained methylene chloride and ether carry out the acicular crystal for being recrystallized to give white.Pass through1H NMR、13C
NMR, which carries out characterization, confirms structure, yield 78%.
Bromination 3- thiophene is obtained by the polymerisation in solution of bromination 3- thenyl-N, N- Dimethyl-N-dodecyl ammonium
The polymer of methyl-N, N- Dimethyl-N-dodecyl ammonium, process are as follows: three dry chloromethanes of 9.5mL being added in flask
Then alkane is added with stirring 0.5g anhydrous ferric trichloride, stir 30min, obtain dirty-green turbid solution.Later, it is dripped to the solution
9.5mL is added to contain the chloroform soln of 0.3g bromination 3- thenyl-N, N- Dimethyl-N-dodecyl ammonium.Solution is rapid
Become rufous.The reaction mixture continues return stirring for 24 hours under nitrogen protection.Solvent is evaporated after reaction, acidification is added
Methanol precipitated.Then it filters, with deionized water repeated flushing sediment.By product methanol soxhlet type 2d, later
The air drying in vacuum tank obtains poly- bromination 3- thenyl-N, N- Dimethyl-N-dodecyl ammonium.
Polymer (Ps-12)/inorganic photochemical catalyst (ZnO) composite material prepares as follows: weighing 300mg zinc oxide in circle
In the flask of bottom, a certain amount of Ps-12 solution (CHCl is then added3), ultrasound 30 minutes divides zinc oxide sufficiently in the solution
It dissipates.It is stirred for 24 hours under room temperature.After completion of the reaction, it is centrifugally separating to obtain product, with water washing 3 times three times.Sample is placed in baking oven
Drying for 24 hours, obtains Ps-12-ZnO (4%) sample that Ps-12 content range is 4% at 60 DEG C.
Two, the structural characterization of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and its polymer is (with s-12 and Ps-
For 12)
Fig. 1 is the infrared spectrum of s-12, infrared (KBr, the cm of s-12-1) spectrum analysis is shown in Table 1.
Fig. 2 is s-121The hydrogen spectrum parsing of H NMR spectra, s-12 is shown in Table 2.
Fig. 3 is s-1213The carbon spectrum parsing of C NMR spectra, s-12 is shown in Table 3.
Infrared (KBr, the cm-1) spectrum analysis of table 1s-12
| cm-1 | Ownership |
| 3085.26 | Alpha position C-H in thiphene ring |
| 2916.83 2852.09 | CH3, CH2 |
| 1450-1640 | Thiophene C=C skeleton |
| 905.53 | C-S |
| 720.99 | -(CH2)n- |
The hydrogen of table 2s-12 composes parsing
The carbon of table 3s-12 composes parsing
Fig. 4 is the mass spectrogram of s-12, and as can be seen from the figure molecular ion peak m/z is 310.2718, and calculated value is
310.2568, difference 0.01, error 0.0048%.
Above-mentioned spectral data analysis illustrates that the product of synthesis is target product s-12.
Fig. 5 be Ps-12 GPC figure, analysis map it is found that the molecular weight measured be 1713, the degree of polymerization 5.
It is analyzed according to GPC data as a result, illustrating that synthesized polymer is target product.
Fig. 6 is Ps-12 (4%)-ZnO photocatalyst XRD diagram, it can be seen from the figure that the addition of Ps-12 does not change
The crystal structure of ZnO.
Fig. 7 is Ps-12 (4%)-ZnO photocatalyst fluorogram, it can be seen from the figure that after the addition of Ps-12, it is glimmering
Luminous intensity reduces, and illustrates that the Ps-12 of zinc oxide surface effectively inhibits the compound of photo-generate electron-hole, improves photocatalysis
The photocatalysis performance of agent.
Fig. 8 is Ps-12 (4%)-ZnO photocatalyst infrared spectrum, in the infrared spectroscopy of composite material, is able to observe that
The characteristic absorption peak of Ps-12 illustrates that Ps-12 is entered in zinc oxide, but the major absorbance peak of Ps-12 is moved to lower wave number
It is dynamic, illustrate that the conjugated system of Ps-12 extends, Ps-12 and zinc oxide effect produce broader conjugated system, Ps-12 with
Covalent bond is formd between zinc oxide.This key can promote transfer charge and induction synergistic effect, enhance photocatalytic activity.
Three, Ps-12 (4%)-ZnO photocatalyst performance evaluation
The present invention evaluates Ps-12 (4%)-ZnO photocatalysis using photocatalytic degradation acid green 50 (LGB) under ultraviolet light
The photocatalytic activity of agent.
The 100mL 10mg L that target contaminant used in the present invention is configured by LGB-1LGB solution.
Experimental method is as follows:
Pass through the photocatalytic degradation LGB at ultraviolet light (λ=254nm).Ultraviolet source is by having installed 254nm optical filter additional
The xenon lamp of 500W provided.The average intensity of light source is 14mW cm-2。
It first weighs 100mgPs-12- hydridization ZnO photocatalyst to be placed in Photoreactor, 100mL 10mg L is then added- 1LGB solution.It is now that mixture is ultrasonic in Ultrasound Instrument before light irradiation, keep photochemical catalyst fully dispersed to LGB aqueous solution
In, 5min is then stirred under dark condition makes up to absorption parsing balance taking-up 4mL solution.Before irradiation and the light period
Between, suspension is all placed under the conditions of air atmosphere.Illumination period takes out 4mL solution every the corresponding time, then in 4000r/
It is centrifuged 10min on the centrifuge of min, then takes its supernatant.Its absorbance, maximum absorption wavelength are surveyed on spectrophotometer
It is set as 633nm.In order to investigate the stability of photochemical catalyst, repeat to test according to the method described above, to determine following for photochemical catalyst
Ring number.Photocatalytic activity (DR) is calculate by the following formula to obtain:
Wherein, A0Reach the initial absorbance of organic dyestuff after absorption parsing balance, A for systemiDyestuff after light-catalyzed reaction
Absorbance.
Active specy in photocatalytic system carries out capture experiment by addition capturing agent to determine.
Fig. 9 is the light degradation curve of LGB under ultraviolet light.From light degradation curve it is found that by 21min ultraviolet light
When afterwards, using in composite material, the degradation rate of LGB is 96.6%, and when use zinc oxide, the degradation rate of LGB is 84.6%.It says
The addition of bright conjugated polymer improves the photocatalysis performance of photochemical catalyst.
Figure 10 is the degradation figure that Ps-12-ZnO (4%) recycles 5 degradation LGB.It can be seen from the figure that being recycled by 5 times
After experiment, Ps-12-ZnO (4%) photocatalytic activity is varied less, and illustrates that the photochemical catalyst has preferable photostability.
Claims (5)
1. bromination 3- thenyl-N, N- dimethyl-N-alkylammonium, structural formula are as follows:
2. the synthetic method of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium as described in claim 1, successively includes
Following steps:
Be added a certain amount of N in three-neck flask, N- dimethyl alkylamine, the carbon atom number of the alkyl be 10,12,14 or
16, it is dissolved with a small amount of acetonitrile, is heated with stirring to 55 DEG C, three-neck flask is added dropwise with constant pressure funnel in 3- bromomethyl thiophene
In, make itself and N, N- dimethyl alkylamine reacts, N, and N- dimethyl alkylamine and the molar ratio of 3- bromomethyl thiophene are
1.0:1-3.0:1, reaction time are for 24 hours, after reaction by solvent rotary evaporation, to cross column purification, obtain bromination 3- thiophene first
Base-N, N- dimethyl-N-alkylammonium.
3. the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium as described in claim 1, structural formula is such as
Under:
4. the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium as claimed in claim 3, preparation process is such as
Under: 8-20mL chloroform is added in flask, 0.3-1g anhydrous ferric trichloride is added under stirring, stirs 0.5-1h, obtains
Dirty-green turbid solution, then 5-15mL is added dropwise to the solution and contains 0.1-1.0g bromination 3- thenyl-N, N- dimethyl-N-alkyl
The chloroform soln of ammonium, solution rapidly go to rufous, which continues return stirring 10- under nitrogen protection
Solvent is evaporated by 30h after reaction, and the methanol that acidification is added is precipitated, and is then filtered, is rinsed, extracting, air drying, obtaining
Poly- bromination 3- thenyl-N, N- dimethyl-N-alkylammonium.
5. the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium as claimed in claim 3 is dropped for photocatalysis
Solve organic matter, the specific steps are as follows:
(1) pass through chemiadsorption for the polymer of bromination 3- thenyl-N, N- dimethyl-N-alkylammonium and inorganic photocatalysis
Agent hydridization obtains the composite photocatalyst material of hydridization；
(2) in organic dyestuff aqueous solution, the composite photocatalyst material of hydridization is added in solution, illumination stirring, so that having
Engine dyeing material decomposes.
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