CN106543416A - Polymer containing pyrimidine sulfuric acid concentration is detected in DMF solution in terms of application - Google Patents
Polymer containing pyrimidine sulfuric acid concentration is detected in DMF solution in terms of application Download PDFInfo
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- CN106543416A CN106543416A CN201610921651.3A CN201610921651A CN106543416A CN 106543416 A CN106543416 A CN 106543416A CN 201610921651 A CN201610921651 A CN 201610921651A CN 106543416 A CN106543416 A CN 106543416A
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- concentration
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- sulphuric acid
- absorbance
- thiophene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- SPHAPKFKSPSKKN-UHFFFAOYSA-N hydrogen sulfate;pyrimidin-1-ium Chemical compound OS(O)(=O)=O.C1=CN=CN=C1 SPHAPKFKSPSKKN-UHFFFAOYSA-N 0.000 title description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 54
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 36
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 36
- 229930192474 thiophene Natural products 0.000 claims abstract description 24
- 238000002835 absorbance Methods 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 150000005006 2-aminopyrimidines Chemical class 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 229920000547 conjugated polymer Polymers 0.000 claims description 2
- 238000002189 fluorescence spectrum Methods 0.000 claims description 2
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical class BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract 1
- 150000005005 aminopyrimidines Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 241000238097 Callinectes sapidus Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYBNHBMRLFSMBU-UHFFFAOYSA-N 2,4-dibromo-3-dodecylthiophene Chemical class BrC=1C(=C(SC1)Br)CCCCCCCCCCCC WYBNHBMRLFSMBU-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- KCXYZQGKUXCZLR-UHFFFAOYSA-N 4,6-diiodopyrimidin-2-amine Chemical compound NC1=NC(I)=CC(I)=N1 KCXYZQGKUXCZLR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IYOYKELENMKJOO-UHFFFAOYSA-N N1=CN=CC=C1.[I].[I] Chemical class N1=CN=CC=C1.[I].[I] IYOYKELENMKJOO-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08G2261/3221—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 nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/415—Sonogashira / Hagihara reactions
Abstract
The invention discloses a kind of present invention is coupled polycondensation reaction by Sonogashira to be prepared for determining sulphuric acid, there is the thiophene acetylene series copolymer poly- [2 containing pyrimidine of fluorescent characteristic, 5 thiophene support 4,62 aminopyrimidines] synthetic method and the concentration of sulphuric acid is determined with this polymer.In the DMF solution of this polymer, the sulphuric acid of Deca variable concentrations measures absorbance with ultraviolet spectrometer again and understands that the concentration of sulphuric acid obeys A=0.12438+1.41896c in the range of the mol/ of 0 mol/L to 0.15 according to concentration absorbance Fig. 9（A is absorbance, and c is the concentration of sulphuric acid）, concentration obeys A=0.289+0.13933c in the range of the mol/L of 0.15 mol/L to 1（A is absorbance, and c is the concentration of sulphuric acid）Formula, we substitute into measured absorbance data the concentration that sulphuric acid can be just calculated inside formula.
Description
Technical field
Contain three key thiophene and the polymer of 2- aminopyrimidines detects sulfuric acid concentration side in DMF solution the present invention relates to a kind of
The application in face, belongs to the technical fields such as information Store, the electrode material sensing material sensitive with new soda acid and has potential
Application prospect.
Background technology
Sulphuric acid is important industrial chemicals, has very big application in many important synthesis fields, so measuring containing for sulphuric acid
Even if amount is in the industrial production, and has very big purposes in experimentation.In existing measure sulphuric acid conventional in the lab
The method of concentration is C.I. 13020 .-methylene blue laws, with C.I. 13020 .-methylene blue as indicator, is entered with standard solution of sodium hydroxide
Row acid base neutralization titration determines sulfuric acid content, but uses in the industrial production and run into many difficulties. such as, in industry batch
The change of color is can't see in amount production with C.I. 13020 .-methylene blue laws. ultraviolet absorptivity is measured i.e. in our inventive method
The concentration of sulphuric acid can be calculated.
The present invention by Sonogashira coupling polycondensation reaction be prepared for preferable heat stability, electric conductivity and
Preferably thiophene acetylene series copolymer poly- [2,5- thiophene supports -4,6-2- aminopyrimidines] is gathered by this
In the DMF solution of compound, the sulphuric acid of Deca variable concentrations measures absorbance according to concentration-absorbance Fig. 9 can with ultraviolet spectrometer again
Know that the concentration of sulphuric acid obeys A=0.12438+1.41896c in the range of the mol/ of 0 mol/L to 0.15（A is absorbance, and c is sulfur
The concentration of acid）, concentration obeys A=0.289+0.13933c in the range of the mol/L of 0.15 mol/L to 1（A is absorbance, and c is sulfur
The concentration of acid）Formula, we substitute into measured absorbance data the concentration that sulphuric acid can be just calculated inside formula.
The content of the invention
The present invention uses 2,5-diacetylene thiophene and 2- amino-4,6- diiodo- pyrimidine monomers, with Pd (PPh3)4For catalysis
Agent, adopts1H-NMR、13The means of testing such as CNMR, infrared spectrum, ultraviolet spectra, fluorescence spectrum, successfully realize this polymer
Synthesis and its structure is characterized, inquired into determine sulfuric acid concentration method.
As a result the conjugated polymer prepared in showing the present invention, its change with sulfuric acid concentration in the DMF solution of sulphuric acid are purple
There is regular change in outer absworption peak. and the concentration of sulphuric acid obeys A=0.12438+ in the range of the mol/ of 0 mol/L to 0.15
1.41896c（A is absorbance, and c is the concentration of sulphuric acid）, concentration obeys A=0.289+ in the range of the mol/L of 0.15 mol/L to 1
0.13933c（A is absorbance, and c is the concentration of sulphuric acid）Formula, we substitute into measured absorbance data
The purpose of the present invention
An object of the present invention is the synthetic method of the polymer that we have invented new, has great in terms of organic synthesiss
Purposes.
The second object of the present invention is that we have accurately measured concentration of the sulphuric acid in DMF solution with ultraviolet spectrometer.
Compared with existing additive method and means of testing, the present invention has the following advantages
One, the present invention is coupled the thiophene acetylene series copolymer poly- [2,5- that polycondensation reaction is prepared for pyridine by Sonogashira
Thiophene supports -4,6-2- aminopyrimidines], then in terms of organic synthesiss, have very big use.
Two, the method for the concentration of existing experiment interior survey sulphuric acid is that C.I. 13020 .-methylene blue is indicator, uses sodium hydroxide mark
Quasi- solution carries out acid base neutralization titration method, and C.I. 13020 .-methylene blue method to be seen the color of titration end-point to judge whether neutralization,
Again with the consumption of sodium hydroxide calculating concentration, there is very big error in C.I. 13020 .-methylene blue method, now great majority experiment
, directly with instrument determining, the method that we invent has the advantages that very big in this respect, directly uses ultraviolet light for room and factory
Spectrometer is determining the concentration of sulphuric acid.
Description of the drawings
Fig. 1：The synthetic route of copolymer.
Fig. 2：2,5- bis- (trimethylsilyl acetylene base) thiophene.
Fig. 3：2,5- diacetylene thiophene1HNMR spectrograms.
Fig. 4：Polymer is in CF3In COOH1H-NMR spectrograms.
Fig. 5：The FT-IR spectrograms of monomer and polymer.
Fig. 6：The UV-Vis spectrograms of polymer solution and film.
Fig. 7：The PL spectrograms of polymer solution and film.
Fig. 8：Polymer is in DMF-H2SO4UV-Vis spectrograms in mixed solution.
Fig. 9：Polymer is in DMF-H2SO4It is purple when the concentration of the sulphuric acid in mixed solution is in the range of the mol/ of 0 mol/L to 0.15
Outer test concentrations-absorbance figure.
Figure 10：Polymer is in DMF-H2SO4It is purple when the concentration of the sulphuric acid in mixed solution is in the range of the mol/ of 0.15mol/L to 1
Outer test concentrations-absorbance figure.
Embodiment
1. the synthesis of polymer
（1）First synthesize 2,5- bis- (trimethylsilyl acetylene base) thiophene：Accurately claim in 50 mL there-necked flasks under room temperature, nitrogen protection
Take 3.08 mmoL, 0.745 g 2,5- bromine Dithiophenes, 29 mg CuI, 0.108 mg Pd (PPh3) 2Cl2, then with injection
Device is slowly injected into 35 mL of diisopropylamine of eliminating water deoxygenation, and room temperature reaction dropwise instilled 1 mL trimethyls after 30 minutes
Silico acetylene, is further continued for room temperature reaction and is gradually heating within 30 minutes 80 DEG C of backflows 3 hours, and now, solution is in yellow green, is cooled down
To room temperature, filter, filter cake is washed with a small amount of dichloromethane, decompression steams solvent, with 4 cm silica gel column chromatographies（Eluant two
Chloromethanes）It is quick to cross post, remove eluent under reduced pressure, use petroleum ether（60℃~90℃）Pillar is crossed, Bluepoint is collected, decompression steams molten
Agent faint yellow solid, yield 75%. refer to Figure of description 2 and may determine that successfully synthesize 2,5-, bis- (trimethylsilyl acetylenes
Base) thiophene.1HNMR (CDC1 3 ) δ: 7.04 (s, 2H, -PhH),0.253(t,18H,-Si(CH3) 3).
（2）2,5- diacetylenes thiophene again：2.4 mmoL 2.5-, bis- (trimethyls are added under room temperature in 50mL single port bottles
Silico acetylene base) thiophene, 42 mL tetrahydrofurans (THF), 24 mL absolute methanols, then dropwise the potassium hydroxide of instillation 20% is molten
0.42 mL of liquid, room temperature reaction 8 hours. filter after stopped reaction, remove solvent under reduced pressure, use petroleum ether（60℃~90℃）Cross
Pillar, decompression obtain weak yellow liquid, yield 95%. after steaming solvent1HNMR (CDC13) δ:7.111 (s, 2H,-PhH),
3.356(s, 2H）Bis- (trimethylsilyl acetylene base) thiophene of monomer 2,5- and 2,5- diacetylenes thiophene to preparing is carried out1HNMR characterizes which1HNMR spectrums are shown in Figure of description 3. in 2,5- diacetylene thiophene1There is oil in the collection of illustrative plates of HNMR
The peak of ether, it has been found that the most of petroleum ether in 2,5- diacetylene thiophene can be to be evaporated under reduced pressure, if fruit will not all stone entirely
Oily ether steams method and removes, need to grow some time and the high temperature of any this operation will in vacuum drying oven or other
Carry out in exsiccator, to very unfavorable for unstable 2,5- diacetylene thiophene, 2,5- diacetylene thiophene can divide for this
Solution, it is believed that a small amount of petroleum ether contained in product not under the influence of one-step polymerization reaction, therefore we in 30 min within
After most of petroleum ether is evaporated under reduced pressure, directly proceed by1HNMR is tested and is carried out next step polyreaction. according to explanation
Book accompanying drawing 3 understands to have synthesized 2,5- diacetylene thiophene.
（3）The synthesis of last polymer：Room temperature, lucifuge, in 50 mL there-necked flasks, 2.44 mmoL of accurate title under nitrogen protection, 1
Bis- bromo- 3- dodecylthiophenes of g 2,5-, 23 mg CuI, 86 mg Pd (PPh3) 2Cl2, then it is slowly injected into syringe
30 mL of diisopropylamine of eliminating water deoxygenation, after being stirred at room temperature 30 minutes, dropwise instills 0.8 mL trimethylsilyl acetylenes, gradually
It is warming up to 80 DEG C to flow back 3.5 hours, now, solution is in brown, after being cooled to room temperature, filters, filtered with a small amount of petroleum ether
Cake, decompression steam solvent, with 4 cm silica gel column chromatographies（Eluent petroleum ether）It is quick to cross post, remove eluent under reduced pressure（Time
Control is within 10 min）, obtain 1.02 g of yellow liquid（Thick yield may have part to be evaporated more than 100%
Petroleum ether）Desiliconization experiment is directly carried out, 42 mL THF, 21 mL methanol, 0.45 mL, 20% KOH, room in product, is poured into
Temperature 8 h of stirring, stop, sucking filtration, and decompression steams solvent（Within 10 min）, petroleum ether crosses column chromatography（Pressurizeed post, 30 min
Within）, Bluepoint is collected, solvent is steamed（Within 10 min, completed before solution colour becomes redness from yellow）Collect
Crude product, directly carries out copolyreaction. estimate 2,5-diacetylene-3- dodecylthiophene percentage compositions are about 50%, take
0.4g crude products（Estimate containing 0.67 mmoL, 0.2g, 2,5-diacetylene-3- dodecylthiophenes）, 0.67 mmoL,
0.234 g, 2- amino -4, bis- iodine pyrimidines of 6-, 47 mg Pd4 (PPh3), 13 mg CuI under nitrogen protection, with 12 mL
Diisopropylamine and 30 mL toluene are added in reactor together, and mixture is heated 30 minutes at 80 DEG C, are generated yellowish-brown
Color polymer. after reactant mixture is cooled to room temperature, it is added dropwise in the acetone in quick stirring and has precipitation to be formed.Cross
Filter, collects filter cake and simultaneously uses acetone, hot ethanol and hot methanol repeated washing. in 40 DEG C of 48 h of drying, regather product.Polymer
：The yield 63% of (poly- [2,5- thiophene supports -4,6-2- aminopyrimidines]).According to Figure of description 4. corresponding to pyrimidine ring
There are 6.168-7.813 ppm with thiophene ring hydrogen（Br, m 2H）In the range of.Because dissolubility is very poor, collection of illustrative plates
There are several peaks for having * in the inside, is CF3Solvent miscellaneous peak inside COOD, accompanying drawing 5 understand 2212 cm again-1Generate one
Strong absworption peak we successfully synthesized polymer.1HNMR is composed（With CF3COOH makees solvent）：6.168–7.81 (br, 2H).
2. the preparation of polymer/sulphuric acid/DMF solution
The polymer solution concentration of preparation is 2.46*10 mol.L-1.The concentration of sulphuric acid is（1）0mol.L-1,（2）
0.0118mol.L-1,（3）0.03850mol.L-1, (4) 0.06051mol.L-1, (5)0.08727mol.L-1,
(6)0.1183mol.L-1,(7)0.1796mol.L-1,(8)0.3102mol.L-1,(9)0.4961mol.L-1,(10)
0.8638mol.L-1Understand that polymer solution has an absworption peak in ultraviolet spectrogram when 397 nm according to Fig. 6. according to Fig. 7
Understand that polymer solution there are fluorescent characteristicss.
3. the concentration of the sulphuric acid in polymer/sulphuric acid/DMF solution is determined with ultraviolet spectrometer
The uv absorption light intensity of the 10 polymer/sulphuric acid/DMF solutions for having prepared is measured in ultraviolet spectrometer, according to
Fig. 8 understands that peak height of the change of the concentration with sulphuric acid in ultraviolet absorption spectrum instrument in 468 nm or so linearly changes, root
According to linear relationship out can calculate the concentration of the sulphuric acid in polymer/DMF solution.
Claims (4)
1. the present invention is in terms of a kind of polymer for containing three key thiophene and 2- aminopyrimidines detects sulfuric acid concentration in DMF solution
Using including following concrete steps：
（1）Polymer is prepared, is synthesized poly- [2,5- thiophene support -4,6-2- aminopyrimidines] route and is seen Figure of description 1；
（2）The preparation of polymer/sulphuric acid/DMF solution；
（3）The measure of sulfuric acid concentration.
2. a kind of according to claims 1 contains three key thiophene and the polymer of 2- aminopyrimidines is detected in DMF solution
Application in terms of sulfuric acid concentration, which is typically characterized by：2- aminopyrimidines replace with 2,5- dibromo thiophenes conjugated polymer and its
The synthesis of monomer is shown in that the synthesis of 1. polymer of Figure of description is coupled polycondensation reaction using Sonogashira and is polymerized.
3. a kind of according to claims 1 contains three key thiophene and the polymer of 2- aminopyrimidines is detected in DMF solution
Application in terms of sulfuric acid concentration, which is typically characterized by：In fluorescence spectra, polymer understands that polymer is in 467 nm and 560
There is absworption peak during nm.
4. a kind of according to claims 1 contains three key thiophene and the polymer of 2- aminopyrimidines is detected in DMF solution
Application in terms of sulfuric acid concentration, which is typically characterized by：In the DMF solution of polymer, the sulphuric acid of Deca variable concentrations is again with ultraviolet
According to concentration-absorbance Fig. 9, spectrometer measurement absorbance understands that the concentration of sulphuric acid is for oral administration in the mol/ of 0 mol/L to 0.15 scopes
From A=0.12438+1.41896c（A is absorbance, and c is the concentration of sulphuric acid）, concentration is in the range of the mol/L of 0.15 mol/L to 1
Obey A=0.289+0.13933c（A is absorbance, and c is the concentration of sulphuric acid）Formula, we are in measured absorbance data generation
Enter just calculate the concentration of sulphuric acid inside formula.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102411035A (en) * | 2011-08-25 | 2012-04-11 | 浙江大学 | New method for detecting trace amount bromate |
| CN102892761A (en) * | 2010-03-31 | 2013-01-23 | 帕罗生物制药有限公司 | 4 - aminopyrimidine derivatives and their as as adenosine a2a receptor antagonists |
| CN103221048A (en) * | 2010-11-18 | 2013-07-24 | 卡斯纳莱拉创新药物私人有限公司 | Substituted 4-(selenophen-2(or 3)-ylamino)pyrimidine compounds and methods of use thereof |
| CN103880823A (en) * | 2012-12-21 | 2014-06-25 | 广东东阳光药业有限公司 | Spiro compound serving as hepatitis c inhibitor and application thereof in medicine |
| CN105352927A (en) * | 2015-11-12 | 2016-02-24 | 新疆大学 | Method for synthesis of novel pyrimidine fluorescent opening type optical probe materials and for applying materials in mercury ion detection |
| CN105445210A (en) * | 2015-11-12 | 2016-03-30 | 新疆大学 | Method for detecting concentration of trifluoroacetic acid with polymer in acidichromism performance |
-
2016
- 2016-10-21 CN CN201610921651.3A patent/CN106543416A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102892761A (en) * | 2010-03-31 | 2013-01-23 | 帕罗生物制药有限公司 | 4 - aminopyrimidine derivatives and their as as adenosine a2a receptor antagonists |
| CN103221048A (en) * | 2010-11-18 | 2013-07-24 | 卡斯纳莱拉创新药物私人有限公司 | Substituted 4-(selenophen-2(or 3)-ylamino)pyrimidine compounds and methods of use thereof |
| CN102411035A (en) * | 2011-08-25 | 2012-04-11 | 浙江大学 | New method for detecting trace amount bromate |
| CN103880823A (en) * | 2012-12-21 | 2014-06-25 | 广东东阳光药业有限公司 | Spiro compound serving as hepatitis c inhibitor and application thereof in medicine |
| CN105352927A (en) * | 2015-11-12 | 2016-02-24 | 新疆大学 | Method for synthesis of novel pyrimidine fluorescent opening type optical probe materials and for applying materials in mercury ion detection |
| CN105445210A (en) * | 2015-11-12 | 2016-03-30 | 新疆大学 | Method for detecting concentration of trifluoroacetic acid with polymer in acidichromism performance |
Non-Patent Citations (4)
| Title |
|---|
| XIRALI MAMTIMIN ET AL.: "Acidochromicity of a Low-Molecular-Weight Pyrimidine-Based Copolymer", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| XIRALI MAMTIMIN ET AL.: "New soluble rigid rod copolymers comprising alternating 2-amino-pyrimidine and phenylene repeat units: Syntheses, characterization, optical and electrochemical properties", 《POLYMER》 * |
| 希尔艾力•买买提依明: "聚2-氨基嘧啶衍生物的合成及性能研究", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
| 陈俊水 等: "《分析检测中的质量控制》", 30 November 2015, 华东理工大学出版社 * |
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